NARILAMIDINE SUBSTITUTED TRIFLUORETHYL SULFIDE DERIVATIVES, THEIR USE AND PREPARATION PROCESS, ACTIV

专利摘要:
n-arylamidine-substituted trifluoroethyl sulfide derivatives as acaricides and insecticides. The present invention relates to novel n-arylamidine-substituted trifluoroethyl sulfide derivatives of the formula (i) (i) in which x1, x2, x3, x4, r1, r2, r3, n have the meanings indicated in the description, to the use of these as acaricides and insecticides in the control of animal pests and to processes and intermediaries for their preparation.
公开号:BR112014015679B1
申请号:R112014015679-4
申请日:2012-12-12
公开日:2021-07-20
发明作者:Takuya Gomibuchi；Adeline Kohler；Bernd Alig；Angela Becker；Arnd Voerste；Ulrich Gorgens；Reiner Fischer；Ahmed Wahed Moradi；Silvia Cerezo-Galvez；Julia Johanna Hahn；Kerstin Ilg；Hans-Georg Schwarz；Masahito Ito；Daiei Yamazaki；Katsuhiko Shibuya；Eiichi Shimojo
申请人:Bayer Cropscience Aktiengesellschaft；Bayer Intellectual Property Gmbh；
IPC主号:

专利说明:

[0001] The present invention relates to novel N-arylamidine-substituted trifluorethyl sulfide derivatives, their use as acaricides and insecticides in the control of animal pests and processes and intermediates for their preparation.
[0002] Several substituted N-arylamidines and their insecticidal and acaricide action have already been described in the literature, in WO 2007/131680.
[0003] In the patent application, the active compounds already known from the mentioned publications have disadvantages, either an insufficient or no insecticidal and/or acaricidal activity against animal pests, in particular at relatively low application rates.
[0004] Thus, it is an object of the present invention to present the N-arylamidine-substituted trifluoroethyl sulfide derivatives that can be employed as insecticides and/or acaricides, with satisfactory insecticidal and/or acaricide activity against animal pests, in particular at rates of relatively low application and with high selectivity and better compatibility in crops of useful plants.
[0005] The present invention now features new compounds of Formula (I)
where n represents the number 0, 1, or 2, X1, X2, X3, X4 independently of one another represent hydrogen, halogen, hydroxyl, amino, OCN, SCN, SF5, trialkylsilyl, alkyl, haloalkyl, cyanoalkyl, hydroxyalkyl, alkoxycarbonylalkyl , alkoxyalkyl, alkenyl, haloalkenyl, cyanoalkenyl, alkynyl, haloalkynyl, cyanoalkynyl, alkoxy, haloalkoxy, cyanoalkoxy, hydroxycarbonylalkoxy, alkoxycarbonylalkoxy, alkoxyalkoxy, alkylhydroxyimino, alkoxyimino, alkylalkoxyimino, haloalkylalkoxyimino, alkylthio,alkylsulfinyl,alkylsulfinyl,alkylthio,alkylthiosulfinylalkylsulfinyl,alkylthio,alkylthiosulfinyl,alkylthio,alkylthiosulfinyl , alkylsulfonyl, haloalkylsulfonyl, alkoxyalkylsulfonyl, alkylsulfonylalkyl, alkylsulfonyloxy, alkylcarbonyl, haloalkylcarbonyl, carboxyl, alkylcarbonyloxy, alkoxycarbonyl, haloalkoxycarbonyl, alkoxycarbonylalkyl, aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, dialkylaminocarbonyl, alkenylaminocarbonyl, uylaminocarbonyl, alkylsulfonylamino, aminosulfonyl, alkylaminosulfonyl, dialkylaminosulfonyl, alkylsulfoximino, aminothiocarbonyl, alkylaminothiocarbonyl, dialkylaminothiocarbonyl, or represent phenylalkyl, phenoxy, phenylalkylaxy, phenoxyalkyl, phenylthio, phenylthioalkyl, optionally substituted hetarylphenylsulfonyl, hetarylalkylsulfonyl, hetarylphenylsulfonyl, or represent cycloalkylalkyl, cycloalkylaxy, cycloalkylalkoxy, cycloalkylthio, cycloalkylalkylthio, cycloalkylsulfinyl, cycloalkylalkylsulfinyl, cycloalkylsulfonyl, cycloalkylalkylsulfonyl, optionally substituted saturated or unsaturated, or represent NR4R5, wherein R4 and R5 independently of one another represent hydrogen, cyano, alkyl cyano, alkylaalkyl, hydroxyalkyl, alkoxyalkyl, alkylthioalkyl, alkenyl, haloalkenyl, cyanoalkenyl, alkynyl, haloalkynyl, cyanoalkynyl, acyl, alkoxycarbonyl, or R4 and R5 together ment with the nitrogen atom to which they are attached may form a five to eight membered, saturated or unsaturated, optionally substituted ring which is optionally interrupted by heteroatoms from the group consisting of O, S and N, or represent a 3 to 6 ring members, saturated, partially saturated or aromatic which may optionally contain one to three heteroatoms from the group consisting of O, S and N and which is optionally mono- or polysubstituted by identical or different substituents from the group consisting of halogen, cyano, nitro, hydroxy, amino , carboxy, alkyl, haloalkyl, alkenyl, haloalkenyl, alkynyl, alkoxy, haloalkoxy, alkylthio, alkylsulfinyl, alkylsulfonyl, alkylsulfonyloxy, haloalkylthio, haloalkylsulfinyl, haloalkylsulfonyl, alkylamino, dialkylamino, alkylcarbonylamino, alkoxycarbonyl, alkylaminocarbonyl,aminoalkylcarbonyl,aminoalkylcarbonyl,aminoalkylcarbonyl,aminoalkyloxycarbonyl,aminoalkyloxycarbonyl, , alkylaminothiocarbonyl, dialkylaminothio carbonyl, cycloalkylamino, alkylsulfonylamino, aminosulfonyl, alkylaminosulfonyl and dialkylaminosulfonyl, or by optionally substituted cycloalkyl, cycloalkoxy, cycloalkylalkyl or cycloalkylalkoxy which are optionally interrupted by heteroatoms from the group consisting of O, S and N, or X2 and X3 or X3 and X4, together form with the carbon atoms to which are attached a 5- or 6-membered ring which is optionally interrupted by heteroatoms from the groups consisting of O, S, N and CO, R3 hydrogen, (C2-C8)-alkyl, cyano, haloalkyl, alkoxyalkyl , cyanoalkyl, alkylthioalkyl, alkenyl, haloalkenyl, alkynyl, haloalkynyl, or represent a 3 to 6 membered, saturated, partially saturated or aromatic ring which may optionally contain one to three heteroatoms from the group consisting of O, S and N and which is optionally monosubstituted or polysubstituted by identical or different substituents from the group consisting of halogen, cyano, nitro, hydroxy, amino, carbox i, alkyl, haloalkyl, alkenyl, haloalkenyl, alkynyl, alkoxy, haloalkoxy, alkylthio, alkylsulfinyl, alkylsulfonyl, alkylsulfonyloxy, haloalkylthio, haloalkylsulfinyl, haloalkylsulfonyl, alkylamino, dialkylamino, alkylcarbonylamino, alkoxycarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, alkylaminocarbonyl, alkylaminothiocarbonyl, dialkylaminothiocarbonyl, cycloalkylamino, alkylsulfonylamino, aminosulfonyl, alkylaminosulfonyl and dialkylaminosulfonyl, or by optionally substituted cycloalkyl, cycloalkoxy, cycloalkylalkyl or cycloalkylalkoxy which are optionally interrupted by heteroatoms from the group consisting of O, S and N, R1 and R2 independently of each other represent hydrogen , cyano, alkyl, haloalkyl, alkoxy, cyanoalkyl, hydroxyalkyl, alkoxyalkyl, alkylthioalkyl, alkenyl, haloalkenyl, cyanoalkenyl, alkynyl, haloalkynyl, cyanoalkynyl, represent alkylcarbonyl, alkoxycarbon yl, arylcarbonyl, hetarylcarbonyl, aryloxycarbonyl, hetaryloxycarbonyl, alkylsulfinyl, haloalkylsulfinyl, arylsulfinyl, arylalkylsulfinyl, hetarylsulfinyl, hetarylalkylsulfinyl, alkylsulfonyl, haloalkylsulfonyl, arylsulfonyl, arylalkylsulfonyl, optionally substituted 3-membered, arylalkylsulfonyl, hetaryl represents an optionally substituted 3-membered alkylsulfonyl, hetaryl, ring alkylsulfonyl, hetaryl saturated or aromatic which may optionally contain one to three heteroatoms from the group consisting of O, S and N, which may optionally be interrupted once or twice by C=O, SO or SO2 and which is optionally mono- or polysubstituted by identical or different substituents from the group consisting of halogen, cyano, nitro, hydroxy, amino, carboxy, alkyl, haloalkyl, alkenyl, haloalkenyl, alkynyl, alkoxy, haloalkoxy, alkylthio, alkylsulfinyl, alkylsulfonyl, alkylsulfonyloxy, haloalkylthio, haloalkylsulfinyl, haloalkylsulfonyl, alkylamino, dialkylamino, alkylamino alkoxycarbonyl, alkylcarbonyl, alkylcarbonyloxy, aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, aminothiocarbonyl, alkylaminothiocarbonyl, dialkylaminothiocarbonyl, cycloalkylamino, alkylsulfonylamino, aminosulfonyl, alkylaminosulfonyl and dialkylaminosulfonyl; , S and N, or represent -(CH2)m-R6, -O-(CH2)m-R6, -(CH2)mO-R6, wherein R6 represents a 3- to 6-membered, saturated, partially saturated or aromatic which may optionally contain one to three heteroatoms from the group consisting of O, S and N, which may optionally be interrupted once or twice by C=O and which is optionally mono- or polysubstituted by identical or different substituents from the group consisting of halogen, cyano, nitro, hydroxy, amino, carboxy, alkyl, haloalkyl, alkenyl, haloalkenyl, alky nyl, alkoxy, haloalkoxy, alkylthio, alkylsulfinyl, alkylsulfonyl, alkylsulfonyloxy, haloalkylthio, haloalkylsulfinyl, haloalkylsulfonyl, alkylamino, dialkylamino, alkylcarbonylamino, alkoxycarbonyl, alkylcarbonyl, alkylcarbonyloxy, aminocarbonyl, alkylaminocarbonyl, dialkylaminoalkylaminocarbonyl, aminoalkylthiocarbonyl, dialkylaminocarbonyl,aminoalkylthiocarbonyl,aminoalkylthiocarbonyl, alkylaminosulfonyl and dialkylaminosulfonyl, or by cycloalkyl, cycloalkoxy, cycloalkylalkyl or optionally substituted cycloalkylalkoxy which are optionally interrupted by heteroatoms from the group consisting of O, S and N, where m represents the number 1, 2, 3 or 4 or R1 and R2 may also form, together with the nitrogen atom to which they are attached, a saturated or unsaturated and optionally substituted 4- to 8-membered ring, which may optionally contain one or more additional heteroatoms from the group consisting of sulfur, oxygen (wherein oxygen atoms do not have to be immediately adjacent) and nitrogen and/or optionally at least one carbonyl group or R1 and R3 may also form, together with the atoms to which they are attached, a saturated or unsaturated and optionally substituted ring from 4 to 8-membered, which may contain one or more additional heteroatoms from the group consisting of sulfur, oxygen (wherein the oxygen atoms do not have to be immediately adjacent) and nitrogen and/or optionally at least one carbonyl group.
[0006] If appropriate, the compounds of Formula (I) may be present in various polymorphic forms or as mixtures of different polymorphic forms. The present invention provides both polymorphs and polymorphic mixtures and can be used in accordance with the invention.
[0007] The compounds of the formula (I) optionally comprise diastereoisomers or enantiomers and further rotamers, tautomers and salts of the compounds of the formula (I).
[0008] The compounds of the Formula (I) include in particular E/Z Diastereoisomers, such as, for example,

ou X2 e X3 ou X3 e X4 podem formar os anéis fundidos seguintes que são opcionalmente monossubstituídos ou polissubstituídos por substituintes idênticos ou diferentes, podenso os substituintes ser, independentemente um do outro, seleccionados do grupo constituído por hidrogênio, halogênio, ciano, alquila-(C1-C6), cicloalquila-(C3-C8), haloalquila-(C1-C6), halocicloalquila-(C3-C8), alcoxi- (C1-C6), haloalcoxi-(C1-C6), alcoxi-(C1-C6)-alquila-(C1-C6), alquiltio-(C1- C6), alquilsulfonil-(C1-C6), amino, alquilamino-(C1-C6), di-alquilamino- (C1-C6) e cicloalquilamino-(C3-C8), R3 preferivelmente hidrogênio, alquila-(C2-C6), ciano, haloalquila-(C1-C6), alcoxi-(C1-C6)-alquila-(C1-C6), cianoalquila-(C1-C6), alquiltio-(C1-C6)-alquila-(C1-C6), alcenila-(C2-C6), haloalcenila-(C2-C6), alcinila-(C2-C6), haloalcinila-(C2-C6), ou representam um anel de 3 a 6 membros, saturado, parcialmente saturado ou aromático que pode conter opcionalmente um a três heteroátomos do grupo constituído por O, S e N e que é opcionalmente monossubstituído ou polissubstituído por substituintes idênticos ou diferentes do grupo constituído por halogênio, ciano, nitro, hidroxi, amino, carboxi, haloalcoxi-(C1-C6), alquiltio-(C1-C6), alquilsulfinila-(C1-C6), alquilsulfonil-(C1-C6), alquilsulfonilxi-(C1-C6), haloalquiltio-(C1-C6), haloalquilsulfinila-(C1-C6), haloalquilsulfonil-(C1- C6), alquilamino-(C1-C6), dialquilamino-(C1-C6), alquilcarbonilamino-(C1- C7), alcoxicarbonila-(C1-C7), alquilcarbonila-(C1-C7), alquilcarbonilaxi- (C1-C7), aminocarbonila, arilaminocarbonila-(C1-C7), dialquil-(C1-C6)- aminocarbonila, aminotiocarbonila, alquilaminotiocarbonila-(C1-C6), dialquilaminotiocarbonila-(C1-C6), cicloalquilamino-(C3-C6), alquilsulfonilamino-(C1-C6), aminosulfonil, alquilaminosulfonil-(C1-C6) e di alquilaminosulfonil-(C1-C6), ou ou substituído por cicloalquila-(C3-C8), cicloalcoxi-(C3-C8), cicloalquil-(C3-C8)-alquil-(C1-C6) ou cicloalquil-(C3- C8)-alcoxi-(C1-C6) opcionalmente substituído por substituintes idênticos ou diferentes do grupo constituído por halogênio, ciano, nitro, hidroxi, amino, carboxi, alquila-(C1-C6), haloalquila-(C1-C6), alcoxi-(C1-C6), haloalcoxi-(C1-C6) e opcionalmente interrompido por heteroátomos do grupo constituído por O, S e N, R1 e R2 independentemente um do outro, representa preferivelmente hidrogênio, ciano, alquila-(C1-C6), haloalquila-(C1-C6), alcoxi-(C1-C6), cianoalquila-(C1-C6), hidroxialquila-(C1-C6), alcoxi-(C1- C6)-alquila-(C1-C6), alquiltio-(C1-C6) alquila-(C1-C6), alcenila-(C2-C6), haloalcenila-(C2-C6), cianoalcenila-(C2-C6), alcinila-(C2-C6), haloalcinila- (C2-C6), cianoalcinila-(C2-C6), representa alquilcarbonila-(C1-C6), alcoxicarbonila-(C1-C7), arilcarbonila, hetarilcarbonila, ariloxicarbonila, hetariloxicarbonila, haloalquilsulfinila-(C1-C6), arilsulfinila, aril hetarilsulfinila, hetaril-alquilsulfinila-(C1-C6), haloalquilsulfonil-(C1-C6), arilsulfonil, aril- hetarilsulfonil, hetaril-alquilsulfonil-(C1-C6) opcionalmente substituído por substituintes idênticos ou diferentes do grupo constituído por halogênio, ciano, nitro, hidroxi, amino, carboxi, alquila-(C1-C6), haloalquila-(C1-C6), alcenila-(C2-C8), haloalcenila-(C2- C8), alcinila-(C2-C8), alcoxi-(C1-C6), haloalcoxi-(C1-C6), alquiltio-(C1-C6), alquilsulfinila-(C1-C6), alquilsulfonil-(C1-C6), alquilamino-(C1-C6), di- alquilamino-(C1-C6), ou representam um anel de 3 a 6 membros, saturado, parcialmente saturado ou aromático que pode conter opcionalmente um a três heteroátomos do grupo constituído por O, S e N que pode ser opcionalmente interrompido uma ou duas vezes por C=O, SO ou SO2 e que é opcionalmente monossubstituído ou polissubstituído por substituintes idênticos ou diferentes do grupo constituído por halogênio, ciano, nitro, hidroxi, amino, carboxi, alquila-(C1-C6), haloalquila-(C1-C6), alcenila-(C2-C6), haloalcenila-(C2-C6), alcinila-(C2-C6), alcoxi-(C1-C6), haloalcoxi-(C1-C6), alquiltio-(C1-C6), alquilsulfinila-(C1-C6), alquilsulfonil- (C1-C6), alquilsulfonilxi-(C1-C6), haloalquiltio-(C1-C6), haloalquilsulfinila- (C1-C6), haloalquilsulfonil-(C1-C6), alquilamino-(C1-C6), di alquilamino- (C1-C6), alquilcarbonilamino-(C1-C7), alcoxicarbonila-(C1-C7), alquilcarbonila-(C1-C7), alquilcarbonilaxi-(C1-C7), aminocarbonila, arilaminocarbonila-(C1-C7), dialquilaminocarbonila-(C1-C7), aminotiocarbonila, alquilaminotiocarbonila-(C1-C7), dialquilaminotiocarbonila-(C1-C7), cicloalquilamino-(C3-C8), alquilsulfonilamino-(C1-C6), aminosulfonil, alquilaminosulfonil-(C1-C6) e dialquilaminosulfonil-(C1-C6) ou por cicloalquila-(C3-C8), cicloalcoxi-(C3- C8), cicloalquil-(C3-C8)alquil-(C1-C6) ou cicloalquil-(C3-C8)-alcoxi-(C1-C6) opcionalmente interrompido por heteroátomos do grupo constituído por O, S e N, ou representa -(C2)m-R6, -O-(C2)m-R6, (C2)m-O-R6, em que R6 representa um anel de 3 a 6 membros saturado, parcialmente saturado ou aromático, que pode conter opcionalmente um a três heteroátomos do grupo constituído por O, S e N, que pode ser opcionalmente interrompido uma ou duas vezes por C=O e que é opcionalmente monossubstituído ou polissubstituído por substituintes idênticos ou diferentes do grupo constituído por halogênio, ciano, nitro, hidroxi, amino, carboxi, alquila-(C1-C6), haloalquila-(C1-C6), alcenila-(C2-C6), haloalcenila-(C2-C6), alcinila-(C2-C6), alcoxi-(C1-C6), haloalcoxi-(C1-C6), alquiltio-(C1-C6), alquilsulfinila-(C1-C6), alquilsulfonil-(C1-C6), alquilsulfonilxi-(C1-C6), haloalquiltio-(C1-C6), haloalquilsulfinila-(C1-C6), haloalquilsulfonil-(C1-C6), alquilamino-(C1-C6), dialquilamino-(C1-C6), alquilcabonilamino-(C1-C7), alcoxicarbonila-(C1-C7), alquilcarbonila-(C1- C7), alquilcarbonilaxi-(C1-C7), aminocarbonila, alquilaminocarbonila-(C1- C7), di alquilaminocarbonila-(C1-C7), aminotiocarbonila, alquilaminotiocarbonila-(C1-C7), dialquilaminotiocarbonila-(C1-C7), cicloalquilamino-(C3-C8), alquilsulfonilamino-(C1-C6), aminosulfonil, alquilaminosulfonil-(C1-C6) ou dialquilaminosulfonil-(C1-C6) ou por substituintes idênticos ou diferentes do grupo constituído por cicloalquila-(C3-C8), cicloalcoxi-(C3-C8), cicloalquil-(C3-C8)-alquil-(C1-C6) e cicloalquil-(C3-C8)-alcoxi-(C1-C6) opcionalmente substituído por halogênio, ciano, nitro, hidroxi, amino, carboxi, alquila-(C1-C6), haloalquila-(C1-C6), alcenila-(C2-C8), haloalcenila-(C2-C8), alicnila-(C2- C8), alcoxi-(C1-C6), haloalcoxi-(C1-C6), alquiltio-(C1-C6), alquilsulfinila- (C1-C6), alquilsulfonil-(C1-C6), alquilsulfonilxi-(C1-C6), haloalquiltio-(C1- C6), haloalquilsulfinila-(C1-C6), haloalquilsulfonil-(C1-C6), alquilamino- (C1-C6), dialquilamino-(C1-C6), alquilcabonilamino-(C1-C7), alcoxicarbonila-(C1-C7), alquilcarbonila-(C1-C7), alquilcarbonilaxi-(C1- C7), aminocarbonila, alquilaminocarbonila-(C1-C6), di alquilaminocarbonila-(C1-C6), aminotiocarbonila, alquilaminotiocarbonila-(C1-C6), dialquilaminotiocarbonila-(C1-C6), cicloalquilamino-(C3-C8), alquilsulfonilamino-(C1-C6), aminosulfonil, alquilaminosulfonil-(C1-C6) ou dialquilaminosulfonil-(C1-C6) e opcionalmente interrompido por heteroátomos do grupo constituído por O, S e N, em que m representa o número 1, 2 ou 3, ou R1 e R2 conjuntamente com os átomos aos quais estão ligados podem formar um anel de 4 a 8-membros, saturado ou insaturado, que pode ser opcionalmente monossubstituído ou polissubstituído por alquila-(C1-C4), alcoxi-(C1-C4), halogênio, haloalquil- (C1-C4) e que pode conter opcionalmente um ou dois heteroátomos adicionais do grupo constituído por enxofre, oxigênio e nitrogênio (em que os átomos de oxigênio não deve estar directamente adjacentes) e/ou pelo menos um grupo carbonila, R1 e R3 conjuntamente com os átomos aos quais estão ligados podem formar um anel de 4 a 8-membros, saturado ou insaturado, que pode ser opcionalmente monossubstituído ou polissubstituído por substituinte idênticos ou diferentes do grupo constituído por alquila-(C1-C4), alcoxi-(C1-C4), halogênio, haloalquila- (C1-C4), ciano, cicloalquila-(C3-C6), halocicloalquila-(C3-C6), cianocicloalquila-(C3-C6), alquil-(C1-C2)-cicloalquil-(C3-C6) - alcanodiila(C2-C4), alcenodiila-(C2-C4), butanodienila (em que alcanodiila, alcenodiila e butanodienila podem ser opcionalmente substituídos por alquila-(C1-C4), alcoxi-(C1-C4), halogênio, haloalquil- (C1-C4) e/ou podem ser opcionalmente interrompidos por pelo menos um átomo de oxigênio e/ou nitrogênio) e que pode opcionalmente conter um ou dois heteroátomos adicionais do grupos constituído por enxofre, oxigênio e nitrogênio (em que os átomos de oxigênio não deve estar directamente adjacentes) e/ou pelo menos um grupo carbonila,[0009] Formula (I) provides a general definition of the compounds according to the invention. Preferred substituents or ranges of radicals indicated in the Formulas given above and below are defined, wherein n preferably represents the number 0, 1, or 2, X1, X2, X3, X4 independently of one another preferably represents hydrogen, halogen, hydroxy, amino, OCN, SCN, SF5, tri-alkylsilyl-(C1-C6), alkyl-(C1-C6), haloalkyl-(C1-C6), cyanoalkyl-(C1-C6), hydroxyalkyl-(C1-C6), hydroxycarbonyl-alkoxy-(C1-C4), alkoxycarbonyl-(C1-C6)-alkyl-(C1-C4), alkoxy-(C1-C6)-alkyl-(C1-C6), alkenyl-(C2-C6), haloalkenyl-(C2-C6), cyanoalkenyl-(C2-C6), alkynyl-(C2-C6), haloalkynyl-(C2-C6), cyanoalkynyl-(C2-C6), alkoxy, haloalkoxy-(C1-C6), cyanoalkoxy-(C1-C6), alkoxycarbonyl-(C1-C7)-alkoxy-(C1-C6), alkoxy-(C1-C6)-alkoxy-(C1-C6), alkylhydroxyimino-(C1-C7), alkoxyimino- (C1-C7), alkyl-(C1-C6)-alkoxyimino-(C1-C7), haloalkyl-(C1-C6)-alkoxyimino, alkylthio-(C1-C6), haloalkylthio-(C1-C6), alkoxy- (C1-C6)-alkylthio, (C1-C6)-alkylthio-(C1-C1)-alkylthio C6), alkylsulfinyl-(C1-C6), haloalkylsulfinyl-(C1-C6), alkoxy-(C1-C6)-alkylsulfinyl, alkylsulfinyl-(C1-C6)-alkyl-(C1-C6), alkylsulfonyl-(C1-C1- C6), haloalkylsulfonyl-(C1-C6), alkoxy-(C1-C6)-alkylsulfonyl-(C1-C6), alkylsulfonyl-(C1-C6)-alkyl-(C1-C6), alkylsulfonyloxy-(C1-C6) , alkylcarbonyl (C1-C7), haloalkylcarbonyl-(C1-C7), carboxyl, alkylcarbonyloxy (C1-C7), alkoxycarbonyl (C1-C7), haloalkoxycarbonyl (C1-C7), alkoxycarbonyl (C1-C7) -alkyl-(C1-C6), aminocarbonyl, alkylaminocarbonyl-(C1-C7), di-alkylaminocarbonyl-(C1-C7), alkenylaminocarbonyl-(C1-C7), di-alkenylaminocarbonyl-(C1-C7), cycloalkylaminocarbonyl-( C3-C8), alkylsulfonylamino-(C1-C6), aminosulfonyl, alkylaminosulfonyl-(C1-C6), di-alkylaminosulfonyl-(C1-C6), alkylsulfoximino-(C1-C6), aminothiocarbonyl, alkylaminothiocarbonyl-(C1-C6) , di-alkylaminothiocarbonyl-(C1-C6), or represents phenyl-alkyl-(C1-C6), phenoxy, phenyl-alkylaxy-(C1-C4), phenoxy-alkyl-(C1-C4), phenylthio, phenylthio-alkyl -(C1-C4), phenylsulfinyl, phenylsulfonyl, hetaryl-alkyl-(C1-C6), hetaryloxy, hetaryl-alkylaxy-(C1-C4), hetarylthio, hetarylsulfinyl, hetarylsulfonyl, cycloalkyl-(C3-C8)-alkyl-( C1-C8), cycloalkylaxy(C3-C8), cycloalkylthio(C3-C8), cycloalkylsulfinyl(C3-C8), cycloalkylsulfonyl(C3-C8), optionally saturated or unsaturated, substituted by cycloalkyl(C3-C8) ), cycloalkoxy-(C3-C8), cycloalkyl-(C3-C8)-alkyl-(C1-C6) or cycloalkyl-(C3-C8)-alkoxy-(C1-C6) optionally saturated or unsaturated, optionally substituted by substituents identical or different from the group consisting of halogen, cyano, nitro, hydroxy, amino, carboxy, alkyl-(C1-C6), haloalkyl-(C1-C6), alkenyl-(C2-C8), haloalkenyl-(C2-C8) , alkynyl-(C2-C6), alkoxy-(C1-C6), haloalkoxy-(C1-C6), alkylthio-(C1-C6), alkylsulfinyl-(C1-C6), alkylsulfonyl(C1-C6), alkylsulfonyloxy -(C1-C6), haloalkylthio-(C1-C6), haloalkylsulfinyl-(C1-C6), haloalkylsulfonyl-(C1-C6), alkylamino-(C1-C6), di-alkylamino-(C1-C1) C6), alkylcarbonylamino-(C1-C7), alkoxycarbonyl-(C1-C7), alkylcarbonyl-(C1-C7), alkylcarbonyloxy-(C1-C7), aminocarbonyl, alkylaminocarbonyl-(C1-C6), di-alkylaminocarbonyl-( C1-C6), aminothiocarbonyl, alkylaminothiocarbonyl-(C1-C6), di-alkylaminothiocarbonyl-(C1-C6), cycloalkylamino-(C3-C8), alkylsulfonylamino-(C1-C6), aminosulfonyl, alkylaminosulfonyl-(C1-C6) and di-alkylaminosulfonyl-(C1-C6) and optionally interrupted by one or two heteroatoms from the group consisting of O, S and N, or represents NR4R5, wherein R4 and R5 independently of one another represent hydrogen, cyano, (C1 alkyl) -C6), haloalkyl-(C1-C6), cyanoalkyl-(C1-C6), hydroxyalkyl-(C1-C6), alkoxy-(C1-C6)-alkyl-(C1-C6), alkyl-(C1-C6) )-thioalkyl-(C1-C6), alkenyl-(C2-C8), haloalkenyl-(C2-C8), cyanoalkenyl-(C2-C8), alkynyl-(C2-C8), haloalkynyl-(C2-C8), cyanoalkynyl-(C2-C8), acyl, alkoxycarbonyl-(C1-C7), or R4 and R5 together with the nitrogen atom to which they are attached can form a five- to seven-membered ring, saturated or unsaturated, which is optionally substituted by identical or different substituents from the group consisting of halogen, cyano, hydroxy, amino, (C1-C6)-alkyl, (C1-C6)-haloalkyl, (C1-C6)-alkoxy- (C1-C6), haloalkoxy-(C1-C6) or bi-cycloalkyl-(C3-C8) or cycloalkyl-(C3-C8)-alkyl-(C1-C6) optionally substituted by identical or different substituents from the group consisting of halogen, cyano, (C1-C6)-alkyl, (C1-C6)-alkoxy, (C1-C6)-haloalkyl and optionally interrupted by heteroatoms from the group consisting of O, S and N and is optionally interrupted by heteroatoms from the consisting group by O, S and N, or represents cycloalkyl(C3-C8), cycloalkoxy(C3-C8), cycloalkylthio(C3-C8), cycloalkenyl(C3-C8), phenyl, pyridyl, pyrimidyl, pyridazinyl, pyrazinyl, triazinyl, thiazolyl, thiadiazolyl, oxazolyl, oxadiazolyl, pyrazolyl or triazolyl which is optionally mono- or polysubstituted by identical or different substituents from the group consisting of halogen, cyano, nitro, alkyl-(C1-C6), haloalkyl-(C1-C6), alkoxy-(C1-C6), haloalkoxy-(C1-C6), alkylthio-(C1-C6), alkylsulfinyl-(C1-C6), alkylsulfonyl(C1-C6), alkylsulfonyloxy-(C1-C6), haloalkylthio-(C1-C6), haloalkylsulfinyl-(C1-C6), haloalkylsulfonyl-(C1-C6) or bi- cycloalkyl-(C3-C8), cycloalkoxy-(C3-C8), cycloalkyl-(C3-C8)alkyl-(C1-C6) or cycloalkyl-(C3-C8)-alkoxy-(C1-C6), optionally substituted by halogen, cyano, (C1-C6)-alkyl, (C1-C6)-alkoxy, (C1-C6)-haloalkyl and optionally interrupted by heteroatoms from the group consisting of O, S and N, or X2 and X3 or X3 and X4 may form the following 5- or 6-membered rings which are optionally substituted by identical or different substituents from the group consisting of halogen, cyano, (C1-C6)-alkyl, (C3-C8)-cycloalkyl, (C1-C6)-haloalkyl , halocycloalkyl (C3-C8), alkoxy (C1-C6), haloalkoxy (C1-C6), or X2 and X3 or X3 and X4 may form the following fused rings which are optionally mono- or polysubstituted by identical or different substituents, the substituents may be independently of one another selected from the group consisting of hydrogen, halogen, cyano, alkyl-( C1-C6), cycloalkyl (C3-C8), haloalkyl (C1-C6), halocycloalkyl (C3-C8), alkoxy-(C1-C6), haloalkoxy-(C1-C6), alkoxy-(C1-C1- C6)-alkyl-(C1-C6), alkylthio-(C1-C6), alkylsulfonyl-(C1-C6), amino, alkylamino-(C1-C6), di-alkylamino-(C1-C6) and cycloalkylamino-( C3-C8), R3 is preferably hydrogen, (C2-C6) alkyl, cyano, haloalkyl-(C1-C6), alkoxy-(C1-C6)-alkyl-(C1-C6), cyanoalkyl-(C1-C6), alkylthio-(C1 -C6)-alkyl-(C1-C6), alkenyl-(C2-C6), haloalkenyl-(C2-C6), alkynyl-(C2-C6), haloalkynyl-(C2-C6), or represent a ring of 3 to 6-membered, saturated, partially saturated or aromatic which may optionally contain one to three heteroatoms from the group consisting of O, S and N and which is optionally mono- or polysubstituted by identical or different substituents from the group consisting of halogen, cyano, nitro, hydroxy , amino, carboxy, haloalkoxy-(C1-C6), alkylthio-(C1-C6), alkylsulfinyl-(C1-C6), alkylsulfonyl-(C1-C6), alkylsulfonyloxy-(C1-C6), haloalkylthio-(C1-C1) C6), haloalkylsulfinyl-(C1-C6), haloalkylsulfonyl-(C1-C6), alkylamino-(C1-C6), dialkylamino-(C1-C6), alkylcarbonylamino-(C1-C7), alkoxycarbonyl (C1-C7) , (C1-C7) alkylcarbonyl, (C1-C7) alkylcarbonyloxy, aminocarbonyl, (C1-C7) arylaminocarbonyl, (C1-C6) dialkyl )- aminocarbonyl, aminothiocarbonyl, alkylaminothiocarbonyl-(C1-C6), dialkylaminothiocarbonyl-(C1-C6), cycloalkylamino-(C3-C6), alkylsulfonylamino-(C1-C6), aminosulfonyl, alkylaminosulfonyl-(C1-C6) and dialkylaminosulfonyl -(C1-C6), or substituted by cycloalkyl-(C3-C8), cycloalkoxy-(C3-C8), cycloalkyl-(C3-C8)-alkyl-(C1-C6) or cycloalkyl-(C3-C8) -alkoxy-(C1-C6) optionally substituted by identical or different substituents from the group consisting of halogen, cyano, nitro, hydroxy, amino, carboxy, (C1-C6)-alkyl, (C1-C6)-haloalkyl,-(C1-C6)-alkoxy-( C1-C6), haloalkoxy-(C1-C6) and optionally interrupted by heteroatoms from the group consisting of O, S and N, R1 and R2 independently of one another, preferably represents hydrogen, cyano, (C1-C6)-alkyl, haloalkyl -(C1-C6), alkoxy-(C1-C6), cyanoalkyl-(C1-C6), hydroxyalkyl-(C1-C6), alkoxy-(C1-C6)-alkyl-(C1-C6), alkylthio-( C1-C6) alkyl-(C1-C6), alkenyl-(C2-C6), haloalkenyl-(C2-C6), cyanoalkenyl-(C2-C6), alkynyl-( C2-C6), haloalkynyl-(C2-C6), cyanoalkynyl-(C2-C6), represents alkylcarbonyl-(C1-C6), alkoxycarbonyl-(C1-C7), arylcarbonyl, hetarylcarbonyl, aryloxycarbonyl, hetaryloxycarbonyl, haloalkylsulfinyl-(C1 -C6), arylsulfinyl, arylhetarylsulfinyl, hetaryl-alkylsulfinyl-(C1-C6), haloalkylsulfonyl-(C1-C6), arylsulfonyl, arylhetarylsulfonyl, hetaryl-alkylsulfonyl(C1-C6) optionally substituted by identical or different substituents from group consisting of halogen, cyano, nitro, hydroxy, amino, carboxy, alkyl-(C1-C6), haloalkyl-(C1-C6), alkenyl-(C2-C8), haloalkenyl-(C2-C8), alkynyl-( C2-C8), alkoxy-(C1-C6), haloalkoxy-(C1-C6), alkylthio-(C1-C6), alkylsulfinyl-(C1-C6), alkylsulfonyl-(C1-C6), alkylamino-(C1-C1) C6), di-alkylamino-(C1-C6), or represent a 3 to 6 membered, saturated, partially saturated or aromatic ring which may optionally contain one to three heteroatoms from the group consisting of O, S and N which may optionally be interrupted once or twice zes by C=O, SO or SO2 and which is optionally mono- or polysubstituted by identical or different substituents from the group consisting of halogen, cyano, nitro, hydroxy, amino, carboxy, (C1-C6)-alkyl, (C1-C1-halo)alkyl C6), alkenyl-(C2-C6), haloalkenyl-(C2-C6), alkynyl-(C2-C6), alkoxy-(C1-C6), haloalkoxy-(C1-C6), alkylthio-(C1-C6) , alkylsulfinyl-(C1-C6), alkylsulfonyl-(C1-C6), alkylsulfonyloxy-(C1-C6), haloalkylthio-(C1-C6), haloalkylsulfinyl-(C1-C6), haloalkylsulfonyl-(C1-C6), alkylamino -(C1-C6), dialkylamino-(C1-C6), alkylcarbonylamino-(C1-C7), alkoxycarbonyl-(C1-C7), alkylcarbonyl-(C1-C7), alkylcarbonyloxy-(C1-C7), aminocarbonyl, arylaminocarbonyl(C1-C7), dialkylaminocarbonyl(C1-C7), aminothiocarbonyl, alkylaminothiocarbonyl(C1-C7), dialkylaminothiocarbonyl(C1-C7), cycloalkylamino(C3-C8), alkylsulfonylamino(C1-C6), aminosulfonyl, alkylaminosulfonyl(C1-C6) and dialkylaminosulfonyl(C1-C6) or by cycloalkyl(C3-C8), cycloalkoxy(C3-C8) ), cycloalkyl-(C3-C8)alkyl-(C1-C6) or cycloalkyl-(C3-C8)-alkoxy-(C1-C6) optionally interrupted by heteroatoms from the group consisting of O, S and N, or represents -( C2)m-R6, -O-(C2)m-R6, (C2)mO-R6, wherein R6 represents a saturated, partially saturated or aromatic 3- to 6-membered ring, which may optionally contain one to three heteroatoms of the group consisting of O, S and N, which may optionally be interrupted once or twice by C=O and which is optionally mono- or polysubstituted by identical or different substituents from the group consisting of halogen, cyano, nitro, hydroxy, amino, carboxy, alkyl-(C1-C6), haloalkyl-(C1-C6), alkenyl-(C2-C6), haloalkenyl-(C2-C6), alkynyl-(C2-C6), alkoxy-(C1-C6), haloalkoxy- (C1-C6), alkylthio-(C1-C6), alkylsulfinyl-(C1-C6), alkylsulfonyl-(C1-C6), alkylsulfonyloxy-(C1-C6), haloalkylthio-(C1-C6), haloalkylsulfinyl-(C1 -C6), haloalkylsulfonyl-(C1-C6), alkylamino-(C1-C6), dialkylamino-(C1-C6), alkylcabonylamino-(C1-C7) ), alkoxycarbonyl(C1-C7), alkylcarbonyl(C1-C7), alkylcarbonyloxy(C1-C7), aminocarbonyl, alkylaminocarbonyl-(C1-C7), di-alkylaminocarbonyl-(C1-C7), aminothiocarbonyl, alkylaminothiocarbonyl-( C1-C7), dialkylaminothiocarbonyl-(C1-C7), cycloalkylamino-(C3-C8), alkylsulfonylamino-(C1-C6), aminosulfonyl, alkylaminosulfonyl-(C1-C6) or dialkylaminosulfonyl-(C1-C6) or by identical substituents or different from the group consisting of cycloalkyl-(C3-C8), cycloalkoxy-(C3-C8), cycloalkyl-(C3-C8)-alkyl-(C1-C6) and cycloalkyl-(C3-C8)-alkoxy-(C1 -C6) optionally substituted by halogen, cyano, nitro, hydroxy, amino, carboxy, alkyl-(C1-C6), haloalkyl-(C1-C6), alkenyl-(C2-C8), haloalkenyl-(C2-C8), allicnyl-(C2-C8), alkoxy-(C1-C6), haloalkoxy-(C1-C6), alkylthio-(C1-C6), alkylsulfinyl-(C1-C6), alkylsulfonyl-(C1-C6), alkylsulfonyloxy- (C1-C6), haloalkylthio-(C1-C6), haloalkylsulfinyl-(C1-C6), haloalkylsulfonyl-(C1-C6), alkylamino-(C1-C6), dialkylamino-(C1-C6), al alkylcarbonylamino(C1-C7), alkoxycarbonyl(C1-C7), alkylcarbonyl(C1-C7), alkylcarbonyloxy(C1-C7), aminocarbonyl, alkylaminocarbonyl(C1-C6), dialkylaminocarbonyl(C1-C6) , aminothiocarbonyl, alkylaminothiocarbonyl-(C1-C6), dialkylaminothiocarbonyl-(C1-C6), cycloalkylamino-(C3-C8), alkylsulfonylamino-(C1-C6), aminosulfonyl, alkylaminosulfonyl-(C1-C6) or dialkylaminosulfonyl-(C1-C1- C6) and optionally interrupted by heteroatoms from the group consisting of O, S and N, where m represents the number 1, 2 or 3, or R1 and R2 together with the atoms to which they are attached can form a 4 to 8 ring. members, saturated or unsaturated, which may optionally be mono- or polysubstituted by (C1-C4)-alkyl, (C1-C4)-alkoxy, halogen, (C1-C4)-haloalkyl and which may optionally contain one or two additional heteroatoms from group consisting of sulfur, oxygen and nitrogen (where the oxygen atoms must not be directly adjacent) and/or at least one ca group Rbonyl, R1 and R3 together with the atoms to which they are attached can form a 4- to 8-membered, saturated or unsaturated ring, which may optionally be mono- or poly-substituted by identical or different substituents from the group consisting of (C1-C4)-alkyl ), alkoxy-(C1-C4), halogen, haloalkyl-(C1-C4), cyano, cycloalkyl-(C3-C6), halocycloalkyl-(C3-C6), cyanocycloalkyl-(C3-C6), alkyl (C1 -C2)-cycloalkyl-(C3-C6)-alkanediyl(C2-C4), alkenediyl(C2-C4), butanedienyl (wherein alkanediyl, alkenediyl and butanedienyl may be optionally substituted by (C1-C4)-alkyl, alkoxy -(C1-C4), halogen, haloalkyl-(C1-C4) and/or may optionally be interrupted by at least one oxygen and/or nitrogen atom) and which may optionally contain one or two additional heteroatoms from the sulfur group , oxygen and nitrogen (where the oxygen atoms must not be directly adjacent) and/or at least one carbonyl group,
ou X2 e X3 ou X3 e X4 podem formar os anéis fundidos abaixo, que são opcionalmente monossubstituídos ou dois por substituintes diferentes, em que os substituintes, independentemente um do outro, podem ser seleccionados do grupo constituído por hidrogênio, flúor, cloro, bromo, ciano, alquila-(C1-C4), cicloalquila-(C3-C6), haloalquila-(C1- C4), alcoxi (C1-C4), haloalcoxi-(C1-C4), R3 com particular preferência representa hidrogênio, alquila-(C2-C4), ciano, haloalquila-(C1-C4), alcoxi-(C1-C4)-alquila-(C1-C4), cianoalquila-(C1-C4), ou representa um anel de 3 a 6 membros, saturado, parcialmente saturado ou aromático que pode conter opcionalmente ium ou dois heteroátomos do grupos constituído por O, S e N e que é opcionalmente monossubstituído ou trissubstituído por substituintes idênticos ou diferentes do grupo constituído por flúor, cloro, bromo, iodo, ciano, nitro, alquila-(C1-C4), haloalquila-(C1-C4), alcenila-(C2-C4), alcinila-(C2-C4), alcoxi-(C1-C4), haloalcoxi-(C1-C4), ou substituído por cicloalquila-(C3-C6), R1 e R2 independentemente um do outro representam com particular preferência hidrogênio, ciano, alquila-(C1-C4), haloalquila-(C1- C4), alcoxi-(C1-C4), cianoalquila-(C1-C4), hidroxialquila-(C1-C4), alcoxi- (C1-C4)-alquila-(C1-C4), alcenila-(C2-C4), alcinila-(C2-C4), representa alquilcarbonila-(C1-C4), alcoxicarbonila-(C1-C5), arilcarbonila, tiofenilcarbonila, piridilcarbonila, pirimidilcarbonila, tiazolilcarbonila, pirazolilcarbonila, alquilsulfinila-(C1-C4), haloalquilsulfinila-(C1-C4), arilsulfinila, arila-(C1-C4) alquilsulfinila, hetarilsulfinila, hetarila-(C1-C4) alquilsulfinila, alquilsulfonil-(C1-C4), haloalquilsulfonil-(C1-C4), arilsulfonil, arila-alquilsulfonil-(C1-C4), hetarilsulfonil, hetarila-alquilsulfonil-(C1-C4) opcionalmente monossubstituído ou trissubstituído, independentemente um do outro, por substituintes idênticos ou diferentes do grupo constituído por flúor, cloro, bromo, iodo, ciano, nitro, alquila-(C1-C4), haloalquila-(C1-C4), alcenila-(C2-C4), haloalcenila-(C2-C4), alcinila-(C2-C4), alcoxi-(C1-C4), haloalcoxi-(C1-C4), alquiltio-(C1-C4), alquilsulfinila-(C1-C4), alquilsulfonil- (C1-C4), alquilamino-(C1-C4), dialquilamino-(C1-C4), ou representa um anel de 3 a 6 membros, saturado ou aromático que pode conter opcionalmente ium ou dois heteroátomos do grupos constituído por O, S e N, que é opcionalmente interrompido uma ou duas vezes por C=O e que é opcionalmente monossubstituído ou trissubstituído por substituintes idênticos ou diferentes do grupo constituído por flúor, cloro, bromo, ciano, nitro, alquila-(C1-C4), haloalquila-(C1-C4), alcenila-(C2-C4), alcinila-(C2-C4), alcoxi-(C1-C4), haloalcoxi-(C1-C4), ou substituído por cicloalquila-(C3-C6), ou representam -(CH2)m-R6, -O-(CH2)m-R6, -(CH2)m-O-R6, em que R6 representa um anel de 3 a 6 membros, saturado ou aromático que pode conter opcionalmente ium ou dois heteroátomos do grupos constituído por O, S e N, que é opcionalmente interrompido uma ou duas vezes por C=O e que é opcionalmente monossubstituído ou trissubstituído por substituintes idênticos ou diferentes do grupo constituído por flúor, cloro, bromo, ciano, nitro, alquila-(C1-C4), haloalquila-(C1-C4), alcenila-(C2-C4), alcinila-(C2-C4), alcoxi-(C1-C4), haloalcoxi-(C1-C4), ou substituído por cicloalquila-(C3-C6), em que m representa o número 1 ou 2 ou R1 e R2 conjuntamente com o átomo de nitrogênio ao qual estão ligados podem formar um anel de 3 a 6 membros, saturado ou insaturado, que pode ser opcionalmente monossubstituído ou tetrassubstituído por flúor, cloro alquila-(C1-C4), alcoxi-(C1-C4), haloalquila-(C1-C4) e que pode conter opcionalmente mais um heteroátomo do grupo constituído por enxofre, oxigênio e nitrogênio e/ou pelo menos um grupo carbonila, R1 e R3 conjuntamente com os átomos aos quais estão ligados podem formar um anel de 5 a 6 membros, saturado ou insaturado, que é opcionalmente monossubstituído ou polissubstituído por metil, etil, metoxi, etoxi, flúor, cloro, trifluorometil, ciclopropil, ciano, clorociclopropil, fluorociclopropil, cianociclopropil, metilciclopropil, alcanodiila-(C2-C4), alcenodiila-(C2-C4), butanodienila (em que o butanodienila pode ser opcionalmente monossubstituído ou dissubstituído por metil, flúor, cloro, bromo, metoxi ou trifluorometil e que pode conter opcionalmente mais um heteroátomo do grupo constituído por enxofre, oxigênio e nitrogênio e/ou pelo menos um grupo carbonila, A Fórmula (I) proporciona uma definição geral dos compostos de acordo com a invenção. São definidos os substituintes muito particularmente preferidos ou intervalos dos radicais indicados nas Fórmulas apresentadas anteriormente e seguidamente, em que n representa com muito particular preferência o número 0 ou 1, X1 e X3 representam de modo muito particularmente preferido hidrogênio. X2 e X4 representam independentemente um do outro, de forma particularmente preferida hidrogênio, flúor, cloro, bromo, metil, etil, trifluorometil, difluorometil, difluorometoxi, trifluorometoxi, OCH2CF3, com especial preferência X2 e X4 representam as seguintes combinações X2/X4: F/F, Cl/Cl, F/Cl, Cl/F, Br/Br, Br/Cl, Cl/Br, Br/F, F/Br, metil/metil, metil/F, F/metil, metil/Cl, Cl/metil, metil/Br, Br/metil, etil/etil, etil/F, F/etil, etil/Cl, Cl/etil, etil/Br, Br/etil, R3 de modo mais particularmente preferido hidrogênio, etil, propil, ciano, trifluorometil, difluorometil, diclorometil, clorometil, triclorometil, difluoroclorometil, diclorofluorometil, (2,2,2)-trifluoroetil, 2- cloro-(2,2)-difluoroetil, (2,2)-dicloro-2-fluoroetil, (2,2,2)-tricloroetil, pentafluoroetil, ou representa arila, com especial preferência fenila, R1 de modo mais particularmente preferido hidrogênio, metil, etil, propil, butil, sec-butil, isopropil, terc-butil, (2,2,2)-trifluoroetil, (2,2)-difluorometil, metoxi, etoxi, metoximetil, metoxietil, ou representa arila que é opcionalmente monossubstituído, dissubstituído ou trissubstituído por substituintes idênticos ou diferentes do grupo constituído por flúor, cloro, bromo, ciano, nitro, metil, etil, trifluorometil, vinila, etinila, metoxi, etoxi, difluorometoxi, trifluorometoxi, trifluoroetoxi ou ciclopropil, com referência explícita ao fenila que pode ser opcionalmente substituído pelos substituintes referidos como mais particularmente preferidos, ou representa -(C2)m-R6, em que R6 representa arila que é opcionalmente monossubstituído, dissubstituído ou trissubstituído por substituintes idênticos ou diferentes do grupo constituído por flúor, cloro, bromo, ciano, nitro, metil, etil, trifluorometil, vinila, etinila, metoxi, etoxi, difluorometoxi, trifluorometoxi, trifluoroetoxi ou ciclopropil, em que m representa o número 1, em especial fenila é explicitamente referido para R6, que pode ser opcionalmente substituído pelos substituintes referidos como mais particularmente preferidos, R2 representa de modo muito particularmente preferido hidrogênio, metil ou etil ou R1 e R2 conjuntamente com o átomo de nitrogênio ao qual estão ligados podem formar um anel de 5 a 6 membros, saturado ou insaturado, que pode opcionalmente conter um átomo de oxigênio, especialmente os seguintes anéis são explicitamente referidos, em que o átomo de nitrogênio que está ligado a R1 e R2 representa o ciclo e a seta aponta para o resto da molécula, R1 e R3 conjuntamente com os átomos aos quais estão ligados podem formar um anel de 5 a 6 membros, saturado ou insaturado e/ou um que é opcionalmente monossubstituído ou dissubstituído por metil, etil, metoxi, etoxi, flúor, cloro, trifluorometil, difluorometil, ciano, clorociclopropil, fluorociclopropil, cianociclopropil, metilciclopropil, alcanodiila-(C3-C4), alcenodiila-(C3-C4), butanodienila (em que a butanodienila pode ser opcionalmente monossubstituído ou dissubstituído por metil, flúor, cloro, bromo, metoxi ou trifluorometil e que pode conter opcionalmente mais um heteroátomo do grupo constituído por enxofre, oxigênio e nitrogênio e/ou pelo menos um grupo carbonila, em especial R1 e R3 conjuntamente com os átomos aos quais estão ligados representam o seguinte grupo, cada um dos quais pode ser opcionalmente monossubstituído ou dissubstituído por metil, etil, metoxi, etoxi, flúor, cloro, trifluorometil, difluorometil, ciclopropil, clorociclopropil, fluorociclopropil, cianociclopropil, metilciclopropil, em que a seta aponta para o resto da molécula.[00010] Formula (I) provides a general definition of the compounds according to the invention. Particularly preferred substituents or ranges of radicals indicated in the Formulas given above and below are defined, wherein n particularly preferably represents the number 0 or 1, X1, X2, X3, X4 independently of one another particularly preferably represent hydrogen, fluorine, chlorine, bromine, iodine, alkyl-(C1-C4), haloalkyl-(C1-C4), alkenyl-(C2-C4), alkynyl-(C2-C4), alkoxy-(C1-C4), haloalkoxy-(C1 -C4), aminothiocarbonyl, or represents phenyl-alkyl-(C1-C4), phenoxy, hetarylalkyl-(C1-C4), hetaryloxy, optionally saturated or unsaturated cycloalkyl-(C1-C6)-alkyl-(C1-C4), cycloalkylaxy(C3-C6), cycloalkyl(C3-C6)-alkoxy-(C1-C4), optionally monosubstituted or disubstituted by identical or different substituents from the group consisting of fluorine, chlorine, bromine, cyano, nitro, alkyl-( C1-C4), haloalkyl-(C1-C4), alkoxy-(C1-C4), haloalkoxy-(C1-C4) or by cycloalkyl-(C3-C6) optionally saturated or unsaturated, which is optionally component interrupted by a heteroatom from the group consisting of O, S and N, or represents (C3-C6)-cycloalkyl, phenyl, pyridyl, pyrimidyl, pyridazinyl, pyrazinyl, triazinyl, thiazolyl, thiadiazolyl, oxazolyl, oxadiazolyl, pyrazolyl, triazolyl or tetrazolyl which is optionally mono- or di-substituted by identical or different substituents from the group consisting of fluorine, chlorine, bromine, cyano, nitro, (C 1 -C 4 )alkyl, (C 1 -C 4 )alkyl, (C 1 -C 4 )alkoxy, haloalkoxy -(C1-C4), cycloalkyl-(C3-C6), or X2 and X3 or X3 and X4 can form the following 5- or 6-membered rings which are optionally monosubstituted or disubstituted by fluorine or (C1-C4)-alkyl, or X2 and X3 or X3 and X4 may form the fused rings below, which are optionally mono-substituted or two by different substituents, wherein the substituents, independently of one another, may be selected from the group consisting of hydrogen, fluorine, chlorine, bromine, cyano, (C1-C4) alkyl, cycloalkyl (C3-C6), haloalkyl (C1-C4), alkoxy (C1-C4), haloalkoxy (C1-C4), R3 particularly preferably represents hydrogen, (C2-C4)-alkyl, cyano, (C1-C4)-haloalkyl, (C1-C4)-alkoxy-(C1-C4)-alkyl, (C1-C4)-cyanoalkyl, or represents a 3- to 6-membered, saturated, partially saturated or aromatic ring which may optionally contain one or two heteroatoms from the group consisting of O, S and N and which is optionally mono- or tri-substituted by identical or different substituents from the group consisting of fluorine, chlorine, bromine, iodine, cyano, nitro, alkyl(C1-C4), haloalkyl-(C1-C4), alkenyl-(C2-C4), alkynyl-(C2-C4), alkoxy-(C1-C4), haloalkoxy-(C1-C4), or substituted by cycloalkyl-(C3-C6), R1 and R2 independently of one another are particularly preferably hydrogen, cyano, (C1-C4)-alkyl, (C1-C4)-haloalkyl, alkoxy-(C1-C4), cyanoalkyl-(C1-C4), hydroxyalkyl-(C1-C4), alkoxy-(C1-C4)-alkyl-(C1-C4), alkenyl-(C2-C4), alkynyl- (C2-C4), represents alkylcarbonyl (C1-C4), alkoxycarbonyl (C1-C5), arylcarbonyl, thiophenylcarbon yl, pyridylcarbonyl, pyrimidylcarbonyl, thiazolylcarbonyl, pyrazolylcarbonyl, alkylsulfinyl (C1-C4), haloalkylsulfinyl (C1-C4), arylsulfinyl, aryl-(C1-C4) alkylsulfinyl, hetarylsulfinyl, hetaryl-(C1-C4) alkylsulfinyl, alkylsulfonyl- (C1-C4), haloalkylsulfonyl-(C1-C4), arylsulfonyl, aryl-alkylsulfonyl-(C1-C4), hetarylsulfonyl, hetaryl-alkylsulfonyl-(C1-C4) optionally mono- or tri-substituted independently of one another by identical substituents or different from the group consisting of fluorine, chlorine, bromine, iodine, cyano, nitro, alkyl-(C1-C4), haloalkyl-(C1-C4), alkenyl-(C2-C4), haloalkenyl-(C2-C4), alkynyl-(C2-C4), alkoxy-(C1-C4), haloalkoxy-(C1-C4), alkylthio-(C1-C4), alkylsulfinyl-(C1-C4), alkylsulfonyl-(C1-C4), alkylamino- (C1-C4), dialkylamino-(C1-C4), or represents a 3- to 6-membered, saturated or aromatic ring which may optionally contain one or two heteroatoms from the group consisting of O, S and N, which is optionally interrupted once or twice by C=O and which is optionally mono- or tri-substituted by identical or different substituents from the group consisting of fluorine, chlorine, bromine, cyano, nitro, (C1-C4)-alkyl, (C1-C4)-haloalkyl, alkenyl-(C2-C4), alkynyl-(C2-C4), alkoxy-(C1-C4), haloalkoxy-(C1-C4), or substituted by cycloalkyl-(C3-C6), or represent -(CH2)m -R6, -O-(CH2)m-R6, -(CH2)mO-R6, wherein R6 represents a 3- to 6-membered, saturated or aromatic ring which may optionally contain one or two heteroatoms from the group consisting of O, S and N, which is optionally interrupted once or twice by C=O and which is optionally mono- or tri-substituted by identical or different substituents from the group consisting of fluorine, chlorine, bromine, cyano, nitro, (C1-C4)-alkyl, haloalkyl-(C1-C4), alkenyl-(C2-C4), alkynyl-(C2-C4), alkoxy-(C1-C4), haloalkoxy-(C1-C4), or substituted by cycloalkyl-(C3-C6) , where m represents the number 1 or 2 or R1 and R2 together with the nit atom Rogen to which they are attached can form a 3 to 6 membered, saturated or unsaturated ring, which can be optionally mono- or tetra-substituted by fluorine, chloro(C1-C4)-alkyl, (C1-C4)-alkoxy, (C1-C1)-haloalkyl -C4) and which may optionally contain one more heteroatom from the group consisting of sulfur, oxygen and nitrogen and/or at least one carbonyl group, R1 and R3 together with the atoms to which they are attached may form a 5- to 6-membered ring, saturated or unsaturated, which is optionally mono- or polysubstituted by methyl, ethyl, methoxy, ethoxy, fluorine, chlorine, trifluoromethyl, cyclopropyl, cyano, chlorocyclopropyl, fluorocyclopropyl, cyanocyclopropyl, methylcyclopropyl, (C2-C4)-alkanediyl,-(C2-C4)-alkenodiyl C4), butanedienyl (wherein butanedienyl may be optionally mono- or disubstituted by methyl, fluorine, chlorine, bromine, methoxy or trifluoromethyl and which may optionally contain one more heteroatom from the group consisting of sulfur, oxygen and nitrogen and/or at least one carbonyl group, Formula (I) provides a general definition of the compounds according to the invention. Very particularly preferred substituents or ranges of radicals indicated in the Formulas given above and below are defined, wherein n very particularly preferably represents the number 0 or 1, X1 and X3 most particularly preferably represent hydrogen. X2 and X4 independently of one another, particularly preferably hydrogen, fluorine, chlorine, bromine, methyl, ethyl, trifluoromethyl, difluoromethyl, difluoromethoxy, trifluoromethoxy, OCH2CF3, especially preferably X2 and X4 represent the following combinations X2/X4: F /F, Cl/Cl, F/Cl, Cl/F, Br/Br, Br/Cl, Cl/Br, Br/F, F/Br, methyl/methyl, methyl/F, F/methyl, methyl/Cl , Cl/methyl, methyl/Br, Br/methyl, ethyl/ethyl, ethyl/F, F/ethyl, ethyl/Cl, Cl/ethyl, ethyl/Br, Br/ethyl, R3 more particularly preferably hydrogen, ethyl , propyl, cyano, trifluoromethyl, difluoromethyl, dichloromethyl, chloromethyl, trichloromethyl, difluorochloromethyl, dichlorofluoromethyl, (2,2,2)-trifluoroethyl, 2-chloro-(2,2)-difluoroethyl, (2,2)-dichloro-2 -fluoroethyl, (2,2,2)-trichloroethyl, pentafluoroethyl, or represents aryl, especially preferably phenyl, R1 more particularly preferably hydrogen, methyl, ethyl, propyl, butyl, sec-butyl, isopropyl, tert-butyl, (2,2,2)-trifluoroethyl, (2,2)-difluoromethyl, methoxy, ethoxy, methoxymethyl, methoxyethyl, or represents aryl which is optionally monosubstituted, disubstituted or trisubstituted by identical or different substituents from the group consisting of fluorine, chlorine, bromine, cyano, nitro, methyl, ethyl, trifluoromethyl, vinyl, ethynyl, methoxy, ethoxy, difluoromethoxy, trifluoromethoxy, trifluoroethoxy or cyclopropyl, with explicit reference to phenyl which may be optionally substituted by the substituents referred to as more particularly preferred, or represents -(C2)m-R6, wherein R6 represents aryl which is optionally mono-, di- or tri-substituted by identical or different substituents from the group consisting of fluorine, chlorine, bromine, cyano, nitro, methyl, ethyl, trifluoromethyl, vinyl, ethynyl, methoxy, ethoxy, difluoromethoxy, trifluoromethoxy, trifluoroethoxy or cyclopropyl, where m represents the number 1, in particular phenyl is explicitly referred to for R6, which may be optionally substituted by the named substituents. as more particularly preferred, R2 very particularly preferably represents hydrogen, methyl or ethyl or R1 and R2 together with the nitrogen atom to which they are attached may form a 5- to 6-membered, saturated or unsaturated ring, which may optionally contain a oxygen atom, especially the following rings are explicitly referred to, where the nitrogen atom which is attached to R1 and R2 represents the cycle and the arrow points to the rest of the molecule, R1 and R3 together with the atoms to which they are attached can form a 5- to 6-membered, saturated or unsaturated ring and/or one which is optionally mono- or di-substituted by methyl, ethyl, methoxy, ethoxy, fluorine, chlorine, trifluoromethyl, difluoromethyl, cyano, chlorocyclopropyl, fluorocyclopropyl, cyanocyclopropyl, methylcyclopropyl, (C3-C4)-alkanediyl, (C3-C4)-alkenediyl C4), butanedienyl (wherein butanedienyl may be optionally mono- or disubstituted by methyl, fluorine, chlorine, bromine, methoxy or trifluoromethyl and which may optionally contain one more heteroatom from the group consisting of sulfur, oxygen and nitrogen and/or at least one carbonyl group, especially R1 and R3 together with the atoms to which they are attached represent the following group, each of which may optionally be mono- or di-substituted by methyl, ethyl, methoxy, ethoxy, fluorine, chlorine, trifluoromethyl, difluoromethyl, cyclopropyl, chlorocyclopropyl, fluorocyclopropyl, cyanocyclopropyl, methylcyclopropyl, where the arrow points to the rest of the molecule.
[00011] Formula (I) provides a general definition of the compounds according to the invention. Also very particularly preferred substituents or ranges of the radicals indicated in the Formulas given above and below are defined, n very particularly preferably represents the number 0 or 1, X1 and X3 very particularly preferably represent hydrogen. X2 and X4 independently of one another, particularly preferably hydrogen, fluorine, chlorine, bromine, methyl, ethyl, trifluoromethyl, difluoromethyl, vinyl, ethynyl, methoxy, ethoxy, difluoromethoxy, trifluoromethoxy, OCH2CF3, aminothiocarbonyl, or phenylmethyl, phenoxy, pyridylmethyl, pyrimidylmethyl, thiazolylmethyl, pyrazolylmethyl, pyridyloxy, pyrimidyloxy, thiazolyloxy, pyrazolyloxy, cyclopropylmethyl, cyclopropylmethoxy optionally monosubstituted or disubstituted by identical or different substituents from the group consisting of fluorine, chlorine, bromine, cyano, nitro, methyl, difluoro, trifluoromethyl, methoxy, trifluoromethoxy, difluoromethoxy or cyclopropyl, or represents (C3-C6)-cycloalkyl, phenyl, pyridyl, pyrimidyl, pyridazinyl, pyrazinyl, triazinyl, thiazolyl, thiadiazolyl, oxazolyl, oxadiazolyl, pyrazolyl, triazolyl or tetrazolyl which is optionally monosubstituted or disubstituted identical or different substituents from the group consisting of fluorine r, chlorine, bromine, cyano, nitro, methyl, ethyl, trifluoromethyl, difluoromethyl, methoxy, trifluoromethoxy, difluoromethoxy or cyclopropyl, with special preference X2 and X4 represent the following combinations X2/X4: F/F, Cl/Cl, F/ Cl, Cl/F, Br/Br, Br/Cl, Cl/Br, Br/F, F/Br, methyl/methyl, methyl/F, F/methyl, methyl/Cl, Cl/methyl, methyl/Br, Br/methyl, ethyl/ethyl, ethyl/F, F/ethyl, ethyl/Cl, Cl/ethyl, ethyl/Br, Br/ethyl, methoxy/methyl, methyl/methoxy, methyl/H, ethyl/H, chlorine/ H, bromine/H, fluorine/H, methoxy/H, H/chlorine, H/fluorine, H/bromine, H/methyl, H/methoxy, H/ethyl R3 more particularly preferably hydrogen, ethyl, propyl, cyano , trifluoromethyl, difluoromethyl, dichloromethyl, chloromethyl, trichloromethyl, difluorochloromethyl, dichlorofluoromethyl, (2,2,2)-trifluoroethyl, 2-chloro-(2,2)-difluoroethyl, (2,2)-dichloro-2-fluoroethyl, ( 2,2,2)-trichloroethyl, pentafluoroethyl, methoxymethyl, cyanomethyl, allyl, butenyl, or represents a 3 to 6 membered, saturated, partially saturated or aromatic ring which may optionally contain a or three heteroatoms from the group consisting of O, S and N and which may be optionally mono- or disubstituted by identical or different substituents from the group consisting of fluorine, chlorine, bromine, iodine, cyano, nitro, methyl, ethyl, trifluoromethyl, vinyl, ethynyl , methoxy, ethoxy, difluoromethoxy, trifluoromethoxy, trifluoroethoxy and cyclopropyl, the following rings are explicitly mentioned: cyclopropyl, phenyl, pyridyl, pyrimidyl, thiazolyl, pyrazolyl and thienyl which may be optionally substituted by the substituents referred to as more particularly preferred, R1 represents so more particularly preferred cyano, cyanomethyl, methylcarbonyl, ethylcarbonyl, propylcarbonyl, isopropylcarbonyl, methoxycarbonyl, ethoxycarbonyl, represents arylcarbonyl, pyridylcarbonyl, pyrimidylcarbonyl, thiazolylcarbonyl, pyrazolylcarbonyl, methylsulfinyl, trifluoromethylsulfinyl, methylsulfonyl, optionally substituted monosubstituted or trifluoromethylsulfonyl one another by fluorine, chlorine, bromine, cyano, nitro, methyl, trifluoromethyl, allyl, butenyl, methoxy, trifluoromethoxy, methylthio, methylsulfinyl, methylsulfonyl, methylamino, dimethylamino, or represents oxetanyl, thiethanyl, trimethylenesulfonyl, trimethylenesulfinyl, oxanyl or methyl which may be mono- or polysubstituted by identical or different substituents from the group consisting of fluorine, chlorine, bromine, cyano, nitro, methyl, ethyl, trifluoromethyl, vinyl, ethynyl, methoxy, ethoxy, difluoromethoxy, trifluoromethoxy, trifluoroethoxy and cyclopropyl, or represents cyclopropyl , cyclobutyl, cyclopentyl, cyclohexyl which may be mono- or polysubstituted by identical or different substituents from the group consisting of fluorine, chlorine, bromine, cyano, nitro, methyl, ethyl, trifluoromethyl, vinyl, ethynyl, methoxy, ethoxy, difluoromethoxy, trifluoromethoxy, trifluoroethoxy and cyclopropyl, R2 very particularly preferably represents hydrogen, methyl or ethyl or R1 and R2 co Together with the atoms to which they are attached they can form a 4- to 8-membered, saturated or unsaturated ring, which can be optionally mono- or tetra-substituted by methyl, ethyl, methoxy, ethoxy, fluorine, chlorine, bromine, trifluoromethyl, difluoromethyl and which contains one or two additional heteroatoms from the group consisting of sulfur and nitrogen, or together with the nitrogen atom to which they are attached form a 4-membered ring which is optionally mono-, di-, tri- or tetra-substituted by methyl, ethyl, methoxy, ethoxy, fluorine , chlorine, bromine, trifluoromethyl, difluoromethyl and which contains one more heteroatom from the group consisting of oxygen, sulfur and nitrogen,
em que o átomo de nitrogênio ao qual R1 e R2 estão ligados representam o ciclo e a seta aponta para o resto da molécula, que podem ser opcionalmente monossubstituídos ou dissubstituídos por metil, etil, metoxi, etoxi, flúor, cloro, bromo, trifluorometil, difluorometil.[00012] the following rings are specifically explicitly referred to, where the nitrogen atom to which R1 and R2 are attached represent the cycle and the arrow points to the rest of the molecule, which may be optionally mono- or di-substituted by methyl, ethyl, methoxy, ethoxy, fluorine, chlorine, bromine, trifluoromethyl, difluoromethyl.
em que o átomo de nitrogênio ao qual R1 e R2 estão ligados representam o ciclo e a seta aponta para o resto da molécula, que podem ser opcionalmente monossubstituídos ou dissubstituídos por metil, etil, metoxi, etoxi, flúor, cloro, bromo, trifluorometil, difluorometil.[00013] Formula (I) provides a general definition of the compounds according to the invention. Also very particularly preferred substituents or ranges of the radicals indicated in the Formulas given above and below are defined, in which n very particularly preferably represents the number 0 or 1, X1 and X3 very particularly preferably represent hydrogen. X2 and X4 independently of one another, particularly preferably hydrogen, fluorine, chlorine, bromine, methyl, ethyl, trifluoromethyl, difluoromethyl, vinyl, ethynyl, methoxy, ethoxy, difluoromethoxy, trifluoromethoxy, OCH2CF3, aminothiocarbonyl, or phenylmethyl, phenoxy, pyridylmethyl, pyrimidylmethyl, thiazolylmethyl, pyrazolylmethyl, pyridyloxy, pyrimidyloxy, thiazolyloxy, pyrazolyloxy, cyclopropylmethyl, cyclopropylmethoxy or optionally monosubstituted or disubstituted by identical or different substituents from the group consisting of fluorine, chlorine, bromine, cyano, nitro, methyl, difluoromethyl, trifluoromethyl , methoxy, trifluoromethoxy, difluoromethoxy or cyclopropyl, or represents (C3-C6)-cycloalkyl, phenyl, pyridyl, pyrimidyl, pyridazinyl, pyrazinyl, triazinyl, thiazolyl, thiadiazolyl, oxazolyl, oxadiazolyl, pyrazolyl, triazolyl or tetrazolyl which is optionally disubstituted or monosubstituted by identical or different substituents from the group consisting of f fluorine, chlorine, bromine, cyano, nitro, methyl, ethyl, trifluoromethyl, difluoromethyl, methoxy, trifluoromethoxy, difluoromethoxy or cyclopropyl, with special preference X2 and X4 represent the following combinations X2/X4: F/F, Cl/Cl, F/ Cl, Cl/F, Br/Br, Br/Cl, Cl/Br, Br/F, F/Br, methyl/methyl, methyl/F, F/methyl, methyl/Cl, Cl/methyl, methyl/Br, Br/methyl, ethyl/ethyl, ethyl/F, F/ethyl, ethyl/Cl, Cl/ethyl, ethyl/Br, Br/ethyl, methoxy/methyl, methyl/methoxy, methyl/H, ethyl/H, chlorine/ H, bromine/H, fluorine/H, methoxy/H, H/chlorine, H/fluorine, H/bromine, H/methyl, H/methoxy, H/ethyl R3 more particularly preferably represents methoxymethyl, methoxyethyl, cyanomethyl, allyl, butenyl, oxolanyl, pentandienyl, butadienyl, or represents cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, pyridyl, pyrimidyl, pyrazinyl, pyridazinyl, pyrrolyl, furanyl, thiazolyl, pyrazolyl or thienyl which may be monosubstituted or polysubstituted by identical or different substituents consisting of fluorine, chlorine, bromine, cyano, nitr o, methyl, ethyl, trifluoromethyl, vinyl, ethynyl, methoxy, ethoxy, difluoromethoxy, trifluoromethoxy, trifluoroethoxy and cyclopropyl, or represents aryl, in particular phenyl which is mono- or polysubstituted by identical or different substituents from the group consisting of fluorine, chlorine, bromine , cyano, nitro, methyl, ethyl, trifluoromethyl, vinyl, ethynyl, methoxy, ethoxy, difluoromethoxy, trifluoromethoxy, trifluoroethoxy and cyclopropyl, R1 and R2 more particularly preferably, independently of each other, represent hydrogen, methyl, ethyl, propyl, butyl, sec-butyl, isopropyl, tert-butyl, (2,2,2)-trifluoroethyl, (2,2)-difluoromethyl, methoxy, ethoxy, cyanomethyl, methoxymethyl, methoxyethyl, allyl, butenyl, propynyl, methylcarbonyl, ethylcarbonyl, propylcarbonyl, isopropylcarbonyl, methoxycarbonyl, ethoxycarbonyl, represents arylcarbonyl, pyridylcarbonyl, pyrimidylcarbonyl, thiazolylcarbonyl, pyrazolylcarbonyl, methylsulfinyl, trifluoromethylsulfinyl, methylsulfonyl, trifluoromethyl lsulfonyl optionally monosubstituted or disubstituted independently of one another by fluorine, chlorine, bromine, cyano, nitro, methyl, trifluoromethyl, allyl, butenyl, methoxy, trifluoromethoxy, methylthio, methylsulfinyl, methylsulfonyl, methylamino, dimethylamino, or represents a 3 to 6 ring membered, saturated or aromatic which may optionally contain one or two heteroatoms from the group consisting of O, S and N, which may optionally be interrupted once, twice or three times by C=O and which may optionally be monosubstituted or trisubstituted by identical or identical substituents other than the group consisting of fluorine, chlorine, bromine, iodine, cyano, nitro, methyl, ethyl, trifluoromethyl, vinyl, ethynyl, methoxy, ethoxy, difluoromethoxy, trifluoromethoxy, trifluoroethoxy and cyclopropyl, the following rings are explicitly mentioned: cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, oxetane, phenyl, thienyl and pyridyl which may be optionally substituted by the substituents referred to as further particularly preferred, or represent -(CH2)m-R6, -O-(CH2)m-R6, -(CH2)mO-R6, wherein R6 represents a 3- to 6-membered, saturated, partially saturated or aromatic ring which may optionally contain one or three heteroatoms from the group consisting of O, S and N, which may optionally be interrupted once or twice by C=O and which may optionally be mono- or tri-substituted by identical or different substituents from the group consisting of fluorine, chlorine , bromine, iodine, cyano, nitro, methyl, ethyl, trifluoromethyl, vinyl, ethynyl, methoxy, ethoxy, difluoromethoxy, trifluoromethoxy, trifluoroethoxy and cyclopropyl, where m represents the number 1, the following R6 are explicitly mentioned: cyclopropyl, phenyl, pyridyl and pyridyl which may be optionally substituted by the substituents referred to as more particularly preferred or R1 and R2 together with the atoms to which they are attached may form a 4- to 8-membered saturated or unsaturated ring, which may be optional. optionally mono- or tetra-substituted by methyl, ethyl, methoxy, ethoxy, fluorine, chlorine, bromine, trifluoromethyl, difluoromethyl which may optionally contain one or two additional heteroatoms from the group consisting of sulfur and nitrogen, (where the oxygen atoms do not have to be immediately adjacent) and/or at least one CH2 group is replaced by a carbonyl group, especially the following rings are specifically explicitly mentioned: where the nitrogen atom to which R1 and R2 are attached represent the cycle and the arrow points to the rest of the molecule, which may be optionally mono- or di-substituted by methyl, ethyl, methoxy, ethoxy, fluorine, chlorine, bromine, trifluoromethyl, difluoromethyl.
em que o átomo de nitrogênio ao qual R1 e R2 estão ligados representam o ciclo e a seta aponta para o resto da molécula, que podem ser opcionalmente monossubstituídos ou dissubstituídos por metil, etil, metoxi, etoxi, flúor, cloro, bromo, trifluorometil, difluorometil. R1 e R3 conjuntamente com os átomos aos quais estão ligados podem formar um anel de 5 a 6 membros, saturado ou insaturado e/ou um que é opcionalmente monossubstituído ou dissubstituído por metil, etil, metoxi, etoxi, flúor, cloro, trifluorometil, difluorometil, ciano, ciclopropil, clorociclopropil, fluorociclopropil, cianociclopropil, metilciclopropil, alcanodiila-(C3-C4), alcenodiila-(C3-C4), butanodienila (em que a butanodienila pode ser opcionalmente monossubstituído ou dissubstituído por metil, flúor, cloro, bromo, metoxi ou trifluorometil e/ou pode ser opcionalmente interrompido por melo menos um átomo de oxigênio e/ou nitrogênio) e pode conter opcionalmente mais um átomo de enxofre ou oxigênio ou nitrogênio e/ou pelo menos um grupo carbonila, em especial R1 e R3 conjuntamente com os átomos aos quais estão ligados representam o seguinte grupo, monossubstituído ou dissubstituído por metil, etil, metoxi, etoxi, flúor, cloro, trifluorometil, difluorometil, ciclopropil, clorociclopropil, fluorociclopropil, cianociclopropil, metilciclopropil, em que a seta aponta para o resto da molécula.[00014] Formula (I) provides a general definition of the compounds according to the invention. Also very particularly preferred substituents or ranges of the radicals indicated in the Formulas given above and below are defined, n very particularly preferably represents the number 0 or 1, X1 and X3 very particularly preferably represent hydrogen. X2 and X4 very particularly preferably represent the following combinations X2/X4: vinyl/H, H/vinyl, ethynyl/H, H/ethynyl, methoxy/H, H/methoxy, ethoxy/H, H/ethoxy, aminothiocarbonyl/ H, H/aminothiocarbonyl, vinyl/methyl, methyl/vinyl, ethynyl/methyl, methyl/ethynyl, methoxy/methyl, methyl/methoxy, ethoxy/methyl, methyl/ethoxy, aminothiocarbonyl/methyl, methyl/aminothiocarbonyl, vinyl/F, F/vinyl, ethynyl/F, F/ethynyl, methoxy/F, F/methoxy, ethoxy/F, F/ethoxy, aminothiocarbonyl/F, F/aminothiocarbonyl, vinyl/Cl, Cl/vinyl, ethynyl/Cl, Cl/ ethynyl, methoxy/Cl, Cl/methoxy, ethoxy/Cl, Cl/ethoxy, aminothiocarbonyl/Cl, Cl/aminothiocarbonyl, or phenylmethyl, phenoxy, pyridylmethyl, pyrimidylmethyl, thiazolylmethyl, pyrazolylmethyl, pyridyloxy, pyrimidyloxy, thiazolyloxy, pyrazolyloxy, cyclopropylmethyl, cyclopropylmethoxy or optionally mono- or di-substituted by identical or different substituents from the group consisting of fluorine, chlorine, bromine, cyano, nitro, methyl, ethyl, trifluoromethyl, difluoromethyl. 1, methoxy, trifluoromethoxy, difluoromethoxy or cyclopropyl, or represents (C3-C6)-cycloalkyl, phenyl, pyridyl, pyrimidyl, pyridazinyl, pyrazinyl, triazinyl, thiazolyl, thiadiazolyl, oxazolyl, oxadiazolyl, pyrazolyl, triazolyl or tetrazolyl which is optionally monosubstituted disubstituted by identical or different substituents from the group consisting of fluorine, chlorine, bromine, cyano, nitro, methyl, ethyl, trifluoromethyl, difluoromethyl, methoxy, trifluoromethoxy, difluoromethoxy or cyclopropyl, R3 more particularly preferably hydrogen, ethyl, propyl, cyano, trifluoromethyl, difluoromethyl, dichloromethyl, chloromethyl, trichloromethyl, difluorochloromethyl, dichlorofluoromethyl, (2,2,2)-trifluoroethyl, 2-chloro-(2,2)-difluoroethyl, (2,2)-dichloro-2-fluoroethyl, (2,2) ,2,2)-trichloroethyl, pentafluoroethyl, methoxymethyl, cyanomethyl, allyl, butenyl, or represents a 3 to 6 membered, saturated, partially saturated or aromatic ring which may optionally contain one or three heteroatoms of the grain. pos consisting of O, S and N and which may be optionally monosubstituted or disubstituted by identical or different substituents from the group consisting of fluorine, chlorine, bromine, iodine, cyano, nitro, methyl, ethyl, trifluoromethyl, vinyl, ethynyl, methoxy, ethoxy , difluoromethoxy, trifluoromethoxy, trifluoroethoxy and cyclopropyl, the following rings are explicitly mentioned: cyclopropyl, phenyl, pyridyl, pyrimidyl, thiazolyl, pyrazolyl and thienyl which may be optionally substituted by the substituents referred to as more particularly preferred, R1 and R2 more particularly preferred , independently of one another, represents hydrogen, methyl, ethyl, propyl, butyl, sec-butyl, isopropyl, tert-butyl, (2,2,2)-trifluoroethyl, (2,2)-difluoromethyl, methoxy, ethoxy, cyanomethyl , methoxymethyl, methoxyethyl, allyl, butenyl, propynyl, methylcarbonyl, ethylcarbonyl, propylcarbonyl, isopropylcarbonyl, methoxycarbonyl, ethoxycarbonyl, represents arylcarbonyl, pyridylcarbonyl, pyrimidi 1carbonyl, thiazolylcarbonyl, pyrazolylcarbonyl, methylsulfinyl, trifluoromethylsulfinyl, methylsulfonyl, trifluoromethylsulfonyl optionally monosubstituted or disubstituted independently of one another by fluorine, chlorine, bromine, cyano, nitro, methyl, trifluoromethyl, allyl, butenyl, methoxy, trifluoromethylsulfonyl, trifluoromethylsulfonyl methylamino, dimethylamino, or represents a 3- to 6-membered, saturated or aromatic ring which may optionally contain one or two heteroatoms from the group consisting of O, S and N, which may optionally be interrupted once, twice or three times by C=O and which may be optionally mono- or tri-substituted by identical or different substituents from the group consisting of fluorine, chlorine, bromine, iodine, cyano, nitro, methyl, ethyl, trifluoromethyl, vinyl, ethynyl, methoxy, ethoxy, difluoromethoxy, trifluoromethoxy, trifluoroethoxy and cyclopropyl , the following rings are explicitly referred to: cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl lo, oxetane, phenyl, thienyl and pyridyl which may be optionally substituted by the substituents referred to as more particularly preferred, or represent -(CH2)m-R6, -O-(CH2)m-R6, -(CH2)mO-R6, wherein R6 represents a 3- to 6-membered, saturated, partially saturated or aromatic ring which may optionally contain one or three heteroatoms from the group consisting of O, S and N, which may optionally be interrupted once or twice by C=O and which may be optionally mono- or tri-substituted by identical or different substituents from the group consisting of fluorine, chlorine, bromine, iodine, cyano, nitro, methyl, ethyl, trifluoromethyl, vinyl, ethynyl, methoxy, ethoxy, difluoromethoxy, trifluoromethoxy, trifluoroethoxy and cyclopropyl, wherein m represents the number 1, the following R6 are explicitly referred to: cyclopropyl, phenyl, pyridyl and pyridyl which may be optionally substituted by the substituents referred to as more particularly preferred or R1 and R2 together with the atoms to which they are attached they can form a 4- to 8-membered, saturated or unsaturated ring, which may optionally be mono- or tetra-substituted by methyl, ethyl, methoxy, ethoxy, fluorine, chlorine, bromine, trifluoromethyl, difluoromethyl which may optionally contain one or two additional heteroatoms from the group consisting of sulfur and nitrogen, (wherein the oxygen atoms do not have to be immediately adjacent) and/or at least one CH2 group is replaced by a carbonyl group, especially the following rings are specifically mentioned explicitly : where the nitrogen atom to which R1 and R2 are attached represent the cycle and the arrow points to the rest of the molecule, which may be optionally mono- or di-substituted by methyl, ethyl, methoxy, ethoxy, fluorine, chlorine, bromine, trifluoromethyl, difluoromethyl. R1 and R3 together with the atoms to which they are attached can form a 5- to 6-membered, saturated or unsaturated ring and/or one that is optionally mono- or di-substituted by methyl, ethyl, methoxy, ethoxy, fluorine, chlorine, trifluoromethyl, difluoromethyl , cyano, cyclopropyl, chlorocyclopropyl, fluorocyclopropyl, cyanocyclopropyl, methylcyclopropyl, (C3-C4)-alkandiyl, (C3-C4)-alkenediyl, butanedienyl (wherein butanedienyl may be optionally monosubstituted or disubstituted by methyl, fluorine, chlorine, bromine, methoxy or trifluoromethyl and/or may optionally be interrupted by at least one oxygen and/or nitrogen atom) and may optionally contain one more sulfur or oxygen or nitrogen atom and/or at least one carbonyl group, in particular R1 and R3 together with the atoms to which they are attached represent the following group, monosubstituted or disubstituted by methyl, ethyl, methoxy, ethoxy, fluorine, chlorine, trifluoromethyl, difluoromethyl, cyclopropyl, chlorocycloprop il, fluorocyclopropyl, cyanocyclopropyl, methylcyclopropyl, where the arrow points to the rest of the molecule.
cada um dos quais pode ser opcionalmente monossubstituído ou dissubstituído por metil, etil, metoxi, etoxi, flúor, cloro, trifluorometil, difluorometil, ciclopropil, clorociclopropil, fluorociclopropil, cianociclopropil, metilciclopropil, em que a seta aponta para o resto da molécula. R2 de modo mais particularmente preferido representa ciano, (2,2,2)-trifluoroetil, (2,2)-difluorometil, 2-cloro-(2,2)-difluoroetil, (2,2)- dicloro-2-fluoroetil, (2,2,2)-tricloroetil, pentafluoroetil, 2- clorotetrafluoroetil, alila, butenila, propinila, metilsulfinila, trifluorometilsulfinila, metilsulfonil, trifluorometilsulfonil, ou representa um anel de 3 a 6 membros, saturado ou aromático que pode conter opcionalmente um ou dois heteroátomos do grupos constituído por O, S e N, que pode ser opcionalmente interrompido uma, duas ou três vezes por C=O e que pode ser opcionalmente monossubstituído ou trissubstituído por substituintes idênticos ou diferentes do grupo constituído por flúor, cloro, bromo, iodo, ciano, nitro, metil, etil, trifluorometil, vinila, etinila, metoxi, etoxi, difluorometoxi, trifluorometoxi, trifluoroetoxi e ciclopropil, são explicitamente referidos os seguintes anéis: ciclopropil, ciclobutil, ciclopentilo, ciclohexilo, oxetano, fenila, tienila e piridila que podem ser opcionalmente substituídos pelos substituintes referidos como mais particularmente preferidos, ou representam -(CH2)m-R6, -O-(CH2)m-R6, -(CH2)m-O-R6, em que R6 representa um anel de 3 a 6 membros, saturado, parcialmente saturado ou aromático que pode conter opcionalmente um ou três heteroátomos do grupos constituído por O, S e N, que pode ser opcionalmente interrompido uma ou duas vezes por C=O e que pode ser opcionalmente monossubstituído ou trissubstituído por substituintes idênticos ou diferentes do grupo constituído por flúor, cloro, bromo, iodo, ciano, nitro, metil, etil, trifluorometil, vinila, etinila, metoxi, etoxi, difluorometoxi, trifluorometoxi, trifluoroetoxi e ciclopropil, em que m representa o número 1, são explicitamente referidos os seguintes R6: ciclopropil, ciclobutil, ciclopentilo, ciclohexilo, fenila, piridila e piridila que podem ser opcionalmente substituídos pelos substituintes referidos como mais particularmente preferidos, As definições referidas de radicais, gerais ou preferidas, ou as ilustrações apresentadas podem ser combinadas facultativamente entre si, isto é, incluindo combinações entre os respectivos intervalos e intervalos preferidos. São aplicadas aos produtos finais e, assim, a precursores e intermediários.[00015] Formula (I) provides a general definition of the compounds according to the invention. Also very particularly preferred substituents or ranges of the radicals indicated in the Formulas given above and below are defined, n very particularly preferably represents the number 0 or 1, X1 and X3 very particularly preferably represent hydrogen. X2 and X4 independently of one another, particularly preferably hydrogen, fluorine, chlorine, bromine, methyl, ethyl, trifluoromethyl, difluoromethyl, vinyl, ethynyl, methoxy, ethoxy, difluoromethoxy, trifluoromethoxy, OCH2CF3, aminothiocarbonyl, or phenylmethyl, phenoxy, pyridylmethyl, pyrimidylmethyl, thiazolylmethyl, pyrazolylmethyl, pyridyloxy, pyrimidyloxy, thiazolyloxy, pyrazolyloxy, cyclopropylmethyl, cyclopropylmethoxy or optionally monosubstituted or disubstituted by identical or different substituents from the group consisting of fluorine, chlorine, bromine, cyano, nitro, methyl, difluoromethyl, trifluoromethyl , methoxy, trifluoromethoxy, difluoromethoxy or cyclopropyl, or represents (C3-C6)-cycloalkyl, phenyl, pyridyl, pyrimidyl, pyridazinyl, pyrazinyl, triazinyl, thiazolyl, thiadiazolyl, oxazolyl, oxadiazolyl, pyrazolyl, triazolyl or tetrazolyl which is optionally disubstituted or monosubstituted by identical or different substituents from the group consisting of f fluorine, chlorine, bromine, cyano, nitro, methyl, ethyl, trifluoromethyl, difluoromethyl, methoxy, trifluoromethoxy, difluoromethoxy or cyclopropyl, with special preference X2 and X4 represent the following combinations X2/X4: F/F, Cl/Cl, F/ Cl, Cl/F, Br/Br, Br/Cl, Cl/Br, Br/F, F/Br, methyl/methyl, methyl/F, F/methyl, methyl/Cl, Cl/methyl, methyl/Br, Br/methyl, ethyl/ethyl, ethyl/F, F/ethyl, ethyl/Cl, Cl/ethyl, ethyl/Br, Br/ethyl, methoxy/methyl, methyl/methoxy, methyl/H, ethyl/H, chlorine/ H, bromine/H, fluorine/H, methoxy/H, H/chlorine, H/fluorine, H/bromine, H/methyl, H/methoxy, H/ethyl R1 and R3 together with the atoms to which they are attached can form a 5 to 6 membered ring, saturated or unsaturated and/or one that is optionally mono- or di-substituted by methyl, ethyl, methoxy, ethoxy, fluorine, chlorine, trifluoromethyl, difluoromethyl, cyano, cyclopropyl, chlorocyclopropyl, fluorocyclopropyl, cyanocyclopropyl, methylcyclopropyl, (C3-C4)-alkanediyl, (C3-C4)-alkenediyl, butanedienyl (wherein butanedienyl may optionally be monos. substituted or disubstituted by methyl, fluorine, chlorine, bromine, methoxy or trifluoromethyl and/or may optionally be interrupted by at least one oxygen and/or nitrogen atom) and may optionally contain one more sulfur or oxygen or nitrogen atom and/or at least one carbonyl group, especially R1 and R3 together with the atoms to which they are attached represent the following group, each of which may optionally be mono- or di-substituted by methyl, ethyl, methoxy, ethoxy, fluorine, chlorine, trifluoromethyl, difluoromethyl, cyclopropyl, chlorocyclopropyl, fluorocyclopropyl, cyanocyclopropyl, methylcyclopropyl, where the arrow points to the rest of the molecule. R 2 more particularly preferably represents cyano, (2,2,2)-trifluoroethyl, (2,2)-difluoromethyl, 2-chloro-(2,2)-difluoroethyl, (2,2)-dichloro-2-fluoroethyl , (2,2,2)-trichloroethyl, pentafluoroethyl, 2-chlorotetrafluoroethyl, allyl, butenyl, propynyl, methylsulfinyl, trifluoromethylsulfinyl, methylsulfonyl, trifluoromethylsulfonyl, or represents a 3 to 6 membered, saturated or aromatic ring which may optionally contain one or two heteroatoms from the group consisting of O, S and N, which may optionally be interrupted once, twice or three times by C=O and which may optionally be mono- or tri-substituted by identical or different substituents from the group consisting of fluorine, chlorine, bromine, iodine, cyano, nitro, methyl, ethyl, trifluoromethyl, vinyl, ethynyl, methoxy, ethoxy, difluoromethoxy, trifluoromethoxy, trifluoroethoxy and cyclopropyl, the following rings are explicitly referred to: cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, oxetane, phenyl, thienyl and pyridyl that can be optionally substituted by the substituents referred to as more particularly preferred, or represent -(CH2)m-R6, -O-(CH2)m-R6, -(CH2)mO-R6, wherein R6 represents a 3- to 6-membered ring , saturated, partially saturated or aromatic which may optionally contain one or three heteroatoms from the group consisting of O, S and N, which may optionally be interrupted once or twice by C=O and which may optionally be monosubstituted or trisubstituted by identical or identical substituents. other than the group consisting of fluorine, chlorine, bromine, iodine, cyano, nitro, methyl, ethyl, trifluoromethyl, vinyl, ethynyl, methoxy, ethoxy, difluoromethoxy, trifluoromethoxy, trifluoroethoxy and cyclopropyl, where m represents the number 1, are explicitly mentioned the following R6: cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, phenyl, pyridyl and pyridyl which may be optionally substituted by the substituents referred to as more particularly preferred. s, general or preferred, or the illustrations shown may optionally be combined with each other, i.e., including combinations between respective ranges and preferred ranges. They are applied to final products and thus to precursors and intermediates.
[00016] According to the invention, preference is given to those compounds of Formula (I) which contain a combination of the meanings listed above as being preferred (preferred).
[00017] According to the invention, particular preference is given to the compounds of Formula (I) which contain a combination of the meanings listed above as being particularly preferred.
[00018] According to the invention, very particular preference is given to the compounds of the Formula (I) which contain a combination of the meanings enumerated above as being very particularly preferred.
[00019] Saturated or unsaturated hydrocarbon radicals, such as alkyl, alkanediyl or alkenyl, in each case may be straight-chained or branched as far as possible, including in combination with heteroatoms, for example, in alkoxy.
[00020] Unless otherwise indicated, optionally substituted radicals can be monosubstituted or polysubstituted, and may, in the case of polysubstitution, have identical or different substituents.
[00021] In the definitions of the radicals referred to as being preferred, halogen represents fluorine, chlorine, bromine and iodine, with particular preference for fluorine, chlorine and bromine and with very particular preference for fluorine and chlorine. Preparation processes
[00022] The compounds of General Formula (I) can be prepared by the methods described in patent application WO 2007/131680. As an alternative to the methods described, the compounds of Formula (I) may also be prepared by process A, process B, process C, process E, process F, process G, process H, process I, process J and process K. The process D provides an alternative for preparing the precursors.
[00023] Various processes for the preparation of amidines are described in S. Patai and Z. Rappoport, The Chemistry of Amidines and Imidates, Vol. 27, John Wiley & Sons, New York, NY, USA, 1991.
[00024] The palladium(II) catalyzed synthesis of arylamiidines with the help of trifluoroborates is also described in the literature, see for example J.Savmarker, Ph.D. thesis of the University of Uppsala, 2012 or J.Savmarker, Org. Lett. 14 (2012), 2394-2397. Process A
[00025] Where X1, X2, X3, X4, R1, R2 and R3 have the meanings indicated above, AG represents a leaving group and PG represents a protecting group.
[00026] Anilines of Formula (VII) are either available for sale or can be prepared by known methods. In the presence of acids, acid anhydrides or acid chlorides of Formula (VIII), the anilines (VII) are converted to the corresponding anilides (VI). Chlorosulfonation of the anilides (VI) with chlorosulfonic acid produces the corresponding sulfonyl chlorides (V). The reduction of sulfonyl chlorides (V) to disulphides (IV) can be carried out by methods known from the literature, such as iron in hydrochloric acid or iodide. Reaction of the disulfides (IV) with trifluoroethyl electrophiles of Formula (XVI), where AG represents a leaving group, such as, for example, chloro-, bromine, tosylate, mesylate or triflate, yields the sulfides (III).
The anilides (III) are chlorinated, for example with diphenyl chlorophosphate or phosphorus pentachloride, to produce imidoyl chlorides of Formula (II) and are reacted with amines to give amidines (Ia).
[00028] The thioethers (Ia) are converted into the corresponding sulfoxides (Ib) by reaction with oxidizing agents such as, for example, meta-chloroperbenzoic acid.
[00029] The oxidation of compounds of Formula (Ia) to compounds of Formula (Ib) can be carried out using an oxidizing agent in a suitable solvent and diluent. Suitable oxidizing agents are, for example, dilute nitric acid, hydrogen peroxide and peroxycarboxylic acids such as meta-chloroperbenzoic acid. Suitable solvents are inert organic solvents, typically acetonitrile and halogenated solvents such as dichloromethane, chloroform or dichloroethane.
[00030] A large number of different methods are suitable for generating enantiomerically enriched sulfoxides as described by AR Maguire in ARKIVOC, 2011(i), 1-110 or by WO2011/006646: meta-catalyzed asymmetric oxidations of thioethers, for example with titanium and vanadium as the most frequently used catalyst sources, in the form of Ti(OiPr4) and VO(acac)2, together with a chiral ligand and an oxidizing agent, such as tert.butyl hydroperoxide (TBHP), hydroperoxide 2-phenylpropane-2-yl -(CHP) or hydrogen peroxide, asymmetric oxidations catalyzed by non-metals employing chiral oxidizing agents or chiral catalysts; asymmetric electrochemical or biological oxidations and also the kinetic resolution of sulfoxides and nucleophilic displacement (according to the Andersen method).
[00031] Enantiomers can also be obtained from the racemate, for example by separating them on a preparative scale by chiral HPLC.
[00032] The compounds of Formulas (II), (III), (IV) and (V) in process A can be prepared particularly under the conditions referred to in the preparation examples.
[00033] Alternatively, the thioethers of Formula (III) can be prepared by process B. Process B
[00034] Where X1, X2, X3, X4 and R3 have the meanings indicated above, AG represents a leaving group and PG represents a protecting group.
[00035] Anilines (VII) can be protected with a suitable protecting group known from the literature, such as, for example, an acetyl group to produce compounds of Formula (XVI). Chlorosulfonation of compounds of Formula (XVI) with chlorosulfonic acid produces the corresponding sulfonyl chlorides (XV). The reduction of sulfonyl chlorides (XV) to disulphides (XIV) can be carried out by methods known from the literature, such as iron in hydrochloric acid or iodide. Reaction of the disulfides (XIV) with trifluoroethyl electrophiles of Formula (IX), where AG represents a leaving group, such as, for example, chloro-, bromine, tosylate, mesylate or triflate, yields the sulfides (XIII). The protecting group is removed by suitable methods, known from the literature, producing anilines of Formula (X). The latter are converted in the presence of acids, acid anhydrides or acid chlorides of the Formula (VIII) to the corresponding anilides (VI).
[00036] Instead of the reduction to disulfide (XIV), it is also possible to reduce with a suitable reducing agent, such as, for example, iodine/phosphorus to produce the alkyl thioate (XI), which is then deprotected using a suitable method, for example with potassium hydroxide solution, to yield compounds of Formula (X). Reaction of thiols (XI) with trifluoroethyl electrophiles of Formula (IX) where AG represents a leaving group, such as, for example, chlorine, bromine, tosylate, mesylate or triflate yields the sulfides (X). The latter are converted in the presence of acids, acid anhydrides or acid chlorides of the Formula (VIII) to the corresponding anilides (III).
Onde X1, X2, X3, X4, R1, R2 e R3 possuem os significados indicados acima.[00037] The compounds of the Formulas (III), (X), (XI), (XII), (XV) and (XVI) in process B can be prepared particularly under the conditions referred to in the preparation examples. Where X1, X2, X3, X4, R1, R2 and R3 have the meanings given above.
[00038] Furthermore it was found that the chiral compounds (Ib) are obtained by process C when the compounds of the Formula (III) are chirally oxidized into sulfoxides of the Formula (XVII).
[00039] The anilides (XVII) are chlorinated, for example with diphenyl chlorophosphate or phosphorus pentachloride, to produce imidoyl chlorides of the Formula (XVIII) and are reacted with amines to give amidines (Ib).
[00040] Some of the compounds of Formula (XVII) in process C are new and can be prepared particularly under the conditions referred to in the preparation examples. Process D
[00041] Alternatively, the thioethers of Formula (X) can be prepared by process D.
[00042] X2, X4 independently of one another represent with particular preference hydrogen, fluorine, chlorine, bromine.
[00043] Chlorosulfonation of the nitroaromatic compounds of Formula (XIX) with chlorosulfonic acid produces the corresponding sulfonyl chlorides (XX). The reduction of the sulfonyl chlorides (XX) to bis(nitroaryl) disulphides (XXI) can be carried out by methods known from the literature, for example iodide. The reduction of disulfides (XXI) to disulfanediyldianilines (XXII), some of which are formed as a mixture with the corresponding aminoarylthiols (XI), is possible using reducing agents such as, for example, hydrogen with the help of heterogeneous catalysts, such as , for example, Raney nickel, platinum or activated carbon or palladium on activated carbon. Reaction of disulfides (XXII) or thiophenols (XI) with trifluoroethyl electrophiles of Formula (IX) whenever AG represents a leaving group, such as, for example, chlorine, bromine, iodine, tosylate, mesylate or triflate, yields the 3 -[(2,2,2-trifluoroethyl)sulfanyl]anilines of Formula (X).
[00044] The compounds of the Formulas (X), (XI), (XII), (XX) and (XXI) in process D can be prepared particularly under the conditions referred to in the preparation examples.
[00045] Where X1, X2, X3, X4, R1, R2 and R3 have the meanings given above.
[00046] Anilines of Formula (X) can be converted to trifluoroethyl sulfide derivatives of Formula (Ia) by methods known in the literature, for example by reaction with amides of Formula (XXIV) and phosphoryl chloride, if appropriate in the presence of an inert organic solvent.
[00047] The sulfoxides (Ib) can be obtained through oxidation of the trioethers (Ia) through methods known in the literature.
(Ia-a) (Ia-b)[00048] When reacted with anilines of Formula (X) in the presence of phosphoryl chloride, amides of Formula (XXIV), wherein R3 represents optionally substituted cyclopropyl and R1 represents hydrogen and R2 represents optionally substituted haloalkyl, yield a mixture of N-arylamidines according to the invention, of the general formulas (Ia-a) and (Ia-b). (Ia-a) (Ia-b)
[00049] Where X1, X2, X3, X4 and R2 have the meanings given above.
[00050] The oxidation of the trioethers (Ia-a) by methods known from the literature produces sulfoxides of the Formula (Ib) in which R3 represents optionally substituted cyclopropyl and R1 represents hydrogen and R2 represents optionally substituted haloalkyl,
[00051] Oxidation of the trioethers (Ia-b) by methods known from the literature produces sulfoxides of Formula (Ib) wherein R1 and R3 together form a 5-membered ring and R2 represents optionally substituted haloalkyl.
[00052] The amides of the Formula (XXIV) are available for sale or can be prepared by processes known in general, for example by reacting acid chlorides with amines, optionally in the presence of bases and optionally in the presence of a solvent, for example analogously to Houben-Weyl VIII, 655.
[00053] The compounds of Formulas (X) and (XXIV) in process E can be prepared particularly under the conditions referred to in the preparation examples. Process F
[00054] The 3-substituted 2-arylamino-1,3-thiazolidines (n=0, A=S), 2-arylimino-1,3-thiazinanes (n=1, A=S), 2-arylimino-1 ,3-oxazolidines (n=0, A=O) and 2-arylimino-1,3-oxazinanes (n=1, A=O) of the General Formula (I) can be prepared, for example, by process F
[00055] Where X1, X2, X3, X4 and R2 have the meanings given above.
[00056] Anilines of Formula (X) can be reacted directly by reaction with isocyanates (XXV, A=O) or isothiocyanates (XXV, A=S) to produce the cyclic amidines of Formula (Ia-c). In the case of isolation of the intermediate of the (thio)ureas of Formula (XXVI), it can be converted in the presence of bases to the cyclic amidines of Formula (Ia-c).
[00057] In patent JP2011/042611, (thio)ureas and their sulfoxides are claimed as acaricides. The (thio)ureas of Formula (XXVI) are new and also form part of the subject of the invention.
[00058] The sulfoxides (Ib-c) can be obtained through oxidation of the trioethers (Ia-c) through methods known in the literature.
[00059] The thioethers (Ia-c) and the sulfoxides (Ib-c) can then be converted by methods known from the literature into the compounds of Formula Gerale (Ia-d) and (Ib-d), respectively where R2 may have the meanings indicated above. Suitable alkylating agents are, for example, alkyl halides (alkyl chlorides, alkyl bromides and alkyl iodides), alkyl triflates, alkyl mesylates and dialkyl sulfates.
[00060] The sulfoxides of Formula (Ib) can be obtained by oxidizing the thioethers of Formula (Ia) by methods known in the literature.
[00061] The compounds of Formulas (X) and (XXVI) in process F can be prepared in particular under the conditions referred to in the preparation examples. Process G
[00062] The 3-substituted 2-arylamino-1,3-oxazoles of the General Formula (I) can be prepared, for example, by process G
[00063] Where X1, X2, X3, X4 and R2 have the meanings given above.
[00064] R7 and R8 are substituents on the ring formed by R1 and R3 together with the atoms to which they are attached.
[00065] Anilines of Formula (XXVIII) can be prepared by oxidizing anilines of Formula (X), for example with meta-chlorobenzoic acid as an oxidizing agent in an inert organic solvent. The anilines of Formula (XXVIII) are new and also form part of the object of the invention.
[00066] Anilines of Formulas (X) and (XXVIII) can be converted into ureas of Formulas (XVII) and (XXIX) respectively, by methods known in the literature, for example according to JP2011/042611 by treating these with isocyanates, optionally in the presence of a base and optionally in the presence of an organic solvent. Alternatively, these amines can be converted by generally known methods into the respective isocyanates, which are then converted with the amines into the ureas.
[00067] The 3-substituted 2-aryliminooxazoles (Ia-e) and (Ib-e) can be synthesized from ureas (XXVII) and (XXIX), respectively, for example by the method of M. Han in Bull. Korean Chem. Soc. 2012, 33(4), 1371-1374, wherein initially, using carbon tetrachloride and triphenylphosphine, an N'-substituted N-arylimidoformamide is prepared which is then reacted with a suitable hydroxycarbonyl compound under Ku( I) in an inert, high boiling solvent to selectively yield 2-arylaminooxazole.
[00068] The sulfoxides (Ib) can be obtained through oxidation of the trioether (Ia) through methods known in the literature.
[00069] These 2-aryliminooxazoles (I) can also be synthesized directly from the anilines of the Formula (X) or (XXVIII), for example by reaction with 3-alkyl-1,3-oxazolinothiones of the Formula (J) or oxazolium salts thereof, optionally in the presence of a base and optionally in an inert solvent, generally at high temperatures, as described by Gompper in Chem. Ber. 1959, 92, 1928-1932.
[00070] 3-Substituted 1,3-oxazolinothiones of Formula (J) can be obtained from commercial sources or can be prepared by methods known in the literature, for example from dicarbonyl compounds of Formula (G), via synthesis of intermediates (H), analogously to the procedures of KN Mehrotra in Bull. Chem. Society of Japan 1985, 58 (8), 2399-2402 for R7=R8=aryl, using carbon disulfide as the sulfur source.
[00071] Formula (K) oxazolium salts can be prepared by alkylation of Formula (J) oxazolinothiones. Suitable alkylating agents are, for example, alkyl halides (alkyl chlorides, alkyl bromides and alkyl iodides), alkyl triflates, alkyl mesylates and dialkyl sulfates. The nature of the anion X of General Formula (K) is determined by this agent and may be, for example, chlorine, bromine, iodine, triflate, mesylate or sulfate.
The compounds of the Formulas (X) and (XXVIII) in process G can be prepared in particular under the conditions referred to in the preparation examples. Process H
[00073] The 3-substituted 2-arylaminothiadiazoles of the General Formula (I) can be prepared, for example, by process H
[00074] Where X1, X2, X3, X4 and R2 have the meanings given above.
[00075] R7 is the substituent on the ring formed by R1 and R3 together with the atoms to which they are attached.
[00076] The anilines of the General Formula (X) of the General Formula (XXVIII) can be reacted, for example with the thiadiazolinethiones of the Formula (XXX) or with the corresponding thiadiazolium salts of the Formula (XXXI) to produce the 2-aryliminothiadiazoles of Formula (Ia-f) and (Ib-f) respectively. This reaction optionally takes place in the presence of a base, optionally in an inert solvent or in an agent which can simultaneously serve as a base and a solvent, for example pyridine.
[00077] The synthesis of the thiadiazolinethiones of the Formula (XXX) and their thiadiazolium salts (XXXI) can be carried out, for example, through the following process:
[00078] The synthesis of N-substituted amidoximes of Formula (XXXIV) has been described in detail in the literature. It can take place, for example, according to J. Org. Chem. 1980, 45 (21), 4198 from the corresponding imidoyl chlorides of Formula (XXXIII) by reaction with the desired amines. Optionally, this operation takes place in an inert solvent, at temperatures between 0 °C and 100 °C, with reaction times from 1 h to 36 h. For the preparation of imidoyl chlorides, it is possible to apply processes known from the literature, for example, the reaction of the appropriate nitro compounds of Formula (XXXII) with alkoxylates, optionally in the corresponding alcohol as solvent, followed by addition of a chlorinating agent, by example, titanium tetrachloride,
[00079] The literature presents a number of methods of synthesis of the oxadiazolinethiones of the Formula (XXXV) for example, the reaction of 1,2,4-oxadiazolin-5-ones with phosphorus pentasulfide, described by D. Sümengen in J. Chem . Soc. Perkin Trans 1 1983, 4, 687-691. The requisite 1,2,4-oxadiazolin-5-ones are commercially available or can be obtained from N-substituted amidoximes (XXXIV) by reaction with a suitable halocarbonyl derivative as described by H. Argibas in Phosp., Sulf., Silicon and rel. elem. 1998, 134/135, 381319. Alternatively, oxadiazolinethiones can be directly obtained from N-substituted amidoximes of Formula (XXXIV), for example, by reaction with thiophosgene, also published by D. Sümengen.
[00080] For the synthesis of the thiadiazolinones of the Formula (XXXVI) of the oxadiazolinethiones of the Formula (XXXV), it is possible to employ the method of D. Sümengen in J. Chem. Soc. Perkin Trans 1 1983, 4, 687-691: is a rearrangement of 3,4-disubstituted 1,2,4-oxadiazoline-5-thiones with copper catalysis in an inert solvent of high boiling point at elevated temperature.
[00081] Thiadiazolinothiones of Formula (XXX) can be prepared, for example, from thiadiazolinones of Formula (XXXVI) by treatment with sulfating agents, such as, for example, phosphorus pentasulfide or Lawesson's reagent, optionally in an inert solvent at temperatures above 140 °C.
[00082] Thiadiazolium salts of Formula (XXXI) can be prepared by methods known from the literature, by alkylation of thiadiazolinothiones of Formula (XXX). Suitable alkylating agents are, for example, alkyl halides (alkyl chlorides, alkyl bromides and alkyl iodides), alkyl triflates, alkyl mesylates and dialkyl sulfates.
[00083] The compounds of Formula (XXVIII) in process H can be prepared in particular under the conditions referred to in the preparation examples. Process I
[00084] The 2-arylimino-1-3-oxazolidin-4-ones (A=O, n=0), 2-arylimino-1-3-oxazinan-4-ones (A=O, n=1), 2-arylimino-1,3-thiazolidin-4-ones (A=S, n=0) and 3-substituted 2-arylimino-1,3-thiazinan-4-ones (A=S, n=1) of the Formula General (I) can be prepared, for example, by process I.
[00085] Where X1, X2, X3, X4 and R2 have the meanings indicated above and n can represent 0 or 1.
[00086] Anilines of Formulas (X) and (XXVIII) can be converted into the ureas (A=O) and thioureas (S) of Formulas (XXXVIII) and (XXXVII) respectively, by methods known in the literature, for example from according to JP2011/042611 by treating them with isocyanates (A=O) and isothiocyanates (for A=S), optionally in the presence of an organic solvent, or by converting them by generally known methods into the respective isocyanates. (A=O) and isothiocyanates (A=S) and reacting these with amines to produce the thioureas.
[00087] From the ureas (A=O) and the thioureas (A=S) of the general formulas (XXXVIII) and (XXXVII), respectively, it is possible to synthesize the 2-arylamino-1,3-oxazolidin-4-ones (A=O) and the thiazolidin-4-ones (A=S) of the general formulas (Ia-g) and (Ib-g), respectively, for example, by cycloacylation with a halocarbonyl derivative in an inert solvent, in in most cases at temperatures above 100 °C. Halocarbonyl derivatives are, for example, for n=0, chloroacetic acid and its acid chloride, bromoacetic acid and its acid chloride or bromide, for n=1 the literature refers to 3-substituted 2-propenoyl chlorides as described by CF Howell in J. Org. Chem. 1962, 27, 1686 and 1691 for analogous conversions to oxazolidinones and V.N.Britsun in Russ. J. Org. Chem. 2006, 41 (11), 1719-1729 for thiazolidinones.
[00088] The compounds of the Formulas (XXVIII), (XXXVIII) and (XXXVII) in process I can be prepared in particular under the conditions referred to in the preparation examples. Process J
[00089] The 3-substituted 2-arylamino-1,3-thiazoles of the General Formula (I) can be prepared, for example, by process J
[00090] Where X1, X2, X3, X4 and R2 have the meanings given above.
[00091] R7 and R8 are substituents on the ring formed by R1 and R3 together with the atoms to which they are attached.
[00092] The 2-aryliminothiazoles (Ia-h) and (Ib-h) 2-substituted can be synthesized from the thioureas (XXXVIII) and (XXXVII), respectively, for example, by reaction with a halocarbonyl derivative suitable in an inert solvent. This operation can be carried out, for example, by cycloacylation with α-halo compounds or derivatives thereof, for example with 3-bromo-2-butanone for R7=R8=methyl, as described by A. Yahyazadeh in J. Pharm. Res. 1998, 9, 536-537(S), 2126-2139(M), or with 2-chloro-1,1-diethoxyethane for R7=R8=H as described in patent US4079144.
[00093] The sulfoxides (Ib) can be obtained through oxidation of the trioether (Ia) through methods known in the literature. For this purpose, known methods of enantioselective enrichment of sulfoxides can be employed.
[00094] These 2-arylimino-1,3-thiazoles (I) can also be synthesized directly from the anilines of Formula (X) or (XXVIII), for example by reaction with 3-alkyl-1,3- thiazolinothiones of Formula (A) or thiazolium salts thereof, optionally in the presence of a base and optionally in an inert solvent.
[00095] 3-Substituted 1,3-thiazolinothiones of Formula (A) can be obtained from commercial sources or can be prepared by methods known in the literature, for example as described by K.N. Mehrotra in Bull. Sulf. Sil. and rel.elem. 2011, 1-6(1), 12-20. As in J. Amer. Chem. Soc. 19-7, 109 (2), 492-507, amines can be reacted with carbon disulfide to produce dithiocarbamates of Formula (D), using a halocarbonyl intermediate, yielding alkylated compounds of Formula (C). Suitable halocarbonyl compounds, for example, chloroethanone or 2-chloro-1,1-diethoxytane for R7=R8=H, chloropropanone for R7=H and R8=methyl, 3-bromo-2-butanone for R7=R8=methyl, 2-bromo-3-pentanone for R7=methyl and R8=ethyl, etc. The compounds of Formula (C) can either cyclize spontaneously to the desired thiazolinothiones (A) or just after dehydration, in most cases under acidic conditions and with heating.
[00096] Thiazolinium salts of Formula (B) can be prepared by alkylation of the corresponding thiadiazolinothiones of Formula (B). Suitable alkylating agents are, for example, alkyl halides (alkyl chlorides, alkyl bromides and alkyl iodides), alkyl triflates, alkyl mesylates and dialkyl sulfates.
[00097] The compounds of the Formulas (XXVIII), (XXXVII) and (XXXVIII) in process J can be prepared in particular under the conditions referred to in the preparation examples. Process K
[00098] The 3-substituted 2-arylaminooxadiazoles of the General Formula (I) can be prepared, for example, by process K
[00099] Where X1, X2, X3, X4 and R2 have the meanings given above.
[000100] R7 is the substituent on the ring formed by R1 and R3 together with the atoms to which they are attached.
[000101] The anilines of the General Formula (X) of the General Formula (XXVIII) can be reacted, for example with the oxadiazolinothiones of the Formula (XXXV) or with the corresponding oxadiazolium salts of the Formula (XXXIX) to produce the 2-aryliminooxadiazoles of Formula (Ia-i) and (Ib-i) respectively. This reaction optionally takes place in the presence of a base, optionally in an inert solvent or in an agent that can assume both functions, for example pyridine.
[000102] The synthesis of oxadiazolinothiones of the Formula (XXXV) and their oxadiazolium salts (XXXIX) can, for example, be carried out, by
[000103] Oxadiazolium salts of Formula (XXXIX) can be prepared by methods known from the literature, by alkylation of oxadiazolinothiones of Formula (XXXV). Suitable alkylating agents are, for example, alkyl halides (alkyl chlorides, alkyl bromides and alkyl iodides), alkyl triflates, alkyl mesylates and dialkyl sulfates.
[000104] The compounds of the Formula (XXVIII) in process K can be prepared in particular under the conditions referred to in the preparation examples.
[000105] All these processes lead to the compounds of the General Formula (I) according to the invention.
[000106] The active compounds according to the present invention, in combination with a good tolerance by plants and favorable toxicity in warm-blooded animals and being well tolerated by the environment, are suitable for the protection of plants and plant organs, to increase crop yields, to improve the quality of harvested material and to control animal pests, in particular insects, arachnids, helminths, nematodes and molluscs found in agriculture, horticulture, livestock, forests, gardens and recreational spaces, in the protection of products and materials stored and in the hygiene sector. These can preferably be used as crop protection agents. They are active against species with normal sensitivity and resistance and also against all or some developmental stages. The aforementioned pests include:
[000107] From the order of Anoplura (Phthiraptera), for example, Damalinia spp., Haematopinus spp., Linognathus spp., Pediculus spp., Trichodectes spp.
From the Arachnida class, for example, Acarus spp., Aceria sheldoni, Aculops spp., Aculus spp., Amblyomma spp., Amphitetranychus viennensis, Argas spp., Boophilus spp., Brevipalpus sppet., Biosaryo ., Dermanyssus gallinae, Eotetranychus spp., Epitrimerus pyri, Eutetranychus spp., Eriophyes spp., Halotydeus destructor, Hemitarsonemus spp., Hyalomma spp., Ixodes spp. Ornithodoros spp., Panonychus spp., Phyllocoptruta oleivora, Polyphagotarsonemus latus, Psoroptes spp., Rhipicephalus spp., Rhizoglyphus spp., Sarcoptes spp., Scorpio maurus, Stenotarspersonemus.
[000109] From the class of Bivalva, for example, Dreissena spp.
[000110] From the order of Chilopoda, for example, Geophilus carpophagus and Scutigera spp.
[000111] From the order Coleoptera, for example, Acalymma vittatum, Acanthoscelides obtectus, Adoretus spp., Agelastica alni, Agriotes spp., Amphimallon solstitialis, Anobium punctatum, Anoplophora spp., Anthonomus spp., Anthrenus spp., Anthrenus spp. Apogonia spp., Atomaria spp., Attagenus spp., Bruchidius obtectus, Bruchus spp., Cassida spp., Cerotoma trifurcata, Ceutorrhynchus spp., Chaetocnema spp., Cleonus mendicus, Conoderus spp. ., Curculio spp., Cryptorhynchus lapathi, Cylindrocopturus spp., Dermestes spp., Diabrotica spp., Dichocrocis spp., Diloboderus spp., Epilachna spp., Epitrix spp. Heteronyx spp., Hylamorpha elegans, Hylotrupes bajulus, Hypera postica, Hypothenemus spp., Lachnosterna consanguinea, Lema spp., Leptinotarsa decemLineata, Leucoptera spp., Lissorhoptrus oryzophilus, Lixus spp. Melanotus spp ., Meligethes aeneus, Melolontha spp., Migdolus spp., Monochamus spp., Naupatus xanthographus, Niptus hololeucus, Oryctes rhinoceros, Oryzaephilus surinamensis, Oryzaphagus oryzae, Otiorrhynchus, Phylle. Popillia japonica, Premnotrypes spp., Psylliodes spp., Ptinus spp., Rhizobius ventralis, Rhizopertha dominica, Sitophilus spp., Sphenophorus spp., Sternechus spp., Symphyletes spp. ., Tychius spp., Xylotrechus spp., Zabrus spp.
[000112] From the order of Collembola, for example, Onychiurus armatus.
[000113] From the order of the Diplopoda, for example, Blaniulus guttulatus.
[000114] From the order Diptera, for example, Aedes spp., Agromyza spp., Anastrepha spp., Anopheles spp., Asphondylia spp., Bactrocera spp., Bibio hortulanus, Calliphora erythrocephala, Ceratitis capitata, Chironomus spp., spp. ., Cochliomyia spp., Contarinia spp., Cordylobia anthropophaga, Culex spp., Cuterebra spp., Dacus oleae, Dasyneura spp., Delia spp., Dermatobia hominis, Drosophila spp., Echinocnemus spp., Gasnia spp., Fannia spp. , Hydrellia spp., Hylemyia spp., Hyppobosca spp., Hypoderma spp., Liriomyza spp., Lucilia spp., Musca spp., Nezara spp., Oestrus spp., Oscinella frit, Pegomyia spp., Phorbia spp., Phorbia spp. ., Psila rosae, Rhagoletis spp., Stomoxys spp., Tabanus spp., Tannia spp., Tetanops spp., Tipula spp.
[000115] From the class of Gastropoda, for example, Arion spp., Biomphalaria spp., Bulinus spp., Deroceras spp., Galba spp., Lymnaea spp., Oncomelania spp., Pomacea spp., Succinea spp.
[000116] From the class of helminths, for example, Ancylostoma duodenale, Ancylostoma ceylanicum, Acylostoma braziliensis, Ancylostoma spp., Ascaris lubricoides, Ascaris spp., Brugia malayi, Brugia timori, Bunostomum spp. spp., Dicrocoelium spp., Dictyocaulus filaria, Diphyllobothrium latum, Dracunculus medinensis, Echinococcus granulosus, Echinococcus multilocularis, Enterobius vermicularis, Faciola spp., Haemonchus spp., Hystrongus lopp. , Oesophagostomum spp., Opisthorchis spp., Onchocerca volvulus, Ostertagia spp., Paragonimus spp., Schistosomen spp., Strongyloides fuelleborni, Strongyloides stercoralis, Stronyloides spp., Taenia saginata, Trichinella solchinia native, Tachinella brischinia, Trichinella solchinia, Tachinella solchinia native nelsoni, Trichinella pseudopsiralis, Trichostrongulus spp., Trichuris trichuria, Wuchereria bancrofti.
[000117] It is also possible to control protozoa such as Eimeria.
From the order Heteroptera, for example, Anasa tristis, Antestiopsis spp., Blissus spp., Calocoris spp., Campylomma livida, Cavelerius spp., Cimex spp., Collaria spp., Creontiades dilutus, Dasynus piperis, Dichelops Diconocoris hewetti, Dysdercus spp., Euschistus spp., Eurygaster spp., Heliopeltis spp., Horcias nobilellus, Leptocorisa spp., Leptoglossus phyllopus, Lygus spp., Macropes excavatus, Miridae, Nepp. , Piesma quadrata, Piezodorus spp., Psallus spp., Pseudacysta persea, Rhodnius spp., Sahlbergella singularis, Scaptocoris castanea, Scotinophora spp., Stephanitis nashi, Tibraca spp., Triatoma spp.
From the order Homoptera, for example, Acyrthosipon spp., Acrogonia spp., Aeneolamia spp., Agonoscena spp., Aleurodes spp., Aleurolobus barodensis, Aleurothrixus spp., Amrasca spp., Aneolamia spp., Agonoscena spp., Aleurodes spp., Aleurolobus barodensis, Aleurothrixus spp., Amrasca spp. piri, Aphis spp., Arboridia apicalis, Aspidiella spp., Aspidiotus spp., Atanus spp., Aulacorthum solani, Bemisia spp., Brachycaudus helichrysii, Brachycolus spp., Brevicoryne spp. spp., Chaetosiphon fragaefolii, Chionaspis tegalensis, Chlorita onukii, Chromaphis juglandicola, Chrysomphalus ficus, Cicadulina mbila, Coccomytilus halli, Coccus spp., Cryptomyzus ribis, Dalbulus spp., Dr. spp. , Dysaphis spp., Dysmicoccus spp., Empoasca spp., Eriosoma spp., Erythroneura spp., Euscelis bilobatus, Ferrisia spp., Geococcus coffeae, Hieroglyphus spp. ocerus spp., Idioscopus spp., Laodelphax striatellus, Lecanium spp., Lepidosaphes spp., Lipaphis erysimi, Macrosiphum spp., Mahanarva spp., Melanaphis sacchari, Metcalfiella spp., Metopolophisis, Monellizus dir. Nasonovia ribisnigri, Nephotettix spp., Nilaparvata lugens, Oncometopia spp., Orthezia praelonga, Parabemisia myricae, Paratrioza spp., Parlatoria spp., Pemphigus spp., Peregrinus spp. aspidistrae, Planococcus spp., Protopulvinaria pyriformis, Pseudaulacaspis pentagona, Pseudococcus spp., Psylla spp., Pteromalus spp., Pyrilla spp., Quadraspidiotus spp., Rhodespidiotus spp. Schizaphis graminum, Selenaspidus articulatus, Sogata spp., Sogatella furcifera, Sogatodes spp., Stictocephala festina, Tenalaphara malayensis, Tinocallis caryaefoliae, Tomaspis spp., Toxoptera spp., Trialeur odes spp., Trioza spp., Typhlocyba spp., Unaspis spp., Viteus vitifolii, Zygina spp.
From the order Hymenoptera, for example, Athalia spp., Diprion spp., Hoplocampa spp., Lasius spp., Monomorium pharaonis, Vespa spp.
[000121] From the order of the Isopoda, for example Armadillidium vulgare, Oniscus asellus, Porcellio scaber.
[000122] From the order of the Isoptera, for example, Acromyrmex spp., Atta spp., Cornitermes cumulans, Microtermes obesi, Odontotermes spp., Reticulitermes spp.
[000123] From the order Lepidoptera, for example, Acronicta major, Adoxophyes spp., Aedia leucomelas, Agrotis spp., Alabama spp., Amyelois transitella, Anarsia spp., Anticarsia spp., Argyroploce spp., Barathra brassicae, Borbo cinnara. Bucculatrix thurberiella, Bupalus piniarius, Busseola spp., Cacoecia spp., Caloptilia theivora, Capua reticulana, Carpocapsa pomonella, Carposina niponensis, Cheimatobia brumata, Chilo spp., Choristoneura spp., Clyppus phappusia ambigu. ., Conotrachelus spp., Copitarsia spp., Cydia spp., Dalaca noctuides, Diaphania spp., Diatraea saccharalis, Earias spp., Ecdytolopha aurantium, Elasmopalpus lignosellus, Eldana saccharina, Ephestiapp. , Eulia spp., Eupoecilia ambiguella, Euproctis spp., Euxoa spp., Feltia spp., Galleria mellonella, Gracillaria spp., Grapholitha spp., Hedylepta spp., Helicoverpa spp., Heliothis spp. a spp., Homona spp., Hyponomeuta padella, Kakivoria flavofasciata, Laphygma spp., Laspeyresia molesta, Leucinodes orbonalis, Leucoptera spp., Lithocolletis spp., Lithophane antennata, Lobesia spp. Malacosoma neustria, Maruca testulalis, Mamestra brassicae, Mocis spp., Mythimna separata, Nymphula spp., Oiketicus spp., Oria spp., Orthaga spp., Ostrinia spp., Oulema oryzae, Panolis flammea, Parnara spp. Perileucoptera spp., Phthorimaea spp., Phyllocnistis citrella, Phyllonorycter spp., Pieris spp., Platynota stultana, Plusia spp., Plutella xylostella, Prays spp., Prodenia spp., Prodenia spp. , Rachiplusia nu, Schoenobius spp., Scirpophaga spp., Scotia segetum, Sesamia spp., Sparganothis spp., Spodoptera spp., Stathmopoda spp., Stomopteryx subsecivella, Synanthedon spp. tort rix spp., Trichoplusia spp., TutaAbsolute, Virachola spp.
[000124] From the order Orthoptera, for example, Acheta domesticus, Blatta orientalis, Blattella germanica, Dichroplus spp., Gryllotalpa spp., Leucophaea maderae, Locusta spp., Melanoplus spp., Periplaneta americana, Schistocerca gregaria.
[000125] From the order of Siphonaptera, for example, Ceratophyllus spp. and Xenopsylla cheopis.
[000126] From the order of Symphyla, for example, Scutigerella spp.
From the order Thysanoptera, for example, Anaphothrips obscurus, Baliothrips biformis, Drepanothris reuteri, Enneothrips flavens, Frankliniella spp., Heliothrips spp., Hercinothrips femoralis, Rhipiphorothrips cruppentatus, Scipprips, Scipprips.
[000128] From the order of Thysanura, for example, Lepisma saccharina.
Phytoparasitic nematodes include, e.g., Aphelenchoides spp., Bursaphelenchus spp., Ditylenchus spp., Globodera spp., Heterodera spp., Longidorus spp., Meloidogyne spp., Pratylenchus Rchodor spp. Tylenchulus semipenetrans, Xiphinema spp.
[000130] If appropriate, the compounds according to the invention can, at certain concentrations or application rates, also be used as herbicides, safeners, growth regulators or agents to improve the properties of plants or as microbicides, for example as fungicides , antimycotics, bactericides, viricides (including agents against viroids) or as agents against MLO (mycoplasma-like organisms) and RLO (rickettsia-like organisms). If appropriate, they can also be used as intermediates and precursors for the synthesis of other active compounds.
[000131] The present invention further relates to formulations and forms of use prepared from these as crop protection compositions and/or pesticides, for example, liquors for impregnation, dropwise and spraying, comprising at least one of the active compounds according to the invention. Use forms optionally comprise other crop protection agents and/or pesticides and/or action enhancing adjuvants such as penetrants, for example vegetable oils, for example rapeseed oil, sunflower oil, mineral oils, for example paraffin oils, alkyl esters of vegetable fatty acids, for example rapeseed oil methyl ester or soy oil methyl ester, or alkoxylated alkanols and/or spreaders, for example alkylsiloxane, and/or salts, for example organic or inorganic ammonia or phosphonium salts, for example ammonium sulphate or diammonium hydrogen phosphate, and/or retention promoters, for example dioctyl sulfosuccinate or hydroxypropyl guar polymers and/or wetting agents, for example glycerol and/or fertilizers, for example fertilizers containing ammonia, potassium or phosphorus.
[000132] The usual formulations are, for example, water-soluble liquids (SL), emulsion concentrates (EC), water emulsions (EW), suspension concentrates (Sc, Se , FS, OD, abbreviations, hydrodispersible granules (WG), granules (GR) and capsule concentrates (CS), these and other possible formulation types are described, for example, in Crop Life International and in Pesticide Specifications, Manual on development and use of FAO and WHO specifications for pesticides, FAO Plant Production and Protection Papers - 173, prepared by the FAO/WHO Joint Meeting on Pesticide Specifications, 2004, ISBN: 9251048576. The formulations optionally comprise , in addition to one or more active compounds according to the invention, other agrochemically active compounds.
[000133] These are preferably formulations or forms of use comprising auxiliaries, for example diluents, solvents, spontaneity promoters, vehicles, emulsifiers, dispersants, antifreeze, biocides, thickeners and/or other auxiliaries, for example adjuvants. In the present context, an adjuvant is a component that enhances the biological effect of the formulation without the component itself having a biological effect. Examples of adjuvants are agents that promote retention, distribution, attachment to the sheet surface or penetration.
[000134] These formulations are produced in a known manner, for example, by mixing the active ingredients with auxiliaries, for example diluents, solvents and/or solid vehicles and/or other auxiliaries, for example surfactants. The formulations are produced either in suitable production units or before or during application.
[000135] The auxiliaries used may be substances suitable to confer special properties, such as certain physical, technical and/or biological properties, to the formulation of the active ingredient or to the forms of use prepared from these formulations (for example, protection compositions from ready-to-use crops such as spray liquors or seed coating products).
[000136] Suitable diluents are, for example, water, organic polar and non-polar chemical liquids, for example from the classes of aromatic and non-aromatic hydrocarbons (such as paraffins, alkylbenzenes, alkylnaphthalenes, chlorobenzenes), alcohols and polyols (which, if appropriate further substituted, etherified and/or esterified), ketones (such as acetone, cyclohexanone), esters (including fats and oils) and (poly)ethers, unsubstituted and substituted amines, amides, lactams ( such as N-alkylpyrrolidones) and lactones, sulfones and sulfoxides (such as dimethylsulfoxide),
[000137] If the diluent used is water, it is also possible to use for example organic solvents as auxiliary solvents. Useful liquid solvents are essentially: aromatic compounds such as xylene, toluene or alkylnaphthalenes, chlorinated aromatic compounds or chlorinated aliphatic hydrocarbons such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatic hydrocarbons such as cyclohexane or paraffins, for example oil fractions mineral, mineral and vegetable oils, alcohols such as butanol or glycol, as well as their ethers and esters, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents such as dimethylformamide and dimethyl sulfoxide and also water.
[000138] In principle it is possible to use all suitable solvents. Examples of suitable solvents are aromatic hydrocarbons such as xylene, toluene or alkylnaphthalenes, chlorinated aromatic compounds or chlorinated aliphatic hydrocarbons such as chlorobenzene, chloroethylene or methylene chloride, aliphatic hydrocarbons such as cyclohexane or paraffins, petroleum fractions, oils minerals and vegetables, alcohols such as methanol, ethanol, isopropanol, butanol or glycol, as well as the respective ethers and esters, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents such as dimethyl sulfoxide and still water .
[000139] In principle it is possible to use all suitable vehicles. Suitable carriers include, in particular: for example ammonium salts and ground natural minerals such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth and ground synthetic materials such as finely divided silica, alumina and silicates natural or synthetic, resins, waxes and/or solid fertilizers. Mixtures of these vehicles can also be used. Useful carriers for granulates include: for example crushed and fractured natural rocks such as calcite, pumice, marble, sepiolite, dolomite and further synthetic granules of inorganic and organic flours and also granules of organic material such as sawdust, paper, bark coconut, corn cobs and tobacco stalks.
[000140] Diluents or liquefied gaseous solvents can also be used. Particularly suitable diluents or vehicles are those which are gaseous at room temperature and under atmospheric pressure, for example aerosol propellant gases such as hydrocarbons and also butane, propane, nitrogen and carbon dioxide.
[000141] Examples of emulsifiers and/or foamers or wetting agents with ionic or non-ionic properties or mixtures of these surfactants include polyacrylic acid salts, lignosulfonic acid salts, phenolsulfonic or naphthalenesulfonic acid salts, ethylene oxide polycondensates with fatty alcohols or with fatty acids or with fatty amines, substituted phenols (in particular alkylphenols or arylphenols), salts of sulfosuccinic acid esters, taurine derivatives (in particular alkyl taurates), phosphoric esters of alcohols or polyoxyethylated phenols, fatty acid esters of polyols and derivatives of sulphate, sulphonate and phosphate compounds, for example polyglycolic alkylaryl ethers, alkylsulphonates, alkylsulphates, arylsulphonates, protein hydrolysates, lignosulfite residue liquors and methylcellulose. The presence of a surfactant is advantageous when one of the active ingredients and/or one of the inert vehicles is insoluble in water and when the application is made in water.
[000142] Other auxiliaries that may be present in the formulations and in the forms of use derived from them include dyes, such as inorganic pigments, for example iron oxide, titanium oxide and Prussian blue and organic dyes, such as alizarin, azo dyes and metallic phthalocyanine dyes and trace nutrients and nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.
[000143] Additional components can be stabilizers, such as cold stabilizers, preservatives, antioxidants, photostabilisers and other agents that improve chemical and/or physical stability. Foamers or defoamers may also be present.
[000144] They may be present as additional auxiliaries in the formulations and forms derived from these adhesives, such as carboxymethylcellulose and natural and synthetic polymers in the form of powders, granules or latexes, such as gum arabic, polyvinyl alcohol and polyvinyl acetate, or phospholipids such as cephalins and lecithins and synthetic phospholipids. Other auxiliaries can be minerals and vegetable oils.
[000145] Optionally, other auxiliaries may be present in the formulations and in the forms of use derived from them. Examples of these additives include fragrances, protective colloids, binders, adhesives, thickeners, thixotropic agents, penetrants, retention enhancers, stabilizers, sequestrants, complexers, humectants, spreaders. In general, the active compounds can be combined with any solid or liquid additive commonly used for formulation purposes.
Included among the useful retention promoters are all substances which reduce dynamic surface tension, for example dioctyl sulfosuccinate, or increase viscoelasticity, for example hydroxypropyl guar polymers.
[000147] Penetrants useful in the present context are all substances that are typically used to improve the penetration of agrochemical active ingredients into plants. Penetrants are defined in the present context by their ability to penetrate from the application liquor (usually aqueous) and/or from the spray layer on the plant cuticle, thus increasing the mobility of the active ingredients into the cuticle. Methods described in the literature (Baur et al., 1997, Pesticide Science 51, 131-152) can be used to determine this property. Examples include alkoxylated alcohols, such as coconut fatty ethoxylate (10) or isotridecyl (12) ethoxylate, fatty acid esters, for example rapeseed oil methyl ester or soybean oil methyl ester, fatty amine alkoxylates, for example for example ethoxylated tallow amine (15) or ammonium and/or phosphonium salts, for example ammonium sulphate or diammonium hydrogen phosphate.
[000148] The formulations preferably contain between 0.00000001% and 98% by weight of the active ingredient or more preferably between 0.01% and 95% by weight of the active ingredient, more preferably between 0.5% and 90% by active ingredient weight based on formulation weight.
[000149] The active ingredient content of use forms (crop protection compositions) prepared from formulations can vary within a wide range. The concentration of active ingredient of the use forms may typically be between 0.00000001% and 98% by weight of the active ingredient, preferably between 0.00001% and 1% by weight based on the weight of the use form. The application is executed in the usual way, appropriate to the ways of use.
[000150] The active compounds according to the invention can be used on their own or in formulations thereof, including in a mixture with one or more fungicides, bactericides, acaricides, nematicides, insecticides, microbicides, fertilizers, attractants, phytotonics, sterilants, suitable synergists, safeners, semiochemicals and/or plant growth regulators, in order to, for example, extend the spectrum of action, prolong the duration of action, increase the rate of action, prevent repulsion or prevent the evolution of resistance. Furthermore, plant development can be improved through combinations that increase tolerance to abiotic factors, for example, high or low temperatures, drought or high soil water content or salinity. It is also possible to improve flowering and fruit production, optimize germination capacity and root development, facilitate harvesting and improve yields, influence maturation, improve the quality and/or nutritional value of harvested products, prolong life in warehouse and/or improve the ease of processing the harvested products. In general, with the combination of the active compounds according to the invention and the mixing partners, synergistic effects are obtained, i.e. the effectiveness of the mixture in question is greater than the effectiveness of the individual components. It is generally possible to use the combinations in premixes, tank mixes and even seed applications.
[000151] Particularly favorable mixing partners are, for example, the following: Insecticide/acaricides/nematicides:
[000152] The active compounds identified by their common name are known and are described, for example, in the pesticide manual ("The Pesticide Manual" 14th ed., British Crop Protection Council 2006) or can be consulted on the Internet (eg. http://www.alanwood.net/pesticides).
[000153] (1) Acetylcholinesterase (AChE) inhibitors such as, for example, carbamates, e.g. Alanicarb, Aldicarb, Bendiocarb, Benfuracarb, Butocarboxim, Butoxycarboxim, Carbaryl, Carbofuran, Carbosulfan, Ethiofencarb, Fenobucarb, Formetanate, Furathiocarb, Isoprocarb, Methiocarb, Methomyl, Metolcarb, Oxamylmate, Ticarb, Tipox, Pirimicar and Xylylcarb; or organophosphates, e.g. Acephate, Azamethyphos, Azinphos-ethyl, Azinphos-methyl, Cadusaphos, Chlorethoxyphos, Chlorphenvinphos, Chlormephos, Chlorpyrifos, Chlorpyrifos-methyl, Coumaphos, Cyanophos, Demeton-S-methyl, Diazinone, Dichlorvos/DDVP, Dichrotophos, Dicrotophos EPN, Ethion, Etoprophos, Famfur, Phenamiphos, Fenitrothion, Fenthion, Phosthiazate, Heptenophos, Imyciaphos, Isofenphos, O-(methoxyaminothio-phosphoryl)salicylate, Isoxation, Malathion, Mecarbam, Metamidophos, Metidation, Metidation, Metidation , Oxidemeton-methyl, Parathion, Parathion-methyl, Phentoate, Phhorate, Phosalone, Fosmet, Phosphamidone, Foxim, Pyrimphos-methyl, Profenophos, Propetamphos, Prothiophos, Piraclophos, Pyridaphenthione, Quinalphos, Sulfotep, Tebupyrimphos, Tembuphos , Triazophos, Trichlorphon, and Vamidothione.
[000154] (2) GABA-mediated chlorine channel antagonists such as, for example, cyclodiene organochlorines, e.g. Chlordan and Endosulfan or phenylpyrazoles (fiprols), e.g. Etiprol and Fipronil.
[000155] (3) voltage-dependent sodium channel modulators/sodium channel blockers, eg pyrethroids, e.g. Acrinathrin, Allethrin, d-cis-trans Allethrin, d-trans Allethrin, Bifenthrin, Bioallethrin, Bioaletrin S-cyclopentenyl isomer, Bioresmethrin, Cycloprothrin, Cyfluthrin, beta-Cyfluthrin, Cyhalothrin, lambda-Cyalothrin, gamma-Cyalothrin, Alpha-Cypermethrin Cypermethrin, beta-Cypermethrin, theta-Cypermethrin, zeta-Cypermethrin, Cyfenotrin [(1R)-trans isomers], Deltamethrin, Empentrin [(EZ)-(1R) isomers), Esfenvalerate, Etofenprox, Fenpropathrin, Fenvalerate, Flucitrinate tau-Fluvalinate, Halfenprox, Imiprothrin, Kadethrin, Permethrin, Phenotrin [(1R)-trans isomer, Praletrine, Pyrethrin (pyrethrum), Resmethrin, Silafluofen, Tefluthrin, Tetramethrin, Tetramethrin [(1R)-isomers], Tralomethrin; and or DDT or methoxychlor.
[000156] (4) Nicotinergic acetylcholine receptor (nAChR) agonists, for example neonicotinoids, e.g. Acetamiprid, Clothianidin, Dinotefuran, Imidacloprid, Nitenpyram, Tiacloprid, and Tiamethoxam or nicotine.
[000157] (5) Allosteric activators of the nicotinergic acetylcholine receptor (nAChR), eg spinosyns, e.g. Spinetoram and Spinosad.
[000158] (6) Chlorine channel activators such as, for example avermectins/milbemycins, e.g. Abamectin, Emamectin benzoate, Lepimectin and Milbemectin.
[000159] (7) Juvenile hormone mimetics, for example juvenile hormone analogues, e.g. Hydroprene, Quinoprene and Methoprene or fenoxycarb or Pyriproxyfen.
[000160] (8) Active compounds with unknown or non-specific mechanisms of action, for example, alkyl halides, e.g. methyl bromide and other alkyl halides or chloropicrin or sulphoryl fluoride or Borax or tartar emetic.
[000161] (9) Selective antinutrients, for example pymetrozine or flonicamid.
[000162] (10) Inhibitors of the growth of mites, e.g. Clofenthezine, Hexithiazox and Diflovidazine or
[000163] etoxazol.
[000164] (11) Microbial disruptors of the digestive membranes of insects, such as Bacillus turingiensis subspecies israelensis, Bacillus sphaericus, Bacillus turingiensis subspecies aizawai, Bacillus turingiensis subspecies kurstaki, Bacillus turingiensis subspecies israelensis, Cri1ABT proteins, plants cri1 , Cri2Ab, mCri3A, Cri3Ab, Cri3Bb, Cri34/35Ab1.
[000165] (12) Inhibitors of oxidative phosphorylation, ATP disruptors, such as diafentiuron; or organotin compounds, for example azocyclotin, cyhexatin, fenbutatin oxide; or propargite or tetradiphone;
[000166] (13) Oxidative phosphorylation uncouplers that act by disrupting the H proton gradient, such as, for example, chlorfenapyr, DNOC and sulfluramide.
[000167] (14) Nicotinergic acetylcholine receptor antagonists such as. for example,bensultape, cartape hydrochloride, thiocyclam, and thiosultape-sodium.
[000168] (15) Inhibitors of chitin synthesis, type 0, such as, for example, bistrifluron, chlorfluazuron, diflubenzuron, flucycloxuron, flufenoxuron, hexaflumuron, lufenuron, novaluron, noviflumuron, teflubenzuron and triflumuron.
[000169] (16) Inhibitors of chitin synthesis, type 1, such as for example buprofezin.
[000170] (17) Moult disruptors, dipterans, such as, for example, cyromazine.
[000171] (18) Ecdysone receptor agonists such as, for example, Chromafenozide, Halofenozide, Methoxyfenozide and Tebufenozide.
[000172] (19) Octopaminergic antagonists such as, for example, amtraz.
[000173] (20) Complex III electron transport inhibitors such as, for example, Hydramethylnon or Acequinocil or Fluacripyrime.
[000174] (13) Inhibitors of complex I of electron transport, for example
[000175] METI acaricides eg Phenazaquin, Fenpyroximate, Pyrimidifen, Pyridaben, Tebufenpirad and Tolfenpirad; or
[000176] rotenone (Derris).
[000177] (22) Voltage-dependent sodium channel blockers eg Indoxacarb; or Metaflumizone.
[000178] (23) Acetyl-CoA carboxylase (ACC) inhibitors such as, for example, derivatives of tetronic and tetramic acid, e.g. spirodiclofen, spiromesifen and spirotetramate.
[000179] (24) Complex IV electron transport inhibitors such as, for example, phosphines, e.g. aluminum phosphide, calcium phosphide, phosphine and zinc phosphide or cyanide.
[000180] (25) Complex II electron transport inhibitors such as, for example, cyenopyrafen.
[000181] (28) Effectors of Rianodine receptors, for example diamides, e.g. Chlorantraniliprole and Flubendiamide.
[000182] Other active compounds with unknown mechanism of action such as, for example amidoflumet, azadirachtin, benclothiaz, benzoximate, bifenazate, bromopropylate, cinomethionate, cryolite, cyantraniliprol (ciazipir), ciflumetofen, dicofol, diflovidazine, fluensulfonate, fluprofenerim, fluensulfone , fufenozide, imidaclotiz, iprodione, meperfluthrin, pyridalyl, pyrifluquinazone, tetramethylfluthrin and iodomethane and additionally preparations based on Bacillus firmus (in particular the CNCM strain I-1582, for example VOTiVO™, BioNem), and the following known active compounds:
[000183] 3-bromo-N-{2-bromo-4-chloro-6-[(1-cyclopropylethyl)carbamoyl]phenyl}-1-(3-chloropyridin-2-yl)-1H-pyrazole-5-carboxamide (known from WO2005/077934), 4-{[(6-bromopyrid-3-yl)methyl](2-fluoroethyl)amino}furan-2(5H)-one (known from WO2007/115644), 4-{[ (6-fluoropyrid-3-yl)methyl](2,2-difluoroethyl)amino}furan-2(5H)-one (known from WO2007/115644), 4-{[(2-chloro-1,3-thiazole) -5-yl)methyl](2-fluoroethyl)amino}furan-2(5H)-one (known from WO2007/115644), 4-{[(6-chloropyrid-3-yl)methyl](2-fluoroethyl) amino}furan-2(5H)-one (known from WO2007/115644), flupyradifurone, 4-{[(6-chloro-5-fluoropyrid-3-yl)methyl](methyl)amino}furan-2(5H) -one (known from WO2007/115643), 4-{[(5,6-dichloropyrid-3-yl)methyl](2-fluoroethyl)amino}furan-2(5H)-one (known from WO2007/115646), 4-{[(6-chloro-5-fluoropyrid-3-yl)methyl](cyclopropyl)amino}furan-2(5H)-one (known from WO2007/115643), 4-{[(6-chloropyrid-3) -yl)methyl](cyclopropyl)amino}furan-2(5H)-one (known from EP-A-0 539 588), 4-{[(6-chloropyrid-3-yl)methyl](meth yl)amino}furan-2(5H)-one (known from EP-A-0 539 588), {[1-(6-chloropyridin-3-yl)ethyl](methyl)oxido-À4-sulfanylidene}cyanamide ( known from WO2007/149134 ) and Diastereoisomers thereof {[(1R)-1-(6-chloropyridin-3-yl)ethyl](methyl)oxide-À4-sulfanylidene}cyanamide (A) and {[(1S)-1- (6-chloropyridin-3-yl)ethyl](methyl)oxide-À4-sulfanylidene}cyanamide (B) (also known from WO2007/149134) and sulfoxaflor and diastereoisomers of these [(R)-methyl(oxide){(1R) -1-[6-(trifluoromethyl)pyridin-3-yl]ethyl}-À4-sulfanylidene]cyanamide (A1) and [(S)-methyl(oxide){(1S)-1-[6-(trifluoromethyl) pyridin-3-yl]ethyl}-À±4-sulfanylidene]cyanamide (A2), designated as Group A diastereoisomer (known from WO 2010/074747, WO 2010/074751), [(R)-methyl(oxide){(1S )-1-[6-(trifluoromethyl)pyridin-3-yl]ethyl}-À4-sulfanilidene]cyanamide (B1) and [(S)-methyl(oxide){(1R)-1-[6-(trifluoromethyl) pyridin-3-yl]ethyl}-À4-sulfanilidene]cyanamide (B2), designated as Group B diastereoisomer (also known from WO 2010/074747, WO 2010/074751 ) and 11-(4-chloro-2,6-dimethylphenyl)-12-hydroxy-1,4-dioxa-9-azadispiro[4.2.4.2]tetradec-11-en-10-one (known from WO2006/089633) , 3-(4'-fluoro-2,4-dimethylbiphenyl-3-yl)-4-hydroxy-8-oxa-1-azaspiro[4.5]dec-3-en-2-one (known from WO2008/067911) , 1-{2-fluoro-4-methyl-5-[(2,2,2-trifluoroethyl)sulfinyl]phenyl}-3-(trifluoromethyl)-1H-1,2,4-triazol-5-amine (known of WO2006/043635), [(3S,4aR,12R,12aS,12bS)-3-[(cyclopropylcarbonyl)oxy]-6,12-dihydroxy-4,12b-dimethyl-11-oxo-9-(pyridine) cyclopropanecarboxylate -3-yl)-1,3,4,4a,5,6,6a,12,12a,12b-decahydro-2H,11H-benzo[f]pyrano[4,3-b]chromen-4-yl] methyl (known from WO2008/066153), 2-cyano-3-(difluoromethoxy)-N,N-dimethylbenzenesulfonamide (known from WO2006/056433), 2-cyano-3-(difluoromethoxy)-N-methylbenzenesulfonamide (known from WO2006/ 100288), 2-cyano-3-(difluoromethoxy)-N-ethylbenzenesulfonamide (known from WO2005/035486), 4-(difluoromethoxy)-N-ethyl-N-methyl-1,2-benzothiazole-1,1-dioxide 3-amine (known from WO2007/057407), N-[1-(2,3-di methylphenyl)-2-(3,5-dimethylphenyl)ethyl]-4,5-dihydro-1,3-thiazol-2-amine (known from WO2008/104503), {1'-[(2E)-3-( 4-chlorophenyl)prop-2-en-1-yl]-5-fluorospiro[indole-3,4'-piperidin]-1(2H)-yl}(2-chloropyridin-4-yl)methanone (known from WO2003 /106457), 3-(2,5-dimethylphenyl)-4-hydroxy-8-methoxy-1,8-diazaspiro[4.5]dec-3-en-2-one (known from WO2009/049851), 3-carbonate -(2,5-dimethylphenyl)-8-methoxy-2-oxo-1,8-diazaspiro[4.5]dec-3-en-4-yl ethyl (known from WO2009/049851), 4-(but-2- n-1-yloxy)-6-(3,5-dimethylpiperidin-1-yl)-5-fluoropyrimidine (known from WO2004/099160), (2,2,3,3,4,4,5,5-octafluoropentyl )(3,3,3-trifluoropropyl)malononitrile (known from WO2005/063094), (2,2,3,3,4,4,5,5-octafluoropentyl)(3,3,4,4,4-pentafluorobutyl) )malononitrile (known from WO2005/063094), 8-[2-(cyclopropylmethoxy)-4-(trifluoromethyl)phenoxy]-3-[6-(trifluoromethyl)pyridazin-3-yl]-3-azabicyclo[3.2.1] octane (known from WO2007/040280), phlomethoquin, PF1364 (CAS Reg. No. 1204776-60-2) (known from JP2010/018 586), 5-[5-(3,5-dichlorophenyl)-5-(trifluoromethyl)-4,5-dihydro-1,2-oxazol-3-yl]-2-(1H-1,2,4- triazol-1-yl)benzonitrile (known from WO2007/075459), 5-[5-(2-chloropyridin-4-yl)-5-(trifluoromethyl)-4,5-dihydro-1,2-oxazol-3- yl]-2-(1H-1,2,4-triazol-1-yl)benzonitrile (known from WO2007/075459), 4-[5-(3,5-dichlorophenyl)-5-(trifluoromethyl)-4, 5-dihydro-1,2-oxazol-3-yl]-2-methyl-N-{2-oxo-2-[(2,2,2-trifluoroethyl)amino]ethyl}benzamide (known from WO2005/085216) , 4-{[(6-chloropyridin-3-yl)methyl](cyclopropyl)amino}-1,3-oxazol-2(5H)-one, 4-{[(6-chloropyridin-3-yl)methyl] (2,2-difluoroethyl)amino}-1,3-oxazol-2(5H)-one, 4-{[(6-chloropyridin-3-yl)methyl](ethyl)amino}-1,3-oxazol- 2(5H)-one, 4-{[(6-chloropyridin-3-yl)methyl](methyl)amino}-1,3-oxazol-2(5H)-one (all known from WO2010/005692), NNI -0711 (known from WO2002/096882), 1-acetyl-N-[4-(1,1,1,3,3,3-hexafluoro-2-methoxypropan-2-yl)-3-isobutylphenyl]-N- isobutyryl-3,5-dimethyl-1H-pyrazole-4-carboxamide (known from WO2002/096882), 2-[2-({[3-bromo-1-(3-c) methyl loropyridin-2-yl)-1H-pyrazol-5-yl]carbonyl}amino)-5-chloro-3-methylbenzoyl]-2-methylhydrazinecarboxylate (known from WO2005/085216), 2-[2-({[ methyl 3-bromo-1-(3-chloropyridin-2-yl)-1H-pyrazol-5-yl]carbonyl}amino)-5-cyano-3-methylbenzoyl]-2-ethylhydrazinecarboxylate (known from WO2005/085216) , 2-[2-({[3-bromo-1-(3-chloropyridin-2-yl)-1H-pyrazol-5-yl]carbonyl}amino)-5-cyano-3-methylbenzoyl]-2-methylhydrazinecarboxylate of methyl (known from WO2005/085216), 2-[3,5-dibromo-2-({[3-bromo-1-(3-chloropyridin-2-yl)-1H-pyrazol-5-yl]carbonyl} methyl amino)benzoyl]-1,2-diethylhydrazinecarboxylate (known from WO2005/085216), 2-[3,5-dibromo-2-({[3-bromo-1-(3-chloropyridin-2-yl)- methyl 1H-pyrazol-5-yl]carbonyl}amino)benzoyl]-2-ethylhydrazinecarboxylate (known from WO2005/085216), (5RS,7RS;5RS,7SR)-1-(6-chloro-3-pyridylmethyl)- 1,2,3,5,6,7-hexahydro-7-methyl-8-nitro-5-propoxyimidazo[1,2-a]pyridine (known from WO2007/101369), 2-{6-[2-( 5-fluoropyridin-3-yl)-1,3-thiazol-5-yl]pyridin-2-yl }pyrimidine (known from WO2010/006713), 2-{6-[2-(pyridin-3-yl)-1,3-thiazol-5-yl]pyridin-2-yl}pyrimidine (known from WO2010/006713) , 1-(3-chloropyridin-2-yl)-N-[4-cyano-2-methyl-6-(methylcarbamoyl)phenyl]-3-{[5-(trifluoromethyl)-1H-tetrazol-1-yl] methyl}-1H-pyrazol-5-carboxamide (known from WO2010/069502), 1-(3-chloropyridin-2-yl)-N-[4-cyano-2-methyl-6-(methylcarbamoyl)phenyl]-3 -{[5-(trifluoromethyl)-2H-tetrazol-2-yl]methyl}-1H-pyrazol-5-carboxamide (known from WO2010/069502), N-[2-(tert-butylcarbamoyl)-4-cyano- 6-methylphenyl]-1-(3-chloropyridin-2-yl)-3-{[5-(trifluoromethyl)-1H-tetrazol-1-yl]methyl}-1H-pyrazole-5-carboxamide (known from WO2010/ 069502), N-[2-(tert-butylcarbamoyl)-4-cyano-6-methylphenyl]-1-(3-chloropyridin-2-yl)-3-{[5-(trifluoromethyl)-2H-tetrazol-2 -yl]methyl}-1H-pyrazole-5-carboxamide (known from WO2010/069502), (1E)-N-[(6-chloropyridin-3-yl)methyl]-N'-cyano-N-(2, 2-difluoroethyl)ethanimidamide (known from WO2008/009360), N-[2-(5-amino-1,3,4-thiadiazol-2-yl)-4-chloro-6-methylphenyl 1]-3-bromo-1-(3-chloropyridin-2-yl)-1H-pyrazole-5-carboxamide (known from CN102057925) and 2-[3,5-dibromo-2-({[3-bromo- Methyl 1-(3-chloropyridin-2-yl)-1H-pyrazol-5-yl]carbonyl}amino)benzoyl]-2-ethyl-1-methylhydrazinecarboxylate (known from WO2011/049233). Fungicides
[000184] (1) ergosterol biosynthesis inhibitors such as, for example (1.1) aldimorph (1704-28-5), (1.2) azaconazole (60207-31-0), (1.3) bitercanol (55179-31-2 ), (1.4) bromuconazole (116255-48-2), (1.5) cyproconazole (113096-99-4), (1.6) diclobutrazol (75736-33-3), (1.7) difenoconazole (119446-68-3), (1.8) diniconazole (83657-24-3), (1.9) diniconazole-M (83657-18-5), (1.10) dodemorph (1593-77-7), (1.11) dodemorph acetate (31717-87-0 ), (1.12) epoxiconazole (106325-08-0), (1.13) etaconazole (60207-93-4), (1.14) fenarimol (60168-88-9), (1.15) fenbuconazole (114369-43-6), (1.16) fenhexamid (126833-17-8), (1.17) fenpropidin (67306-00-7), (1.18) fenpropimorph (67306-03-0), (1.19) fluquinconazole (136426-54-5), (1.20 ) flurprimidol (56425-91-3), (1.21) flusilazol (85509-19-9), (1.22) flutriafol (76674-21-0), (1.23) furconazol (112839-33-5), (1.24) furconazol -cis (112839-32-4), (1.25) hexaconazole (79983-71-4), (1.26) imazalyl (60534-80-7), (1.27) imazalyl sulfate (58594-72-2), (1.28) imibenconazole ( 86598-92-7), (1.29) ipconazole (125225-28-7), (1.30) metconazole (125116-23-6), (1.31) myclobutanil (88671-89-0), (1.32) naftifin (65472- 88-0), (1.33) nuarimol (63284-71-9), (1.34) oxpoconazole (174212-12-5), (1.35) paclobutrazol (76738-62-0), (1.36) pefurazoate (101903-30- 4), (1.37) penconazole (66246-88-6), (1.38) piperalin (3478-94-2), (1.39) prochloraz (67747-09-5), (1.40) propiconazole (60207-90-1) , (1.41) prothioconazole (178928-70-6), (1.42) pyributicarb (88678-67-5), (1.43) pyrifenox (88283-41-4), (1.44) quinconazol (103970-75-8), ( 1.45) simeconazole (149508-90-7), (1.46) spiroxamine (118134-30-8), (1.47) tebuconazole (107534-96-3), (1.48) terbinafin (91161-71-6), (1.49) tetraconazole (112281-77-3), (1.50) triadimefon (43121-43-3), (1.51) triadimenol (89482-17-7), (1.52) tridemorph (81412-43-3), (1.53) triflumizole ( 68694-11-1), (1.54) triforine (26644-46-2), (1.55) triticonazole (131983-72-7), (1.56) uniconazole (83657-22-1), (1.57) uniconazole-p ( 83657-17-4), (1.58) viniconazole (77174-66-4), (1.59) voriconazol (137234-62-9), (1.60) 1-(4-chlorophenyl)-2-(1H-1,2,4-triazol-1-yl)cycloheptanol (129586-32-9), ( 1.61) Methyl 1-(2,2-dimethyl-2,3-dihydro-1H-inden-1-yl)-1H-imidazol-5-carboxylate (110323-95-0), (1.62) N'-{ 5-(difluoromethyl)-2-methyl-4-[3-(trimethylsilyl)propoxy]phenyl}-N-ethyl-N-methylimidoformamide, (1.63) N-ethyl-N-methyl-N'-{2-methyl- 5-(trifluoromethyl)-4-[3-(trimethylsilyl)propoxy]phenyl}imidoformamide and (1.64) O-[1-(4-methoxyphenoxy)-3,3-dimethylbutan-2-yl] 1H-imidazol-1- carbothioate (111226-71-2).
[000185] (2) Respiratory inhibitors (respiratory chain inhibitors) such as, for example, (2.1) bixafen (581809-46-3), (2.2) boscalid (188425-85-6), (2.3) carboxin (5234 -68-4), (2.4) diflumethorim (13033907-0), (2.5) fenfuran (24691-80-3), (2.6) fluopiram (658066-35-4), (2.7) flutolanil (66332-96-5 ), (2.8) fluxapiroxad (907204-31-3), (2.9) furametpyr (123572-88-3), (2.10) furmeciclox (60568-05-0), (2.11) mixture of isopyrazam of syn-epimeric racemate 1RS ,4SR,9RS and the 1RS,4SR,9SR anti-empimeric racemate (881685-58-1), (2.12) isopyrazam (anti-empimeric racemate), (2.13) isopyrazam (1R,4S,9S anti-empimeric enantiomer), (2.14) isopyrazam (1S,4R,9R anti-empimeric enantiomer), (2.15) isopyrazam (1RS,4SR,9RS syn-epimeric racemate), (2.16) isopyrazam (1R,4S,9R syn-epimeric enantiomer), (2.17 ) isopyrazam (1S,4R,9S syn-epimeric enantiomer), (2.18) mepronil (55814-41-0), (2.19) oxycarboxin (5259-88-1), (2.20) penflufen (494793-67-8), (2.21) penthiopyrad (183675-82-3), (2.22) silk xane (874967-67-6), (2.23) tifluzamid (130000-40-7), (2.24) 1-methyl-N-[2-(1,1,2,2-tetrafluoroethoxy)phenyl]-3-( trifluoromethyl)-1H-pyrazole-4-carboxamide, (2.25) 3-(difluoromethyl)-1-methyl-N-[2-(1,1,2,2-tetrafluoroethoxy)phenyl]-1H-pyrazole-4-carboxamide , (2.26) 3-(difluoromethyl)-N-[4-fluoro-2-(1,1,2,3,3,3-hexafluoropropoxy)phenyl]-1-methyl-1H-pyrazole-4-carboxamide, ( 2.27) N-[1-(2,4-dichlorophenyl)-1-methoxypropan-2-yl]-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxamide (1092400-95-7), ( 2.28) 5,8-difluoro-N-[2-(2-fluoro-4-{[4-(trifluoromethyl)pyridin-2-yl]oxy}phenyl)ethyl]quinazolin-4-amine (1210070-84-0 ) (known from WO2010025451), (2.29) N-[9-(dichloromethylene)-1,2,3,4-tetrahydro-1,4-methanonaphthalen-5-yl]-3-(difluoromethyl)-1-methyl- 1H-pyrazole-4-carboxamide, (2.30) N-[(1S,4R)-9-(dichloromethylene)-1,2,3,4-tetrahydro-1,4-methanonaphthalen-5-yl]-3-( difluoromethyl)-1-methyl-1H-pyrazole-4-carboxamide and (2.31) N-[(1R,4S)-9-(dichloromethylene-1,2,3,4-tetrahydro-1,4-methanonaphthalen-5- yl]-3-(difluoromethyl)-1 -methyl-1H-pyrazole-4-carboxamide.
[000186] (3) Respiratory inhibitors (respiratory chain inhibitors) that act on complex III of the respiratory chain such as, for example, (3.1) ametoctradin (865318-97-4), (3.2) amisulbrom (348635-87-0 ), (3.3) azoxystrobin (131860-33-8), (3.4) ciazofamid (120116-88-3), (3.5) coumethoxystrobin (850881-30-0), (3.6) coumoxystrobin (850881-70-8), (3.5) dimoxystrobin (141600-52-4), (3.6) enestroburin (238410-11-2) (known from WO 2004/058723), (3.9) famoxadone (131807-57-3) (known from WO 2004/058723 ), (3.10) fenamidone (161326-34-7) (known from WO 2004/058723), (3.11) phenoxystrobin (918162-02-4), (3.12) fluoxastrobin (361377-29-9) (known from WO 2004 /058723), (3,13) kresoxim-methyl (143390-89-0) (known from WO 2004/058723), (3.14) metominostrobin (133408-50-1) (known from WO 2004/058723), (315) orisastrobin (189892-69-1) (known from WO 2004/058723), (316) picoxystrobin (117428-22-5) (known from WO 2004/058723), (317) pyraclostrobin (175013-18-0) (known from WO 2004/058723), (318) pyramethostrobin (915410-70-7) (known from WO 2004/058723), (3.19) pyraoxystrobin (862588-11-2) (known from WO 2004/058723), (3.20) piribencarb (799247-52-2) (known from WO 2004/058723), (3.21) triclopyricarb (902760-40-1), (3.22) trifloxystrobin (141517-21-7) (known from WO 2004/058723), ( 3.23) (2E)-2-(2-{[6-(3-chloro-2-methylphenoxy)-5-fluoropyrimidin-4-yl]oxy}phenyl)-2-(methoxyimino)-N-methylethanamide (known from WO 2004/058723), (3.24) (2E)-2-(methoxyimino)-N-methyl-2-(2-{[({(1E)-1-[3-(trifluoromethyl)phenyl]ethylidene}amino) oxy]methyl}phenyl)ethanamide (known from WO 2004/058723), (3.25) (2E)-2-(methoxyimino)-N-methyl-2-{2-[(E)-({1-[3- (trifluoromethyl)phenyl]ethoxy}imino)methyl]phenyl}ethanamide (158169-73-4), (3.26) (2E)-2-{2-[({[(1E)-1-(3-{[( E)-1-fluoro-2-phenylethenyl]oxy}phenyl)ethylidene]amino}oxy)methyl]phenyl}-2-(methoxyimino)-N-methylethanamide (326896-28-0), (3.27) (2E)- 2-{2-[({[(2E,3E)-4-(2,6-dichlorophenyl)but-3-en-2-ylidene]amino}oxy)methyl]phenyl}-2-(me toxinimino)-N-methylethanamide, (3.28) 2-chloro-N-(1,1,3-trimethyl-2,3-dihydro-1H-inden-4-yl)pyridine-3-carboxamide (119899-14-8 ), (3.29) 5-methoxy-2-methyl-4-(2-{[({(1E)-1-[3-(trifluoromethyl)phenyl]ethylidene}amino)oxy]methyl}phenyl)-2,4 - dihydro-3H-1,2,4-triazol-3-one, (3.30) methyl (2E)-2-{2-[({cyclopropyl[(4-methoxyphenyl)imino]methyl}sulfanyl)methyl]phenyl} -3-methoxyprop-2-enoate (149601-03-6), (3.31) N-(3-ethyl-3,5,5-trimethylcyclohexyl)-3-(formylamino)-2-hydroxybenzamide (226551-21-9 ), (3.32) 2-{2-[(2,5-dimethylphenoxy)methyl]phenyl}-2-methoxy-N-methylacetamide (173662-97-0) and (3.33) (2R)-2-{2- [(2,5-dimethylphenoxy)methyl]phenyl}-2-methoxy-N-methylacetamide (394657-24-0).
[000187] (4) Inhibitors of mitosis and cell division such as, for example, (4.1) benomyl (17804-35-2), (4.2) carbendazim (10605-21-7), (4.3) chlorphenazol (3574-96 -7), (4.4) dietofencarb (87130-20-9), (4.5) ethaboxam (162650-77-3), (4.6) fluopicolid (239110-15-7), (4.7) fuberidazole (3878-19-1 ), (4.8) pencycuron (66063-05-6), (4.9) thiabendazole (148-79-8), (4.10) thiophanate-methyl (23564-05-8), (4.11) thiophanate (23564-06-9 ), (4.12) zoxamide (156052-68-5), (4.13) 5-chloro-7-(4-methylpiperidin-1-yl)-6-(2,4,6-trifluorophenyl)[1,2,4 ]triazolo[1,5-a]pyrimidine (214706-53-3) and (4.14) 3-chloro-5-(6-chloropyridin-3-yl)-6-methyl-4-(2,4,6- trifluorophenyl)pyridazine (1002756-87-7).
[000188] (5) Compounds with multisite activity such as, for example (5.1) Bordeaux mixture (8011-63-0), (5.2)captafol (2425-06-1), (5.3)captan (133-06-2 ) (known from WO 02/12172), (5.4) chlorothalonil (1897-45-6), (5.5) copper-based preparations such as copper hydroxide (20427-59-2), (5.6) copper naphthenate ( 1338-02-9), (5.7) copper oxide (1317-39-1), (5.8) copper oxychloride (1332-40-7), (5.9) copper sulfate (7758-98-7), ( 5.10) dichlofluanid (1085-98-9), (5.11) dithionone (3347-22-6), (5.12) dodine (2439-10-3), (5.13) dodine free base, (5.14) ferbam (14484-64 -1), (5.15) fluorofolpet (719-96-0), (5.16) folpet (13307-3), (5.17) guazatine (108173-90-6), (5.18) guazatine acetate, (5.19) iminoctadine (13516 -27-3), (5.20) iminoctadine albesylate (16920206-6), (5.21) iminoctadine triacetate (57520-17-9), (5.22) mancobre (53988-93-5), (5.23) mancozeb (8018 -01-7), (5.24) maneb (12427-382), (5.25) metal (9006-42-2), (5.26) zinc metal (9006-42-2), (5.27) oxine-cobr and (10380-28-6), (5.28) propamidine (104-32-5), (5.29) propineb (12071-83-9), (5.30) sulfur and sulfur-based preparations such as calcium polysulfide ( 7704-34-9), (5.31) tiram (137-26-8), (5.32) tolylfluanid (731-27-1), (5.33) zineb (12122-67-7) and (5.34) ziram (137- 30-4).
[000189] (6) Resistance inducers such as, for example (6.1) acibenzolar-S-methyl (135158-54-2), (6.2) isothianil (224049-04-1), (6.3) probenazol (27605-76 -1) and (6.4) tiadinil (223580-51-6).
[000190] (7) Inhibitors of amino acid and protein biosynthesis such as, for example (7.1) andoprim (23951-85-1), (7.2) blasticidin-S (2079-00-7), (7.3) cyprodinil ( 121552-61-2), (7.4) kasugamycin (6980-18-3), (7.5) kasugamycin hydrochloride hydrate (19408-46-9), (7.6) mepanipyrim (110235-47-7), (7.7) pyrimethanil (5311228-0) and (7.8) 3-(5-fluoro-3,3,4,4-tetramethyl-3,4-dihydroisoquinolin-1-yl)quinoline (861647-32-7) (known from WO2005070917).
[000191] (8) Inhibitors of ATP production, such as, for example, (8.1) fentin acetate (900-95-8), (8.2) fentin chloride (639-58-7), (8.3) hydroxide of fentin (76-87-9) and (8.4) silthiofam (175217-20-6).
[000192] (9) Cell wall synthesis inhibitors such as, for example (9.1) bentiavalcarb (177406-68-7), (9.2) dimethomorph (11048870-5), (9.3) flumorph (211867-47-9) , (9.4) iprovalicarb (140923-17-7), (9.5) mandipropamide (374726-62-2), (9.6) polyoxins (11113-80-7), (9.7) polyoxorim (22976-86-9), ( 9.8) validamycin A (37248-47-8) and (9.9) valifenalate (283159-94-4; 283159-90-0).
[000193] (10) Inhibitors of lipid and membrane synthesis such as, for example (10.1) biphenyl (92-52-4), (10.2) chlorneb (2675-776), (10.3) dichloran (99-30- 9), (10.4) edifenphos (17109-49-8), (10.5) etridiazole (2593-15-9), (10.6) iodocarb (55406-53-6), (10.7) iprobenfos (26087-47-8) , (10.8) isoprothiolane (50512-35-1), (10.9) propamocarb (25606-41-1), (10.10) propamocarb hydrochloride (25606-41-1), (10.11) prothiocarb (19622-08-3) , (10.12) pyrazolophos (13457-18-6), (10.13) quintazene (82-68-8), (10.14) technazene (117-18-0) and (10.15) tolclophos-methyl (57018-04-9) .
[000194] (11) Inhibitors of melanin biosynthesis such as, for example (11.1) carpropamid (104030-54-8), (11.2) diclocimet (139920-32-4), (11.3) fenoxanil (115852-48-7 ), (11.4) phthalide (27355-22-2), (11.5) pyroquilone (57369-32-1), (11.6) tricyclazole (41814-78-2) and (11.7) (3-methyl-1-[( 2,2,2-Trifluoroethyl 4-methylbenzoyl)amino]butan-2-yl}carbamate (851524-22-6) (WO2005042474).
[000195] (12) Inhibitors of nucleic acid synthesis such as, for example (12.1) benalaxyl (71626-11-4), (12.2) benalaxyl-M (kiralaxyl) (98243-83-5), (12.3) bupirimate (41483-43-6), (12.4) clozilacon (6793285-8), (12.5) dimethirimol (5221-53-4), (12.6) ethirimol (23947-60-6), (12.7) furalaxyl (57646-30 -7), (12.8) hyhexazol (10004-44-1), (12.9) metalaxyl (57837-19-1), (12.10) metalaxyl-M (mefenoxam) (70630-17-0), (12.11) ofurace ( 58810-48-3), (12.12) oxadixyl (77732-09-3) and (12.13) oxolinic acid (14698-29-4).
[000196] (13) Inhibitors of signal transduction such as, for example (13.1) clozolinate (84332-86-5), (13.2) fenpiclonil (74738-17-3), (13.3) fludioxonil (131341-86-1 ), (13.4) iprodione (36734-19-7), (13.5) procymidone (32809-16-8), (13.6) quinoxyphen (124495-18-7) and (13.7) vinclozoline (50471-44-8).
[000197] (14) Uncouplings such as, for example, (14.1) binapacril (485-31-4), (14.2) dinocap (131-72-6), (14.3) ferimzone (89269-64-7), ( 14.4) fluazinam (79622-59-6) and (14.5) meptildinocap (131-72-6).
[000198] (15) Other compounds such as, for example (15.1) bethiazole (21564-17-0), (15.2) betoxazine (163269-30-5), (15.3) capsimycin (70694-08-5), ( 15.4) carvone (99-49-0), (15.5) cynomethionate (2439-01-2), (15.6) pyriophenone (clazafenone) (68804661-9), (15.7) cufraneb (11096-18-7), (15.8 ) ciflufenamid (180409-60-3), (15.9) cymoxanil (57966-95-7), (15.10) cyprosulfamide (221667-31-8), (15.11) dazomet (533-74-4), (15.12) debacarb (62732-91-6), (1513) dichlorophen (97-23-4), (1514) diclomezine (62865-36-5), (1515) difenzoquat (49866-87-7), (1516) difenzoquat methylsulfate (43222-48-6), (15.17) diphenylamine (122-39-4), (15.18) echomate, (15.19) phenpyrazamine (473798-59-3), (15.20) flumetover (154025-04-4), ( 15.21) fluoroimide (41205-21-4), (15.22) flusulfamide (106917-52-6), (15.23) fluthianil (304900-25-2), (15.24) fosetyl-aluminum (39148-24-8), ( 15.25) fosetyl-calcium, (15.26) fosetyl-sodium (39148-16-8), (15.27) hexachlorobenzene (118-74-1), (15.28) irumamycin (81604-73-1), (15.29 ) metasulfocarb (66952-49-6), (15.30) methyl isothiocyanate (55661-6), (15.31) metrafenone (220899-03-6), (15.32) mildiomycin (6752771-3), (15.33) natamycin (7681 -93-8), (15.34) nickel dimethyldithiocarbamate (15521-65-0), (15.35) nitrothal-isopropyl (10552-74-6), (15.36) octylinone (26530-20-1), (15.37) oxamocarb (917242-12-7), (15.38) oxifentiin (34407-87-9), (15.39) pentachlorophenol and salts (87-86-5), (15.40) phenothrin, (15.41) phosphorous acid and salts thereof (13598- 36-2), (15.42) propamocarb-fosetylate, (15.43) propanosine-sodium (88498-02-6), (15.44) proquinazid (189278-12-4), (15.45) pyrimorph (868390-90-3), (15.45e) (2E)-3-(4-tert-butylphenyl)-3-(2-chloropyridin-4-yl)-1-(morpholin-4-yl)prop-2-en-1-one (1231776 -28-5), (15.45z) (2Z)-3-(4-tert-butylphenyl)-3-(2-chloropyridin-4-yl)-1-(morpholin-4-yl)prop-2-en -1-one (1231776-29-6), (15.46) pyrrolnitrine (1018-71-9) (known from EP-A 1 559 320), (15.47) tebufloquine (376645-78-2), (15.48) teclophthalam (76280-91-6), (15.49) tolnifanide (3 04911-98-6), (15.50) triazoxide (72459-58-6), (15.51) triclamide (70193-21-4), (15.52) zarilamid (84527-51-5), (15.53) 2-methylpropanoate (3S,6S,7R,8R)-8-benzyl-3-[({3-[(isobutyryloxy)methoxy]-4-methoxypyridin-2-yl}carbonyl)amino]-6-methyl-4,9-dioxo -1,5-dioxonan-7-yl (517875-34-2) (known to known from WO2003035617), (15.54) 1-(4-{4-[(5R)-5-(2,6-difluorophenyl) -4,5-dihydro-1,2-oxazol-3-yl]-1,3-thiazol-2-yl}piperidin-1-yl)-2-[5-methyl-3-(trifluoromethyl)-1H- pyrazol-1-yl]ethanone (1003319-79-6) (known from WO 2008013622), (15.55) 1-(4-{4-[(5S)-5-(2,6-difluorophenyl)-4,5 -dihydro-1,2-oxazol-3-yl]-1,3-thiazol-2-yl}piperidin-1-yl)-2-[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1- yl]ethanone (1003319-80-9) (known from WO 15.56), (15.56) 1-(4-{4-[5-(2,6-difluorophenyl)-4,5-dihydro-1,2-oxazole -3-yl]-1,3-thiazol-2-yl}piperidin-1-yl)-2-[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]ethanone (1003318-67- 9) (known from WO 15.57), (15.57) 1-(4-methoxyphenoxy)-3,3-dimethylbut 1H-imidazol-1-carboxylate an-2-yl (111227-17-9), (15.58) 2,3,5,6-tetrachloro-4-(methylsulfonyl)pyridine (13108-52-6), (15.59) 2,3-dibutyl-6 -chlorothieno[2,3-d]pyrimidin-4(3H)-one (221451-58-7), (15.60) 2,6-dimethyl-1H,5H-[1,4]dithiino[2,3-c : 5,6-c']dipyrrole-1,3,5,7(2H,6H)-tetrone, (15.61) 2-[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]- 1-(4-{4-[(5R)-5-phenyl-4,5-dihydro-1,2-oxazol-3-yl]-1,3-thiazol-2-yl}piperidin-1-yl) ethanone (1003316-53-7) (known from WO 15.62), (15.62) 2-[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]-1-(4-{4-[( 5S)-5-phenyl-4,5-dihydro-1,2-oxazol-3-yl]-1,3-thiazol-2-yl}piperidin-1-yl)ethanone (1003316-54-8) (known of WO 2008013622), (15.63) 2-[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]-1-{4-[4-(5-phenyl-4,5-dihydro-1 ,2-oxazol-3-yl)-1,3-thiazol-2-yl]piperidin-1-yl}ethanone (1003316-51-5) (known from WO 2008013622), (1564) 2-butoxy-6- iodo-3-propyl-4H-chromen-4-one, (15.65) 2-chloro-5-[2-chloro-1-(2,6-difluoro-4-methoxyphenyl)-4-methyl-1H-imidazol- 5-yl]pyridine, (15.66) 2-phenylphenol and salts (90-4 3-7), (15.67) 3-(4,4,5-trifluoro-3,3-dimethyl-3,4-dihydroisoquinolin-1-yl)quinoline (861647-85-0) (known from WO2005070917), ( 15.68) 3,4,5-trichloropyridine-2,6-dicarbonitrile (17824-85-0), (15.69) 3-[5-(4-chlorophenyl)-2,3-dimethyl-1,2-oxazolidin-3 - yl]pyridine, (15.70) 3-chloro-5-(4-chlorophenyl)-4-(2,6-difluorophenyl)-6-methylpyridazine, (15.71) 4-(4-chlorophenyl)-5-(2, 6-difluorophenyl)-3,6-dimethylpyridazine, (15.72) 5-amino-1,3,4-thiadiazol-2-thiol, (15.73) 5-chloro-N'-phenyl-N'-(prop-2- in-1-yl)thiophene-2-sulfonohydrazide (134-31-6), (15.74) 5-fluoro-2-[(4-fluorobenzyl)oxy]pyrimidin-4-amine (1174376-11-4) (known from WO2009094442), (15.75) 5-fluoro-2-[(4-methylbenzyl)oxy]pyrimidin-4-amine (1174376-25-0) (known from WO2009094442), (15.76) 5-methyl-6-octyl[ 1,2,4]triazolo[1,5-a]pyrimidin-7-amine, (15.77) Ethyl (2Z)-3-amino-2-cyano-3-phenylprop-2-enoate, (15.78) N' -(4-{[3-(4-chlorobenzyl)-1,2,4-thiadiazol-5-yl]oxy}-2,5-dimethylphenyl)-N-ethyl-N-methylimidoformamide, (15.79) N-( 4-chlorobenzyl)-3-[3- methoxy-4-(prop-2-yn-1-yloxy)phenyl]propanamide, (15.80) N-[(4-chlorophenyl)(cyano)methyl]-3-[3-methoxy-4-(prop-2- n-1-yloxy)phenyl]propanamide, (15.81) N-[(5-bromo-3-chloropyridin-2-yl)methyl]-2,4-dichloropyridine-3-carboxamide, (15.82) N-[1- (5-bromo-3-chloropyridin-2-yl)ethyl]-2,4-dichloropyridine-3-carboxamide, (15.83) N-[1-(5-bromo-3-chloropyridin-2-yl)ethyl]- 2-fluoro-4-iodopyridine-3-carboxamide, (15.84) N-{(E)-[(cyclopropylmethoxy)imino][6-(difluoromethoxy)-2,3-difluorophenyl]methyl}-2-phenylacetamide (221201- 92-9), (15.85) N-{(Z)-[(cyclopropylmethoxy)imino][6-(difluoromethoxy)-2,3-difluorophenyl]methyl}-2-phenylacetamide (221201-92-9), (15.86 ) N'-{4-[(3-tert-butyl-4-cyano-1,2-thiazol-5-yl)oxy]-2-chloro-5-methylphenyl}-N-ethyl-N-methylimidoformamide, ( 15.87) N-methyl-2-(1-{[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]acetyl}piperidin-4-yl)-N-(1,2,3,4 -tetrahydronaphthalen-1-yl)-1,3-thiazole-4-carboxamide (922514-49-6) (known from WO 2007014290), (1588) N-methyl-2-(1-{[5-methyl-3 -(trifluoromethyl)-1H-pyr zol-1-yl]acetyl}piperidin-4-yl)-N-[(1R)-1,2,3,4-tetrahydronaphthalen-1-yl]-1,3-thiazole-4-carboxamide (922514 -07-6) (known from WO 2007014290), (15.89) N-methyl-2-(1-{[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]acetyl}piperidin-4- yl)-N-[(1S)-1,2,3,4-tetrahydronaphthalen-1-yl]-1,3-thiazole-4-carboxamide (922514-48-5) (known from WO 15.90), (15.90) pentyl {6-[({[(1-methyl-1H-tetrazol-5-yl)(phenyl)methylidene]amino}oxy)methyl]pyridin-2-yl}carbamate, (15.91) phenazine acid- 1-carboxylic, (15.92) quinolin-8-ol (134-31-6), (15.93) quinolin-8-ol sulfate (2:1) (134-31-6) and (15.94) (6-[ tert-butyl ({[(1-methyl-1H-tetrazol-5-yl)(phenyl)methylene]amino}oxy)methyl]pyridin-2-yl}carbamate.
[000199] (16) Other compounds such as, for example (16.1) 1-methyl-3-(trifluoromethyl)-N-[2'-(trifluoromethyl)biphenyl-2-yl]-1H-pyrazole-4-carboxamide, (16.2) N-(4'-chlorobiphenyl-2-yl)-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxamide, (16.3) N-(2',4'-dichlorobiphenyl-2- yl)-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxamide, (16.4) 3-(difluoromethyl)-1-methyl-N-[4'-(trifluoromethyl)biphenyl-2-yl]- 1H-pyrazole-4-carboxamide, (16.5) N-(2',5'-difluorobiphenyl-2-yl)-1-methyl-3-(trifluoromethyl)-1H-pyrazole-4-carboxamide, (16.6) 3- (difluoromethyl)-1-methyl-N-[4'-(prop-1-in-1-yl)biphenyl-2-yl]-1H-pyrazole-4-carboxamide, (16.7) 5-fluoro-1,3 -dimethyl-N-[4'-(prop-1-yn-1-yl)biphenyl-2-yl]-1H-pyrazole-4-carboxamide, (16.8) 2-chloro-N-[4'-(prop -1-yn-1-yl)biphenyl-2-yl]pyridine-3-carboxamide, (16.9) 3-(difluoromethyl)-N-[4'-(3,3-dimethylbut-1-yn-1-yl )biphenyl-2-yl]-1-methyl-1H-pyrazole-4-carboxamide, (16.10) N-[4'-(3,3-dimethylbut-1-yn-1-yl)biphenyl-2-yl] - 5-fluoro-1,3-dimethyl-1H-pyrazole-4-carboxamide, (16.11) 3-(di fluoromethyl)-N-(4'-ethynylbiphenyl-2-yl)-1-methyl-1H-pyrazole-4-carboxamide, (16.12) N-(4'-ethynylbiphenyl-2-yl)-5-fluoro-1, 3-dimethyl-1H-pyrazole-4-carboxamide, (16.13) 2-chloro-N-(4'-ethynylbiphenyl-2-yl)pyridine-3-carboxamide, (16.14) 2-chloro-N-[4'- (3,3-dimethylbut-1-yn-1-yl)biphenyl-2-yl]pyridine-3-carboxamide, (16.15) 4-(difluoromethyl)-2-methyl-N-[4'-(trifluoromethyl)biphenyl -2-yl]-1,3-thiazol-5-carboxamide, (16.16) 5-fluoro-N-[4'-(3-hydroxy-3-methylbut-1-yn-1-yl)biphenyl-2- yl]-1,3-dimethyl-1H-pyrazole-4-carboxamide, (16.17) 2-chloro-N-[4'-(3-hydroxy-3-methylbut-1-yn-1-yl)biphenyl-2 -yl]pyridine-3-carboxamide, (16.18) 3-(difluoromethyl)-N-[4'-(3-methoxy-3-methylbut-1-yn-1-yl)biphenyl-2-yl]-1- methyl-1H-pyrazole-4-carboxamide, (16.19) 5-fluoro-N-[4'-(3-methoxy-3-methylbut-1-yn-1-yl)biphenyl-2-yl]-1,3 -dimethyl-1H-pyrazole-4-carboxamide, (16.20) 2-chloro-N-[4'-(3-methoxy-3-methylbut-1-yn-1-yl)biphenyl-2-yl]pyridine-3 -carboxamide, (16.21) (5-bromo-2-methoxy-4-methylpyridin-3-yl)(2,3,4-trimethoxy-6-methylphenyl)methanon a (known from EP-A 1 559 320), (16.22) N-[2-(4-{[3-(4-chlorophenyl)prop-2-yn-1-yl]oxy}-3-methoxyphenyl)ethyl ]-N2-(methylsulfonyl)valinamide (220706-93-4), (16.23) 4-oxo-4-[(2-phenylethyl)amino]butanoic acid and (16.24) {6-[({[(Z)- but-3-yn-1-yl (1-methyl-1H-tetrazol-5-yl)(phenyl)methylene]amino}oxy)methyl]pyridin-2-yl}carbamate.
[000200] All the indicated mixing partners of classes (1) to (16), if the functional groups so permit, can optionally form salts with suitable bases or acids.
[000201] A mixture with other known active compounds, such as herbicides, or with fertilizers and growth regulators, protective compounds or semiochemicals, or with agents to improve the properties of plants, is also possible.
[000202] When used as insecticides, the active compounds according to the invention can also be present in their commercially available formulations and in the forms of use prepared from these formulations as a mixture with synergistic effect. Synergistic compounds are compounds that enhance the action of the active compounds, without any need to add synergistic compounds to be active itself.
[000203] When used as insecticides, the active compounds according to the invention may also be present in their commercially available formulations and in the forms of use prepared from these formulations as a mixture with inhibitors that reduce the degradation of the active compound after use in the plant environment, on the surface of plant parts or plant tissue.
[000204] According to the invention it is possible to treat all plants and plant parts. It is understood that "plants" means, in the present context, all plants and plant populations, such as wild desired and unwanted plants or crops (including crops endemic to a region). Crop plants can be plants that can be obtained by conventional or other cultivation and optimization methods, such as biotechnology and genetic engineering methods, or by a combination of these methods, including transgenic plants and including plant cultivars capable or not capable of being protected by the rights of the person responsible for the development of the plant. "Plant parts" are understood to mean all parts, aerial and underground, and organs of plants, such as shoots, leaves, flowers and roots, including by way of example leaves, needles, stalks, stems, flowers, bodies of fruits, fruits and seeds as well as roots, tubers and rhizomes. Plant parts further include harvested material and vegetative and generative propagation material, for example cuttings, tubers, rhizomes, seedlings and seeds.
[000205] The treatment according to the invention with the active compounds, of plants and plant parts is carried out directly or by letting the compounds act on the environment, habitat or storage through the usual treatment methods, for example, by means of dipping, spraying, vaporizing, nebulizing, spreading, applying, injecting and, in the case of propagating material, particularly in the case of seeds, even by application with one or more layers.
[000206] As already mentioned, it is possible to treat all plants and their parts according to the invention in a preferred embodiment, wild plant species and cultivars are treated, or those obtained through conventional biological reproduction methods, such as as sectional or protoplastic fusion and also parts thereof. in a more preferred embodiment, transgenic plants and cultivars obtained by genetic engineering methods are treated, if appropriate in combination with conventional methods (Genetically Modified Organisms) and parts thereof. The terms "parts", "parts of plants", "parts derived from plants" are explained above.
[000207] More preferably, the plants of the cultivars, each commercially available or in use, are treated in accordance with the invention. Cultivars are understood to be plants with new properties ("characteristics") and which have been obtained by conventional breeding, mutagenesis or recombinant DNA techniques. These plants can be cultivars, biotypes and genotypes.
[000208] Depending on the plant species or cultivar, its location and growing conditions (soil, climate, vegetation period, diet), the treatment according to the invention may also result in superaddition ("synergistic") effects . For example, possibilities include reduced application rates and/or a broadening of the spectrum of activity and/or an increase in the activity of substances and compositions, which can be used according to the invention, allow for better, larger plant growth. tolerance to high or low temperatures, greater tolerance to periods of drought, rain or soil salt content, increased development when flowering, easier harvesting, accelerated maturation, better crop yield, better quality and/or nutritional value of harvested products , better stability in terms of storage and/or processing of the harvested products, which allows the effects that were normally expected to be exceeded.
[000209] The preferred transgenic plants or cultivars (obtained through genetic engineering), which will be treated in accordance with the present invention, include all plants that, by virtue of their genetic modification, received genetic material which confers particularly advantageous characteristics and useful to these plants. Examples of these characteristics are: better plant growth, greater tolerance to high or low temperatures, greater tolerance to periods of drought, rain, or salt content in the soil, increased flowering development, easier harvesting, accelerated maturation, better yield. harvest, better quality and/or nutritional value of harvested products, better stability in terms of storage and/or processing of harvested products. Other particularly important examples of these characteristics are a better defense of plants against animals and microbial pests such as insects, mites, phytopathogenic fungi, bacteria and/or viruses and also a greater tolerance of plants towards active ingredients in terms of herbicides. Examples of transgenic plants that can be mentioned are important cultivated plants such as cereals (wheat, rice), corn, soybeans, potatoes, sugar beet, tomatoes, peas and other types of vegetables, cotton, oilseed rape and also fruit plants (apple, pear, citrus and grapes), with particular emphasis on corn, soy, potatoes, cotton and oilseed rape. The "characteristics" that are particularly highlighted are the defense of plants against insects, arachnids, nematodes and slugs and snails due to toxins formed in plants, especially those that form in plants through genetic material from Bacillus thuringiensis (by example, by the genes CryIA(a), CryIA(b), CryIA(c), CryIIA, CryIIIA, CryIIIB2, Cry9c Cry2Ab, Cry3Bb and CryIF and also combinations thereof) (referred to below as "Bt plants"). Characteristics that are also particularly highlighted are the optimized defense by plants against fungi, bacteria and viruses by acquired systemic resistance (SAR), sistemin, phytoalexins, elicitors and also resistance to correspondingly expressed genes and proteins and toxins. The “characteristics” that are particularly highlighted are the increased tolerance of plants to certain active herbicidal compounds, eg imidazolinones, sulfonylureas, glyphosate or phosphinothricin (eg the “PAT” gene) Genes that transmit the desired characteristics in question may equally be present in combinations with one another in transgenic plants. Examples of “Bt plants” include corn varieties, cotton varieties, soybean varieties and potato varieties, which are sold under the trade names YIELD GARD® (eg corn, cotton, soybeans), KnockOut® (by example corn), StarLink® (eg corn), Bollgard® (cotton), Nucotn® (cotton) and NewLeaf® (potato) Examples of herbicide tolerant plants include corn varieties, cotton varieties, and cotton varieties. soybeans that are sold under the trade names Roundup Ready® (tolerance to glyphosate, for example corn, cotton, soybeans), Liberty Link® (tolerance to phosphinothricin, for example oilseed rape), IMI® (tolerance to imidazolinones) and STS® ( tolerance to sulfonylureas, for example maize). Herbicide resistant plants (plants grown in a conventional way to develop tolerance to herbicides) that may be mentioned include those varieties marketed under the Clearfield® designation (eg corn). Naturally, these statements apply equally to cultivars, which have these genetic characteristics or genetic characteristics that are still to be developed and that will be developed and/or commercialized in the future.
[000210] The indicated plants can, according to the invention, be treated in a particularly advantageous manner with the compounds of the General Formula (I) and/or with active compound mixtures according to the invention. The preferred ranges given above for the active compounds or mixtures apply equally to the treatment of these plants. Particular attention is paid to the treatment of plants with the compounds and mixtures specifically mentioned in this text.
[000211] The compounds according to the invention not only act against pests of plants, hygiene and stored products but also in the veterinary sector against animal parasites (ectoparasites and endoparasites), such as hard ticks, soft ticks, demodex, mites leaves, flies (sucking and licking), parasitic fly larvae, lice, hair louse, feather louse and fleas. These parasites include:
[000212] From the order Anopluride, for example Haematopinus spp., Linognathus spp., Pediculus spp., Phtirus spp. and Solenopotes spp.
From the order Mallophagida and the suborders Amblycerina and Ischnocerina, for example, Trimenopon spp., Menopon spp., Trinoton spp., Bovicola spp., Werneckiella spp., Lepikentron spp., Damalina spp., Trichodectes. and Felicola spp.
From the order Diptera and the suborders Nematocerin and Brachycerina, for example, Aedes spp., Anopheles spp., Culex spp., Simulium spp., Eusimulium spp., Phlebotomus spp., Lutzomyia spp., Culicoides spp. spp., Hybomitra spp., Atylotus spp., Tabanus spp., Haematopota spp., Philipomyia spp., Braula spp., Musca spp., Hydrotaea spp., Stomoxys spp., Haematobia spp., Morellia spp., Morellia spp. , Glossina spp., Calliphora spp., Lucilia spp., Chrysomyia spp., Wohlfahrtia spp., Sarcophaga spp., Oestrus spp., Hypoderma spp., Gasterophilus spp., Hippobosca spp., Lipoptena spp. and Melophagus spp.
[000215] From the order of Siphonapterida, for example, Pulex spp., Ctenocephalides spp., Xenopsylla spp. and Ceratophyllus spp.
[000216] From the order Heteropterides, for example Cimex spp., Triatoma spp., Rhodnius spp. and Panstrongylus spp.
[000217] From the order of the Blattarida, for example, Blatta orientalis, Periplaneta americana, Blattella germanica and Supella spp.
[000218] From the subclass of mites (Acarina) and the orders Metastigmata and Mesostigmata, for example, Argas spp., Ornithodorus spp., Otobius spp., Ixodes spp., Amblyomma spp., Boophilus spp., Dermacentor spp. Haemophysalis spp., Hyalomma spp., Rhipicephalus spp., Dermanyssus spp., Raillietia spp., Pneumonyssus spp., Sternostoma spp. and Varroa spp.
[000219] From the order of Actinedida (Prostigmata) and Acaridida (Astigmata), for example, Acarapis spp., Cheyletiella spp., Ornithocheyletia spp., Myobia spp., Psorergates spp., Demodex spp., Tromppro phorus spp. , Acarus spp., Tyrophagus spp., Caloglyphus spp., Hypodectes spp., Pterolichus spp., Psoroptes spp., Chorioptes spp., Otodectes spp., Sarcoptes spp., Notoedres spp. and Laminosioptes spp.
[000220] The active compounds of Formula (I) according to the invention are also suitable for the control of arthropods that attack livestock, for example, cattle, sheep, goats, horses, mules, camelid, buffaloes, rabbits, chickens, turkeys, ducks, geese, bees, other domestic animals such as, for example, dogs, cats, caged birds, aquarium fish and laboratory animals, for example hamsters, guinea pigs, rats and mice. It is intended, with the control of these arthropods, to reduce the cases of death and reduced productivity (of meat, milk, wool, skins, eggs, honey, etc.), enabling a more economical and easier livestock exploitation through the use of compounds actives according to the invention.
[000221] The active compounds according to the invention are used in the veterinary sector and in livestock, in a known way, through enteral administration in the form of, for example, tablets, capsules, potions, baths, granules, pastes, bolus , feed-through process and suppositories, by means of parenteral administration, such as, for example, by means of injection (intramuscular, subcutaneous, intravenous, intraperitoneal and the like), implants, nasal administration, dermal use in the form of, for example, soaking or bathing, spraying, general or local application, washing and powdering, and even with the help of molded articles containing the active compound, such as collars, ear tags, tail tags, limb bands, marking devices and similar.
[000222] When used for livestock, poultry, domestic animals and the like, the active compounds of Formula (I) can be used as formulations (eg powders, emulsions, fluids) comprising the active compounds in an amount of 1 to 80% by weight, either directly or afterwards or after a dilution of 100 to 10 000 times or can be used as a chemical bath.
[000223] It was also found that the compounds according to the invention have a strong insecticidal action against insects that destroy industrial materials.
Preferred but non-limiting examples include the following insects: beetles such as Hylotrupes bajulus, Chlorophorus pilosis, Anobium punctatum, Xestobium rufovillosum, Ptilinus pecticornis, Dendrobium pertinex, Ernobius mollis, Priobium carpini, Lyctus Lyctus brunneus, brunneus Lyctus linearis, Lyctus pubescens, Trogoxylon aequale, Minthes rugicollis, Xyleborus spec., Tryptodendron spec., Apate monachus, Bostrychus capucins, Heterobostrychus brunneus, Sinoxylon spec., Dinoderus minutus; dermatomes such as Sirex juvencus, Urocerus gigas, Urocerus gigas taignus, Urocerus augur; termites, such as Kalotermes flavicollis, Cryptotermes brevis, Heterotermes indicola, Reticulitermes flavipes, Reticulitermes santonensis, Reticulitermes lucifugus, Mastotermes darwiniensis, Zootermopsis nevadensis, Coptotermes formosanus; silver fish such as Lepisma saccarina.
[000225] Industrial materials are assumed in the present context to be inanimate materials, such as preferably plastics, adhesives, gums, paper and cardboard, leather, wood, processed wood products and coating compositions.
[000226] Ready-to-use compositions may optionally further comprise other insecticides and optionally one or more fungicides.
[000227] Furthermore, the compounds according to the invention can be used in the protection of objects that come into contact with salt water or brackish water, in particular hulls, meshes, nets, buildings, anchorages and signaling systems against incrustation.
[000228] Furthermore, the compounds according to the invention can be used as antifouling compositions, alone or in combination with other active compounds.
[000229] The active compounds are also suitable for the control of animal pests in the domestic sector, in the hygiene sector and in the protection of stored products, in particular in the control of insects, arachnids and mites, which are found in closed spaces, for example , home, industrial buildings, offices, vehicle cabins and the like. They can be used to control these pests themselves or in combination with other active and auxiliary compounds in household insecticide products. They are effective against sensitive and resistant species and against all stages of development. These pests include:
[000230] From the order of Scorpionidea, for example, Buthus occitanus.
[000231] From the order Acarina, for example, Argas persicus, Argas reflexus, Bryobia spp., Dermanyssus gallinae, Glyciphagus domesticus, Ornithodorus moubat, Rhipicephalus sanguineus, Trombicula alfreddugesi, Neutrombicula autumnalis, Dermatoophagus forphagides p.
[000232] From the order of Araneae, eg Aviculariidae, Araneidae.
[000233] From the order of Opiliones, for example, Pseudoscorpiones chelifer, Pseudoscorpiones cheiridium, Opiliones phalangium.
[000234] From the order of the Isopoda, for example, Oniscus asellus, Porcellio scaber.
[000235] From the order of Diplopoda, for example, Blaniulus guttulatus, Polydesmus spp.
[000236] From the order of Chilopoda, for example, Geophilus spp.
[000237] From the order of Zygentoma, for example, Ctenolepisma spp., Lepisma saccharina, Lepismodes inquilinus.
[000238] From the order of Blattaria, for example, Blatta orientalies, Blattella germanica, Blattella asahinai, Leucophaea maderae, Panchlora spp., Parcoblatta spp., Periplaneta australasiae, Periplaneta americana, Periplaneta brunnea, Periplaneta longi.
[000239] From the order of the Saltatoria, for example, Acheta domesticus.
[000240] From the order of Dermaptera, for example, Forficula auricularia.
[000241] From the order of the Isoptera, for example, Kalotermes spp., Reticulitermes spp.
[000242] From the order of Psocoptera, for example, Lepinatus spp., Liposcelis spp.
[000243] From the order Coleoptera, for example, Anthrenus spp., Attagenus spp., Dermestes spp., Latheticus oryzae, Necrobia spp., Ptinus spp., Rhizopertha dominica, Sitophilus granarius, Sitophilus oryzae, Sitophilus panicium.
[000244] From the order Diptera, for example, Aedes aegypti, Aedes albopictus, Aedes taeniorhynchus, Anopheles spp., Calliphora erythrocephala, Chrysozona pluvialis, Culex quinquefasciatus, Culex pipiens, Culex tarsalis, Phlecania cannicularis. spp., Sarcophaga carnaria, Simulium spp., Stomoxys calcitrans, Tipula paludosa.
[000245] From the order of Lepidoptera, for example, Achroia grisella, Galleria mellonella, Plodia interpunctella, Tinea cloacella, Tinea pellionella, Tineola bisselliella.
[000246] From the order of Siphonaptera, for example, Ctenocephalides canis, Ctenocephalides felis, Pulex irritans, Tunga penetrans, Xenopsylla cheopis.
[000247] From the order of Hymenoptera, for example, Camponotus herculeanus, Lasius fuliginosus, Lasius niger, Lasius umbratus, Monomorium pharaonis, Paravespula spp., Tetramorium caespitum.
[000248] From the order of Anoplura, for example, Pediculus humanus capitis, Pediculus humanus corporis, Pemphigus spp., Phylloera vastatrix, Phthirus pubis.
[000249] From the order Heteroptera, for example, Cimex hemipterus, Cimex lectularius, Rhodinus prolixus, Triatoma infestans.
[000250] In the field of household insecticides, they are used alone or in combination with other suitable active compounds, such as phosphoric acid esters, carbamates, pyrethroids, neonicotinoids, growth regulators or active compounds from other known classes of insecticides.
[000251] They are used in aerosols, pressureless spray products, for example pump sprays or atomizers, automatic fogging systems, nebulizers, foams, gels, evaporator products with evaporator tablets made of cellulose or plastic, liquid evaporators, evaporators gel or membrane, propellant driven evaporators, powerless or passive evaporation systems, paper, anti-moth bags and gels, granules or powders, on baiting baits or at bait stations. Illustration of Processes and Intermediaries
[000252] The following preparation and use examples illustrate the invention without limiting it.
[000253] Preparation Examples 1 2,2,2-Trifluoro-N"-{2-fluoro-4-methyl-5-[(2,2,2-trifluoroethyl)sulfinyl]phenyl}-N,N-dimethylethanimidamide ( Ib-01)
[000254] Stage 1: 2,2,2-Trifluoro-N-(2-fluoro-4-methylphenyl)acetamide

[000255] At 0°C, 27.5 g of 2-fluoro-4-methylaniline are initially charged in 300 ml of dichloromethane, 26.7 g of triethylamine are added and then 50.8 g of are added dropwise trifluoroacetic anhydride. The mixture is stirred at 0°C for a further 2 h and then concentrated by rotary evaporation. The residue is taken up in water and extracted twice with ethyl acetate. The combined organic phases are dried over sodium sulphate and filtered and the solvent removed under reduced pressure. Yielded 49.0 g (100% of theory) of the trifluoroacetamide (VI-1). logP(HCOOH): 2.40 Step 2: 4-Fluoro-2-methyl-5-[(trifluoroacetyl)amino]benzenesulfonyl chloride (V-1)

[000256] 258 g of chlorosulfonic acid are initially charged and 49 g of 2,2,2--trifluoro-N-(2-fluoro-4-methylphenyl)acetamide (VI-1) are added a little at a time, to the room temperature. The mixture is stirred at room temperature for a further 16 h. Under stirring, the mixture is added to ice and extracted twice with ethyl acetate. The combined organic phases are dried over sodium sulphate and filtered and the solvent is removed under pressure reduced. Yield 70.8 g of chlorosulfonyl (V-1). The crude product is immediately applied to the next reaction. Step 3: N,N'-[Disulfanediylbis(6-fluoro-4-methylbenzene-3,1-diyl)]bis(2,2,2-trifluoroacetamide) (IV-1)

[000257] 298.8 g of sodium iodide are dissolved in 1000 ml of trifluoroacetic acid and 70.8 g of 4-fluoro-2-methyl-5-[(trifluoroacetyl)amino]benzenesulfonyl chloride (V-1) are added ) at room temperature. The mixture is stirred at room temperature for a further 16 h and the solvent is then removed under reduced pressure. The residue is triturated with water and removed by suction filtration. 62.3 g (86% of theory) of the disulphide (IV-1) were obtained as a solid.
[000258] logP(HCOOH): 4.41 Step 4: 2,2,2-Trifluoro-N-{2-fluoro-4-methyl-5-[(2,2,2-trifluoroethyl)sulfanyl]phenyl}acetamide (III-1)
3.4 g of N,N'-[disulfanediylbis(6-fluoro-4-methylbenzene-3,1-diyl)]bis(2,2,2-trifluoroacetamide) (IV-1) are dissolved in 150 ml of N ,N-dimethylformamide and 1.86 g of potassium carbonate, 3.11 g of 1,1,1-trifluoroiodoethane (XVI-1), 2.39 g of Rongalite and a few drops of water are added. The resulting reaction mixture is stirred for 16 hours. Most of the N,N-dimethylformamide is distilled off under reduced pressure. The residue is taken up in water and extracted twice with ethyl acetate. The combined organic phases are dried over sodium sulfate and filtered and the solvent is removed. under reduced pressure. 4.48 g (90% of theory) of the thioether (III-1) were obtained.
[000259] logP(HCOOH): 3.31 Step 5: 2,2,2-Trifluoro-N-{2-fluoro-4-methyl-5-[(2,2,2-trifluoroethyl)sulfanyl]phenyl chloride }ethanidoyl (II-1)

[000260] 1 g of 2,2,2-trifluoro-N-{2-fluoro-4-methyl-5-[(2,2,2-trifluoroethyl)sulfanyl]phenyl}acetamide (III-1), 1, 51 g of triethylamine and 4.01 g of diphenyl chlorophosphate in 20 ml of acetonitrile are heated under reflux for 1 g h. After cooling, ethyl acetate is added and the precipitated solid is filtered off and discarded. The filtrate is adsorbed onto silica gel and chromatographed with cyclohexane/ethyl acetate (98/2). Removal of solvent yields 1 g of imidoyl chloride (II-1). Step 6: 2,2,2-Trifluoro-N'-{2-fluoro-4-methyl-5-[(2,2,2-trifluoroethyl)sulfanyl]phenyl}-N,N-dimethylethanimidamide (Ia-01)

[000261] 0.77 g of dimethylamine (2M in THF) are initially charged in 40 ml of acetonitrile and 1 g of 2,2,2-trifluoro-N-{2-fluoro-4-methyl-5-chloride [(2,2,2-trifluoroethyl)sulfanyl]phenyl}ethanimidoyl (II-1) dissolved in 10 ml of acetonitrile are added dropwise at room temperature. The reaction mixture is stirred at room temperature for a further 16 h and the solvent is then added dropwise removed under reduced pressure. The residue is taken up in water and extracted twice with ethyl acetate. The combined organic phases are dried over sodium sulphate and filtered and the solvent is removed under reduced pressure. 0.36 g (35% of theory) of the amidine (III-1) are obtained.
[000262] logP(HCOOH): 4.48 Step 7: 2,2,2-Trifluoro-N'-{2-fluoro-4-methyl-5-[(2,2,2-trifluoroethyl)sulfinyl]phenyl} -N,N-dimethylethanimidamide (Ib-01)

[000263] 0.36 g of 2,2,2-trifluoro-N'-{2-fluoro-4-methyl-5-[(2,2,2-trifluoroethyl)sulfanyl]phenyl}-N,N-dimethylethanimidamide (Ia-01) are dissolved in 30 ml of dichloromethane and 0.21 g of meta-chloroperbenzoic acid are added at room temperature. The resulting reaction mixture is stirred for a further 16 hours. and then it is made alkaline with sodium carbonate solution. Excess meta-chloroperbenzoic acid is reduced with sodium thiosulfate. After phase separation, the solvent is removed under reduced pressure. The residue is chromatographed with cyclohexane/acetone (9/1). 0.31 g (79% of theory) of amidine (Ib-01) was obtained.
[000264] logP(HCOOH): 3.15 Preparation Example 2: 5-Amino-4-fluoro-2-methylbenzenethiol (XI1) Step 1: S-(5-Acetamido-4-fluoro-2-methylphenyl) Ethanethioate (XII-1)

[000265] 99.3 g of 5-acetamido-4-fluoro-2-chloride are suspended in 700 ml of glacial acetic acid, 0.9 g of iodine and 38.7 g of red phosphorus are added and the mixture is added stirred under reflux for 5 h. After cooling, the solid is filtered off and the filtrate is concentrated by rotary evaporation. The residue is triturated with water and removed by suction filtration. 57.6 g (67% of theory) of the thioate (XII1) were obtained as a solid. (1) logP(HCOOH): 1.78 Step 2: 5-Amino-4-fluoro-2-methylbenzenethiol (XI-1)

[000266] 57.4 g of S-(5-Acetamido-4-fluoro-2-methylphenyl) ethanethioate (XII-1) are dissolved in 750 ml of water and 96.6 g of potassium hydroxide. The reaction mixture is boiled under reflux for 16 hours. After cooling, the solution is adjusted to pH 2-3 with hydrochloric acid and the precipitated solid is filtered off with suction. 35.8 g (94% of theory) of the thiol (XI-1) were obtained as a solid.
[000267] logP(HCooH): 3.70 Chiral oxidation of (III) to (XVII) Example 1: Synthesis of 2,2,2-trifluoro-N-{4-fluoro-2-methyl-5-[(2 ,2,2-trifluoroethyl)sulfinyl]phenyl}acetamide

[000268] In a three-neck flask, 500 mg (1.49 mmol) of 2,2,2-trifluoro-N-{4-fluoro-2-methyl-5-[(2,2,2-trifluoroethyl) were dissolved )sulfanyl]phenyl}acetamide in 5 g of chloroform and allowed to cool to 15°C. A solution of 15.82 mg (0.06 mmol) of vanadium acetylacetonate and 29.84 mg (0.089 mmol) of (S)(2,4-di-tert-butyl-6-{() were added to this mixture. E)-[(1-hydroxy-3,3-dimethylbutan-2-yl)imino]methyl}phenol 1 g of chloroform After 5 minutes, a solution of 225.5 mg (1.79 mmol) was added. ) of 30% H2O2 and 300 mg of buffer solution at pH 7 (KH2PO4/Na2HPO4) over 20 minutes. The evolution of the reaction was monitored by HPLC. After a reaction time of 2 h, 100 mg were added of thiosulfate solution and most of the chloroform was evaporated under reduced pressure.5 g of cyclohexane were added to the residue and the precipitated solid was removed by filtration.
[000269] Yield 1-{2,4-dimethyl-5-[(2,2,2-trifluoroethyl)sulfinyl]phenyl}-3-(trifluoromethyl)-1H-1,2,4-triazole (91.24% HPLC purity) as a beige solid. Enantiomeric excess was determined by chiral phase HPLC (Daicel Chiracel OJ-RH 150) with a ratio of 25.90: 74.10. Chiral oxidation of (Ia) to (Ib) Example 1: Synthesis of N'-{2,4-dichloro-5-[(2,2,2-trifluoroethyl)sulfinyl]phenyl}-2,2,2-trifluoroethanimidamide
[000270] In a three-neck flask was dissolved 1 mg (2.69 mmol) of N'-{2,4-dichloro-5-[(2,2,2-trifluoroethyl)sulfanyl]phenyl}-2.2 ,2-trifluoroethanimidamide in 10 g of chloroform and allowed to cool to 15°C. A solution of 29 mg (0.10 mmol) of vanadium acetylacetonate and 54 mg (0.16 mmol) of (S)(2,4-di-tert-butyl-6-{(E) were added to this mixture -[(1-hydroxy-3,3-dimethylbutan-2-yl)imino]methyl}phenol in 2 ml of chloroform A solution of 367 mg (3.23 mmol) of H2O2 at 30% and 750 mg was metered in. of buffer solution at pH 7 (KH2PO4/Na2HPO4) for 4 hours. The evolution of the reaction was monitored by TLC. After a reaction time of 2 h, 128 mg of thiosulfate solution (1M) and the The mixture was stirred overnight.The phases were separated and most of the chloroform (except about 3 ml) was evaporated under reduced pressure.Cyclohexane was added to the residue and the precipitated solid was removed by filtration.
[000271] Yielded 980 mg of N'-{2,4-dichloro-5-[(2,2,2-trifluoroethyl)sulfinyl]phenyl}-2,2,2-trifluoroethanimidamide (HPLC purity >99%) under the shape of a solid. Enantiomeric excess was determined by chiral phase HPLC (Daicel Chiracel OJ-RH 150) with a ratio of 89.63: 10.37. Preparation Example 3: N'-{4-Chloro-3-[(2,2,2-trifluoroethyl)sulfinyl]phenyl}-2,2,2-trifluoroethanimidamide (Ib-108) Step 1: 1,1'- Disulfanediylbis(2-chloro-5-nitrobenzene)
[000272] Under vigorous stirring, 236.1 chlorosulfonic is added to 52.0 g (203.1 mmol) of 2-chloro-5-nitrobenzenesulfonyl chloride and the mixture is stirred at room temperature overnight. After adding 40% aqueous sodium disulphide solution, the solid formed is filtered off with suction, washed with water and dried on a clay plate overnight. Yielded 36.1 g (100% purity, 94% of theory) of the title compound as a gray-brown solid.
[000273] logP(HCOOH): 5.03; logP (neutral): 5.01; 1H-NMR (D6-DMSO, 400MHz) ppm 8.40(d,2H), 8.18-8.16(m,2H), 7.91(d,2H); GC-MS: Mass EI (m/z): 376 (2Cl) [M]+ Stage 2: 3,3-disulfanediylbis(4-chloroaniline)
[000274] 8.00 g (21.2 mmol of 1,1'-disulfanediylbis(2-chloro-5-nitrobenzene) are dissolved in 150 ml of THF, 1.6 g of Raney nickel are added and the mixture is stirred at 50 °C under a hydrogen atmosphere (20 bar) for 72 h. With THF, the reaction mixture is filtered through silica gel and the filtrate is freed from the solvent under reduced pressure. purity, 89% of theory) of a mixture of 1,1'-disulfanediylbis(2-chloro-5-nitrobenzene) and 5-amino-2-chlorobenzenethiol which is eluted without further purification.
[000275] 1,1'-Disulfanediylbis(2-chloro-5-nitrobenzene):
[000276] logP(HCOOH): 3.31; logP (neutral): 3.35; 1H-NMR (D6-DMSO, 400 MHz) ppm 7.10(d,2H), 6.73(d,2H), 6.47-6.44(m,2H), 5.51(broad,4H) ); GC-MS: EI Mass (m/z): 316 (2Cl) [M]+
[000277] 5-Amino-2-chlorobenzenethiol:
[000278] logP(HCOOH): 1.64; logP(neutral): not measurable; 1H-NMR (D6-DMSO, 400MHz) ppm 7.01(d,1H), 6.54(d,1H), 6.35-6.32(m,1H), 5.28(broad,3H ); GC-MS: Mass EI (m/z): 159 (1Cl) [M]+ Step 3: 4-Chloro-3-[(2,2,2-trifluoroethyl)sulfanyl]aniline
[000279] 6.40 of a mixture of disulfanediylbis(2-chloro-5-nitrobenzene) and 5-amino-2-chlorobenznothiol (about 20 mmol) are initially charged in 100 ml of N,N-dimethylformamide and added 7 0.02 g (40.3 mmol) of sodium dithionite, 5.58 g (40.3 mmol) of potassium carbonate and 5.49 (40.3 mmol) of Rongalit and the mixture is cooled to 0°C. 9.32 g of 1,1,1-trifluoro-2-iodoethane are added dropwise at 0°C. The reaction mixture is stirred overnight. Most of the solvent is removed under reduced pressure, water is added to the residue and the mixture is extracted with ethyl acetate. The combined organic phases are washed successively with water and saturated aqueous sodium chloride solution, dried over magnesium sulfate. , filtered and freed from solvent under reduced pressure. Purification by silica gel column chromatography, through MPLC, using the cyclohexane/ethyl acetate mobile phase yielded 4.70 g (98% purity, 47% of the theoretical) of the title compound as a yellow liquid.
[000280] logP(HCOOH): 2.64; logP (neutral): 2.69; 1H-NMR (D6-DMSO, 400 MHz) ppm 7.09(d,1H), 6.78(d,1H), 6.49-6.46(m,1H), 5.37(broad,2H) ), 3.90(q,2H); GC-MS: Mass EI (m/z): 241 (1Cl) [M]+ Stage 4: N-{4-Chloro-3-[(2,2,2-trifluoroethyl)sulfanyl]phenyl}-2,2 ,2-trifluoroacetamide
[000281] 1.00 g (4.14 mmol) trifluoroethyl)sulfanyl]aniline is initially charged in 14 ml of dichloromethane and 0.50 g (4.97 mmol) of triethylamine are added at 0 °C. 0.96 g (4.55 mmol) of trifluoroacetic anhydride are added dropwise at 0 °C. The reaction mixture is stirred overnight at room temperature, then it is washed with water and saturated aqueous sodium chloride solution. dried over magnesium sulfate, filtered and freed from solvent under reduced pressure. Purification by silica gel column chromatography, through MPLC, using the cyclohexane/ethyl acetate mobile phase yielded 1.00 g (99% of purity, 71% of theory) of the title compound as a colorless solid.
[000282] logP(HCOOH): 3.46; logP (neutral): 3.41; 1H-NMR (D6-DMSO, 400MHz) ppm 11.43(s,1H), 7.91(d,1H), 7.63-7.69(m,1H), 7.56-7.58 (m,1H), 4.05(q,2H); 1H-NMR (CDCl3, 400 MHz) ppm 7.85(broad,1H), 7.82(d,1H), 7.52-7.45(m,2H), 3.53(q,2H); GC-MS: Mass EI (m/z): 337 (1Cl) [M]+ Step 5: N-{4-Chloro-3-[(2,2,2-trifluoroethyl)sulfanyl]phenyl}-2 chloride ,2,2- trifluoroethaniidoyl
[000283] 880 g (2.61 mmol) of N-{4-chloro-3-[(2,2,2-trifluoroethyl)sulfanyl]phenyl-2,2,2-trifluoroacetamide are initially charged in 17 ml of acetonitrile , 1.32 (13.03 mmol) of triethylamine and 3.50 g (13.03 mmol) of diphenyl chlorophosphate are added at room temperature and the mixture is heated under reflux overnight. After cooling, ethyl acetate is added and the mixture is filtered and concentrated. The residue is directly subjected to purification by silica gel column chromatography, through MPLC, using the mobile phase cyclohexane/ethyl acetate. Yield 640 mg (93% purity, 64% of theory) of the title compound as a yellow oil.
[000284] logP(HCOOH): 4.77; logP (neutral): 4.73; 1H-NMR (CDCl3, 400 MHz) ppm 7.51(d,1H), 7.24(d,1H), 7.02-7.00(m,1H), 3.51(q,2H); GC-MS: Mass EI (m/z): 355 (2Cl) [M]+ Stage 6: N'-{4-Chloro-3-[(2,2,2-trifluoroethyl)sulfanyl]phenyl}-2, 2,2-trifluoroethanimidamide (Ia-204)
[000285] 210 mg (0.59 mmol) of N-{4-chloro-3-[(2,2,2-trifluoroethyl)sulfanyl]phenyl}-2,2,2-trifluoroethanimidoyl chloride are initially charged in 5 ml of acetonitrile and a solution of 241 mg (3.54 mmol) of 25% aqueous ammonia solution in 5 ml of acetonitrile is added. The reaction mixture is stirred overnight at room temperature and then concentrated. The residue is extracted with water and ethyl acetate. The combined organic phases are dried over magnesium sulfate, filtered and freed from solvent under reduced pressure. Purification by silica gel column chromatography, through MPLC, using the cyclohexane/ethyl acetate mobile phase yielded 120 mg ( 100% purity, 60% of theory) of the title compound as a yellow oil.
[000286] logP(HCOOH): 3.10; logP (neutral): 3.10; 1H-NMR (D6-DMSO, 400MHz) ppm 7.42(d,1H), 7.26(broad,2H), 7.05(d,1H), 6.75-6.72(m,1H), 4, 13(q,2H) Step 7: N'-{4-Chloro-3-[(2,2,2-trifluoroethyl)sulfinyl]phenyl}-2,2,2-trifluoroethanimidamide (Ib-108)
[000287] 90 mg (0.27 mmol) of N'-{4-Chloro-3-[(2,2,2-trifluoroethyl)sulfanyl]phenyl}-2,2,2-trifluoroethanimidamide are dissolved in 6 ml of dichloromethane and 68 mg (0.29 mol) of meta-chlorobenzoic acid are added at 0°C. After two hours of stirring at 0°C, an additional 23 mg (0.13 mmol) was added. The reaction mixture is stirred overnight at room temperature and then diluted and washed successively with 40% sodium bisulfite solution and saturated aqueous sodium bicarbonate. The organic phase is dried over magnesium sulfate, filtered and freed of solvent under reduced pressure. Purification by silica gel column chromatography via MPLC using the cyclohexane/ethyl acetate mobile phase yielded 90 mg (95% purity, 91% of theory) of the title compound as a beige solid.
[000288] logP(HCOOH): 2.25; logP (neutral): 2.21; 1H-NMR (D6-DMSO, 400 MHz) ppm 7.57(d,1H), 7.42(broad,2H), 7.30(d,1H), 7.10-7.07(m,1H) ), 4.22-4.04(m,2H) Preparation Example 4: N'-{2-Fluoro-4-methyl-5-[(2,2,2-trifluoroethyl)sulfanyl]phenyl}-N- methyl-4-(trifluoromethyl)benzenecarboximidamide (Ia-250) Step 1: N-{2-Fluoro-4-methyl-5-[(2,2,2-trifluoroethyl)sulfanyl]phenyl}-4-(trifluoromethyl)benzamide
[000289] 1.00 g (4.18 mmol) of 2-Fluoro-4-methyl-5-[(2,2,2-trifluoroethyl)sulfanyl]aniline is initially charged in 25 ml of dichloromethane and 0. 47 g (4.60 mmol) of triethylamine and the mixture is cooled to 0 °C. 0.96 g (4.60 mmol) of 4-(trifluoromethyl)benzoyl chloride in 25 ml of dichloromethane are added dropwise at 0°C. The reaction mixture is stirred overnight. 0.17 g (0.84 mol) of 4-(trifluoromethyl)benzoyl chloride is added and the mixture is stirred at room temperature for a further 3 h. The reaction mixture is diluted with dichloromethane, washed successively with semi-saturated aqueous ammonium chloride solution and saturated aqueous sodium chloride solution, dried over magnesium sulfate, filtered and freed from solvent under reduced pressure. The residue is triturated with ether. oil and removed by suction filtration and dried. Yield 1.69 g (95% purity, 93% of theory) of the title compound as a colorless solid.
(III-1) (II-3)[000290] logP(HCOOH): 4.20; logP (neutral): 4.17; 1H-NMR (D6-DMSO, 400MHz) ppm 10.40(s,1H), 8.17(d,2H), 7.93(d,2H), 7.82(d,1H), 7. 31(d,1H), 3.89(q,2H), 2.42(s,3H); 1H-NMR (CD3CN, 400 MHz) ppm 8.70(broad,1H), 8.12(d,1H), 8.08(d,2H), 7.84(d,2H), 7.17( d,1H), 3.57(q,2H), 2.46(s,3H); GC-MS: Mass EI (m/z): 411 [M]+ Step 2: N-{2-Fluoro-4-methyl-5-[(2,2,2-trifluoroethyl)sulfanyl]phenyl}- chloride 4-(trifluoromethyl)benzenecarboximidoyl (III-1) (II-3)
[000291] 1.00 g (2.43 mmol) of N-{2-Fluoro-4-methyl-5-[(2,2,2-trifluoroethyl)sulfanyl]phenyl}-4-(trifluoromethyl)benzamide is initially charged with 20 ml of dichloromethane and 0.51 g (2.43 mmol) of phosphorus pentachloride are added and the mixture is stirred at room temperature overnight. An additional 0.51 g (2.43 mol) of phosphorus pentachloride is added and the mixture is stirred at room temperature overnight. A further 0.51 g (2.43 mol) of phosphorus pentachloride is added and the reaction mixture is stirred at room temperature for a further 3 hours and then filtered through silica gel and concentrated. Yields 0.91 g (74% purity, 65% of theory) of the title compound as a yellow oil which is applied directly to the next reaction.
[000292] 1H-NMR (CD3CN, 400 MHz) ppm 8.32(d,2H), 7.86(d,2H), 7.32(d,1H), 7.21(d,1H), 3 .58(q,2H), 2.47(s,3H); GC-MS: Mass EI (m/z): 429 (1Cl) [M]+ Step 3: N'-{2-Fluoro-4-methyl-5-[(2,2,2-trifluoroethyl)sulfanyl]phenyl }-N-methyl-4-(trifluoromethyl)benzenecarboximidamide
[000293] 150 g (4.65 mmol) of methylamine (2M in THF) are initially charged in 25 ml of acetonitrile, 400 mg (0.93 mmol) of N-{2-fluoro-4-methyl chloride are added -5-[(2,2,2-trifluoroethyl)sulfanyl]phenyl}-4-(trifluoromethyl)benzenecarboximidoyl in 25 ml of acetonitrile at 0 °C and the mixture is stirred at room temperature overnight and then concentrated . The residue is purified by column chromatography on silica gel, through MPLC, using the mobile phase cyclohexane/ethyl acetate. Yield 220 mg (99% purity, 56% of theory) of the title compound in the form of a yellow solid.
[000294] logP(HCOOH): 1.96; logP (neutral): 4.08; 1H-NMR (D6-DMSO, 400 MHz) ppm 7.64(d,2H), 7.46(d,1H), 7.39(d,2H), 6.88(d,1H), 7. 76(d,1H), 3.53(q,2H), 2.89(d,3H), 2.20(s,3H); GC-MS: Mass EI (m/z): 424 [M]+ Preparation Example 5: 5-Chloro-N'-{2-fluoro-4-methyl-5-[(2,2,2-trifluoroethyl) sulfanyl]phenyl}-N,N-dimethylthiophene-2-carboximidamide (Ia-149) Step 1: 5-Chloro-N'-{2-fluoro-4-methyl-5-[(2,2,2-trifluoroethyl) sulfanyl]phenyl}-N,N-dimethylthiophene-2-carboximidamide
[000295] 743 mg (0.84 mmol) of phosphoryl chloride are added to 200 mg (0.84 mmol) of 2-fluoro-4-methyl-5-[(2,2,2-trifluoroethyl)sulfanyl]aniline and 206 g (1.09 mmol) of 5-chloro-N,N-dimethylthiophene-2-carboxamide and the mixture is heated under reflux overnight. After cooling, the reaction mixture is poured into water, made alkaline with potassium carbonate and extracted with dichloromethane. The combined organic phases are dried over magnesium sulphate, filtered and freed from solvent under reduced pressure. Purification by silica gel column chromatography, through MPLC, using the mobile phase cyclohexane/ethyl acetate yielded 165 mg ( 92% purity, 44% of theory) of the title compound as a reddish-brown oil.
[000296] logP(HCOOH): 2.11; logP (neutral): 4.89; 1H-NMR (D6-DMSO, 400MHz) ppm 7.00(d,1H), 7.93(d,1H), 6.87-6.84(m,2H), 3.68(q,2H) ), 2.97(broad,6H), 2.23(s,3H) Preparation Example 6: N'-{2-Fluoro-4-methyl-5-[(2,2,2-trifluoroethyl)sulfanyl] phenyl}-N,N,1-trimethyl-1H-pyrrole-2-carboximidamide (Ia-162) Step 1: N'-{2-Fluoro-4-methyl-5-[(2,2,2-trifluoroethyl) sulfanyl]phenyl}-N,N,1-trimethyl-1H-pyrrole-2-carboximidamide (Ia-162)
[000297] 743 mg (0.84 mmol) of phosphoryl chloride are added to 200 mg (0.84 mmol) of 2-fluoro-4-methyl-5-[(2,2,2-trifluoroethyl)sulfanyl]aniline and 165 g (1.09 mmol) of N,N,1-trimethyl-1H-pyrrole-2-carboxamide and the mixture is heated under reflux overnight. After cooling, the reaction mixture is poured into water, made alkaline with potassium carbonate and extracted with dichloromethane. The combined organic phases are dried over magnesium sulfate, filtered and freed from solvent under reduced pressure. Purification by silica gel column chromatography, through MPLC, using the cyclohexane/ethyl acetate mobile phase yielded 177 mg ( 99% pure, 56% of theory) of the title compound as a yellow oil.
[000298] logP(HCOOH): 1.67; logP (neutral): 4.11; 1H-NMR (D6-DMSO, 400MHz) ppm 6.88(d,1H), 6.70-6.68(m,1H), 6.64(d,1H), 5.91-5.89 (m,2H), 3.59(q,2H), 3.39(s,3H), 3.05(broad,3H), 2.77(broad,3H), 2.21(s,3H) Preparation Example 7: N'-{2-Fluoro-4-methyl-5-[(2,2,2-trifluoroethyl)sulfanyl]phenyl}-N,N-dimethylfuran-2-carboximidamide (Ia-166) Step 1 : N'-{2-Fluoro-4-methyl-5-[(2,2,2-trifluoroethyl)sulfanyl]phenyl}-N,N-dimethylfuran-2-carboximidamide
[000299] 743 mg (0.84 mmol) of phosphoryl chloride are added to 200 mg (0.84 mmol) of 2-fluoro-4-methyl-5-[(2,2,2-trifluoroethyl)sulfanyl]aniline and 139 g (1.09 mmol) of N,N-dimethyl-2-furanamide and the mixture is heated under reflux overnight. After cooling, the reaction mixture is poured into water, made alkaline with potassium carbonate and extracted with dichloromethane. The combined organic phases are dried over magnesium sulfate, filtered and freed from solvent under reduced pressure. Purification by silica gel column chromatography, through MPLC, using the cyclohexane/ethyl acetate mobile phase yielded 64 mg ( 98% purity, 21% of theory) of the title compound as a yellow oil.
[000300] logP(HCOOH): 1.57; logP (neutral): 3.94; 1H-NMR (D6-DMSO, 400 MHz) ppm 7.69-7.67(m,1H), 6.91(d,1H), 6.76(d,1H), 6.43-6.40 (m,1H), 6.25(d,1H), 3.69(q,2H), 2.94(s,6H), 2.24(s,3H) Preparation Example 8: 2-Methoxy- 4-methyl-5-[(2,2,2-trifluoroethyl)sulfanyl]aniline Step 1: 5-acetamido-4-methoxy-2-methylbenzenesulfonyl chloride
[000301] 19.5 g (108.8 mmol) of N-(2-methoxy-4-methylphenyl)acetamide [CAS-RN 89345-81-3] were added a little at a time to 150 g (1287) mmol) of chlorosulfonic acid and the mixture is stirred at 80 °C for a further 4 h. After cooling, the mixture is added to ice water and the solid obtained is filtered off with suction, yielding 25.4 g of product (84.1% of theory, 100% purity according to 1H-NMR).
[000302] 1H-NMR(D6-DMSO) ppm: 9.04(s,1H), 8.14(s,1H), 6.80(s,1H), 3.80(s,3H), 2 .48(s,3H), 2.04(s,3H) Step 2: N,N'-[Disulfanediylbis(6-methoxy-4-methylbenzene-3.1-diyl)]diacetamide
[000303] 25.3 g (91.1 mmol) of 5-acetamido-4-methoxy-2-methylbenzenesulfonyl chloride and 14.6 g (261.4 mmol) of iron powder in 400 ml of ethanol and 36, 7 g of concentrated hydrochloric acid are heated under reflux for 12 h. After removing the solvent under reduced pressure, the residue is triturated with water and separated by subsection filtration, yielding 9.4 g of crude product (49.1% of theory, 86.4% purity according to LC/MS ) as a light brown solid.
[000304] logP(HCOOH): 2.73 Step 3: trifluoroethyl)sulfanyl]phenyl}acetamide
[000305] 9.4 (22.35 mmol) of a mixture of N,N'-[disulfanediylbis(6-methoxy-4-methylbenzene-3.1-diyl)]diacetamide are initially charged in 60 ml of dimethylformamide, are 6.5 g of sodium dithionite, 15.9 g of sodium bisphosphate and 40 ml of water are added and the mixture is then stirred at 60°C for 3 h. After cooling, 12.5 g (59.54 mol) of 1,1,1-trifluoro-2-iodoethane are added and the mixture is stirred at 75°C for a further 12 h. After removing the solvent under reduced pressure, the residue that remains is acidified with concentrated hydrochloric acid and the precipitate formed is filtered off with suction. 5.3 g of product are produced (80.8% of theory, purity >95% according to 1H-NMR).
[000306] 1H-NMR(D6-DMSO) ppm: 9.15(s,1H), 8.14(s,1H), 6.98(s,1H), 3.83(s,3H), 3 .69-3.61(q,2H), 2.40(s,3H), 2.06(s,3H) Step 4: 2-Methoxy-4-methyl-5-[(2,2,2- trifluoroethyl)sulfanyl]aniline
[000307] 5.3 g (22.35 mmol) of N-{2-Methoxy-4-methyl-5-[(2,2,2-trifluoroethyl)sulfanyl]phenyl}acetamide chloride in 125 ml of hydrochloric acid 5 molar, are stirred under reflux for 18 h. The reaction mixture is made alkaline with aqueous sodium hydroxide solution and extracted with dichloromethane. The organic phase is separated, dried over sodium sulphate and freed from solvent under reduced pressure. 3.6 g of the product are produced as a dark orange oil (79.3% of theory, 96.8% purity according to LC/MS).
[000308] 1H-NMR(D6-DMSO) ppm: 6.83(s,1H), 6.72(s,1H), 4.64(broad,2H), 3.75(s,3H), 3 .64-3.56(q,2H), 2.30(s,3H) Preparation Example 9: 3-[(2,2,2-Trifluoroethyl)sulfanyl]aniline
[000309] 6.5 g (51.92 mmol) of 3-aminobenzenethiol are initially loaded in 200 ml of acetonitrile, 13.7 g of potassium carbonate, 1.6 g of sodium hydroxide, 1 ml of dimethyl are added sulfoxide and 13 g (61.93 mmol) of 1,1,1-trifluoro-2-iodoethane and the mixture is stirred at 45 °C for 18 h. The reaction mixture is diluted with 250 ml of water and extracted with dichloromethane. The organic phase is separated, dried over sodium sulphate and freed from solvent under reduced pressure. 9.5 g of the product are produced as a brown oil (88.3% of theory, purity 97.9% according to LC/MS).
[000310] 1H-NMR(D6-DMSO) ppm: 7.00-6.97(m,1H), 6.61(m,1H), 6.59(m,1H), 6.47-6, 45(m,1H), 5.19(broad,2H), 3.88-3.80(q,2H)
(XXIV-1)[000311] logP(HCOOH): 2.01 Preparation Example 10: N-(2,2-Difluoroethyl)cyclopropanecarboxamide (XXIV-1) (XXIV-1)
[000312] 14.4 g (137.75 mmol) of cyclopropanecarbonyl chloride was dissolved in 300 ml of anhydrous tetrahydrofuran. After the addition of 1 g of triethylamine, a solution of 16.8 g (207.24 mmol) of 2,2-difluoroethanamine in 50 ml of anhydrous tetrahydrofuran was added dropwise. Once the addition is complete, the mixture is stirred at room temperature for a further 18 h and then at 40°C for a further 1 h. The reaction mixture is diluted with 200 ml of water and extracted with dichloromethane. The combined organic phases are separated, dried over sodium sulphate and freed from solvent under reduced pressure. A residue of 18.9 g of the product (92% of theory, 100% purity according to 1H-NMR) is produced as a white solid.
[000313] 1H-NMR(D6-DMSO) ppm: 8.46(t,1H), 5.99(tt,1H), 3.54-3.43(m,2H), 1.65-1, 59(m,1H), 0.70-0.60(m,4H) Preparation Example 11: 1-Fluorocyclopropanecarboxamide (XXIV-2)
[000314] 600 mg (4.9 mmol) of 1-fluorocyclopropanecarbonyl chloride [CAS-RN 149961-53-5] are added a little at a time to 15 g of ammonium hydroxide (NH3 solution in water at concentration 28-30% by weight) and the mixture is stirred at room temperature for a further 18 h. The resulting precipitate is filtered off with suction, yielding 470 g of product (93.1% of theory, 100% purity according to 1H-NMR) as a white solid.
[000315] 1H-NMR(D6-DMSO) ppm: 7.80(broad,1H), 7.58(broad,1H), 1.29-1.12(m,4H) Preparation example 12: (4 -Chlorophenyl)(4,4-difluoropiperidin-1-yl)methanone (XXIV-3)
[000316] 470 mg (2.98 mmol) of 4,4-difluoropiperidinium chloride are initially charged in 35 ml of anhydrous toluene. After the addition of 1.4 g of triethylamine, 690 mg (3.94 mmol) of 4-chlorobenzoyl chloride are added a little at a time and the mixture is stirred at 100°C for a further 18 h. The reaction mixture is diluted with 250 ml of water and the organic phase is separated, dried over sodium sulphate and freed from the solvent under reduced pressure. 480 mg of the product are produced as an orange oil (62% of theory, 88% purity according to LC/MS).
[000317] 1H-NMR(D6-DMSO) ppm: 7.54-7.49(m,4H), 3.70(m,2H), 3.39(m,2H), 2.03(m, 4H) Preparation Example 13: N-{2-[3-Chloro-5-(trifluoromethyl)pyridin-2-yl]ethyl}cyclopropanecarboxamide (XXIV-4)
[000318] 550 mg (2.11 mmol) of 2-[3-chloro-5-(trifluoromethyl)pyridin-2-yl]ethanamine are initially charged in 20 ml of anhydrous dichloromethane. After addition of 1 g of triethylamine, 270 mg (2.58 mmol) of cyclopropanecarbonyl chloride dissolved in 5 ml of anhydrous dichloromethane are added dropwise and the mixture is stirred at 50°C for a further 12 h. The reaction mixture is diluted with 50 ml of water and the organic phase is separated, dried over magnesium sulphate and freed from the solvent under reduced pressure. 450 mg of the product is produced as an orange solid (73% of theory, 87.1% purity according to LC/MS).
[000319] 1H-NMR(D6-DMSO) ppm: 8.89(d,1H), 8.41(d,1H), 8.17(t,1H), 3.53-3.48(m, 2H), 3.11(t,2H), 1.51-1.46(m,1H), 0.63-0.59(m,4H) Preparation Example 14: 1-Fluoro-N'-{ 2-fluoro-4-methyl-5-[(2,2,2-trifluoroethyl)sulfinyl]phenyl}cyclopropanecarboximidamide (Ib-19) Stage 1: 1-Fluoro-N'-{2-fluoro-4-methyl-5 -[(2,2,2-trifluoroethyl)sulfanyl]phenyl}cyclopropanecarboximidamide (Ia-27)
[000320] 1.4 mg (9.13 mmol) of phosphoryl chloride are added to 400 mg (1.67 mmol) of 2-fluoro-4-methyl-5-[(2,2,2-trifluoroethyl)sulfanyl ]aniline and 470 g (4.56 mmol) of 1-fluorocyclopropanecarboxamide and the mixture is stirred at 95 °C for 18 h. The residue which remains after rotary evaporation is stirred with water, made alkaline with potassium carbonate and extracted with dichloromethane. The combined organic phases are separated, dried over sodium sulphate and freed from solvent under reduced pressure. 380 mg of product are produced (70.1% of theory, purity 88.8% according to LC/MS) as residue.
[000321] logP(HCOOH): 1.2 Step 2: 1-Fluoro-N'-{2-fluoro-4-methyl-5-[(2,2,2-trifluoroethyl)sulfinyl]phenyl}cyclopropanecarboximidamide (Ib- 19)
[000322] At 0-4 °C, 310 mg (0.96 mmol) of 1-fluoro-N'-{2-fluoro-4-methyl-5-[(2,2,2-trifluoroethyl)sulfanyl]phenyl }cyclopropanecarboximidamide are initially charged in 30 ml of trichloromethane. After the addition of 335 mg of pH 7 buffer solution (KH2PO4/Na2HPO4) and 65 mg of benzyltriethylammonium chloride, 230 mg (70%, 1.03 mmol) of m-chloroperbenzoic acid are added a little at a time between 0 -4 °C and the reaction mixture was stirred at room temperature for 24 h. 33% Aqueous sodium bisulfite solution was added and the mixture is then extracted twice with dichloromethane. The combined organic phases are washed with water, dried over sodium sulfate and filtered. After removing the solvent under reduced pressure, the residue is purified by column chromatography using MPLC on RPC-18) with water/acetonitrile. 42 mg of product are produced (12.9% of theory, purity 98.1% according to LC/MS). Preparation Example 15: 2,2,2-Trifluoro-N'-{2-methoxy-4-methyl-5-[(2,2,2-trifluoroethyl)sulfanyl]phenyl}ethanimidamide (Ia-236)
[000323] 2.5 mg (16.3 mmol) of phosphoryl chloride are added to 300 mg (1.19 mmol) of 2-methoxy-4-methyl-5-[(2,2,2-trifluoroethyl)sulfanyl ]aniline and 400 g (3.54 mmol) of trifluoroacetamide and the mixture is stirred at 95 °C for 18 h. The residue which remains after rotary evaporation is stirred with water, made alkaline with potassium carbonate and extracted with dichloromethane. The combined organic phases are separated, dried over sodium sulphate and freed from solvent under reduced pressure. 61.3 g of the product (14.1% of theory, purity > 95% according to 1H-NMR) are produced as residue. Preparation Example 16: N-[(4-Chlorophenyl)(morpholin-4-yl)methylene]-2-methoxy-4-methyl-5-[(2,2,2-trifluoroethyl)sulfanyl]aniline (Ia-268 )
[000324] 2.5 mg (16.3 mmol) of phosphoryl chloride are added to 300 mg (1.19 mmol) of 2-methoxy-4-methyl-5-[(2,2,2-trifluoroethyl)sulfanyl ]aniline and 360 g (1.60 mmol) of (4-chlorophenyl)(morpholin-4-yl)methanone and the mixture is stirred at 95 °C for 18 h. The residue which remains after rotary evaporation is stirred with water, made alkaline with potassium carbonate and extracted with dichloromethane. The combined organic phases are separated, dried over sodium sulphate and freed from solvent under reduced pressure. 247 mg of the product are produced (40.9% of theory, 90.9% purity according to LC/MS) as residue. Preparation Example 17: N'-{2-Fluoro-4-methyl-5-[(2,2,2-trifluoroethyl)sulfinyl]phenyl}-N-methylpyridine-3-carboximidamide (Ib-28) Stage 1: N '-{2-Fluoro-4-methyl-5-[(2,2,2-trifluoroethyl)sulfanyl]phenyl}-N-methylpyridines-3-carboximidamide (Ia-61)
[000325] 1.5 mg (9.78 mmol) of phosphoryl chloride are added to 400 mg (1.67 mmol) of 2-fluoro-4-methyl-5-[(2,2,2-trifluoroethyl)sulfanyl ]aniline and 450 mg (3.31 mmol) of N-methylnicotinamide and the mixture is stirred at 95 °C for 18 h. The residue which remains after rotary evaporation is stirred with water, made alkaline with potassium carbonate and extracted with dichloromethane. The combined organic phases are separated, dried over sodium sulphate and freed from solvent under reduced pressure. 550 mg of the product (92.1% of theory, 92.9% purity according to LC/MS) are produced as residue. Stage 2: N'-{2-Fluoro-4-methyl-5-[(2,2,2-trifluoroethyl)sulfinyl]phenyl}-N-methylpyridine-3-carboximidamide (Ib-28)
[000326] At 0-4 °C, 460 mg (1.29 mmol) of N'-{2-fluoro-4-methyl-5-[(2,2,2-trifluoroethyl)sulfanyl]phenyl}-N- methylnicotinamide are initially charged in 40 mL of trichloromethane. After the addition of 460 mg of pH 7 buffer solution (KH2PO4/Na2HPO4) and 90 mg of benzyltriethylammonium chloride, 320 mg (70%, 0.261 mmol) of m-chloroperbenzoic acid are added a little at a time between 0-4° C and the reaction mixture was stirred at room temperature for 24 h. 33% aqueous sodium bisulfite solution was added and the mixture is then extracted twice with dichloromethane. The combined organic phases are washed with water, dried over sodium sulfate and filtered. After removing the solvent under reduced pressure, the residue is purified by column chromatography using MPLC on RPC-18) with water/acetonitrile. 145 mg of product are produced (30.2% of theory, purity 98.7% according to LC/MS). Preparation Example 18: N'-{2-Fluoro-4-methyl-5-[(2,2,2-trifluoroethyl)sulfinyl]phenyl}pyrazine-2-carboximidamide (Ib-62) Step 1: N'-{ 2-Fluoro-4-methyl-5-[(2,2,2-trifluoroethyl)sulfanyl]phenyl}pyrazine-2-carboximidamide (Ia-117)
[000327] 2 mg (13.04 mmol) of phosphoryl chloride are added to 300 mg (1.25 mmol) of 2-fluoro-4-methyl-5-[(2,2,2-trifluoroethyl)sulfanyl]aniline and 190 mg (1.54 mmol) of pyrazinecarboxamide and the mixture is stirred at 95 °C for 18 h. The residue which remains after rotary evaporation is stirred with water, made alkaline with potassium carbonate and extracted with dichloromethane. The combined organic phases are separated, dried over sodium sulphate and freed from solvent under reduced pressure. 365 mg of the product are produced (84.5% of theory, 91.2% purity according to LC/MS) as residue.
[000328] logP(HCOOH): 1.24
(Ia-117) (Ib-62)[000329] Stage 2: N'-{2-Fluoro-4-methyl-5-[(2,2,2-trifluoroethyl)sulfinyl]phenyl}pyrazine-2-carboximidamide (Ib-62) (Ia-117) (Ib-62)
[000330] At 0-4°C, 305 mg (0.89 mmol) of N'-{2-fluoro-4-methyl-5-[(2,2,2-trifluoroethyl)sulfanyl]phenyl}pyrazine-2 -carboximidamide are initially charged in 30 ml of trichloromethane. After the addition of 320 mg of pH 7 buffer solution (KH2PO4/Na2HPO4) and 60 mg of benzyltriethylammonium chloride, 225 mg (70%, 1.04 mmol) of m-chloroperbenzoic acid are added a little at a time between 0- 4 °C and the reaction mixture was stirred at room temperature for 24 h. 33% aqueous bisulfite solution was added and the mixture is then extracted twice with dichloromethane. The combined organic phases are washed with water, dried over sodium sulfate and filtered. After removing the solvent under reduced pressure, the residue is adsorbed onto material RPC-18). Purification by column chromatography using MPLC on RP(C-18) with water/acetonitrile yields 55 mg of product (17.2% of theory, 100% purity according to LC/MS) of product as a light beige solid.
[000331] logP(HCOOH): 0.84; logP (neutral): 1.77 Preparation Example 19: 2-Fluoro-4-methyl-N-[1-(2,2,2-trifluoroethyl)pyrrolidin-2-ylidene]-5-[(2.2, 2-trifluoroethyl)sulfinyl]aniline (Ib-115) Step 1: N'-{2-Fluoro-4-methyl-5-[(2,2,2-trifluoroethyl)sulfanyl]phenyl}-N-(2,2 ,2-trifluoroethyl)cyclopropanecarboximidamide (Ia-145) and 2-fluoro-4-methyl-N-[1-(2,2,2-trifluoroethyl)pyrrolidin-2-ylidene]-5-[(2,2,2- trifluoroethyl)sulfanyl]aniline (Ia-189)
[000332] 1.5 mg (9.78 mmol) of phosphoryl chloride are added to 300 mg (1.25 mmol) of 2-fluoro-4-methyl-5-[(2,2,2-trifluoroethyl)sulfanyl ]aniline and 430 mg (2.57 mmol) of N-(2,2,2-trifluoroethyl)cyclopropanecarboxamide and the mixture is stirred at 95 °C for 18 h. The residue which remains after rotary evaporation is stirred with water, made alkaline with potassium carbonate and extracted with dichloromethane. The combined organic phases are separated, dried over sodium sulphate and freed from solvent under reduced pressure. 630 mg of the crude product is produced as a 3:1 mixture of the isomers described above as a residue.
[000333] Purification by column chromatography using MPLC on RP(C-18) with water/acetonitrile yields 239.8 mg of product (49.2% of theory, 80% purity according to 1H-NMR) of N'-{ 2-Fluoro-4-methyl-5-[(2,2,2-trifluoroethyl)sulfanyl]phenyl}-N-(2,2,2 trifluoroethyl)cyclopropanecarboximidamide (Ia-145) (Ia-145)
[000334] 13C-NMR(D6-DMSO) ppm: 161.0, 153.5, 137.0, 133.9, 128.1, 127.2, 117.5, 41.0, 35.6, 19 .6, 11.6, 6.2
[000335] logP(HCOOH): 1.99; logP (neutral): 4.12
[000336] and 72.4 mg (14.9% of theory, 100% purity according to HPLC) of 2-fluoro-4-methyl-N-[1-(2,2,2-trifluoroethyl)pyrrolidin-2 -ylidene]-5-[(2,2,2-trifluoroethyl)sulfanyl]aniline (Ia-189). (Ia-189)
[000337] 1H-NMR(D6-DMSO) ppm: 7.09-7.01(m,2H), 4.28-4.21(q,2H), 3.89-3.81(q,2H) ), 3.51-3.47(t,2H), 2.36-2.30(t,2H), 2.32(s,3H), 1.98-1.90(m,2H),
[000338] logP(HCOOH): 2.32; logP (neutral): 4.37 Step 2: 2-Fluoro-4-methyl-N-[1-(2,2,2-trifluoroethyl)pyrrolidin-2-ylidene]-5-[(2,2,2- trifluoroethyl)sulfinyl]aniline (Ib-115)
[000339] At 0-4°C, 900 mg (2.32 mmol) of 2-fluoro-4-methyl-N-[1-(2,2,2-trifluoroethyl)pyrrolidin-2-ylidene]-5- [(2,2,2-trifluoroethyl)sulfanyl]aniline (Ia-189) are initially charged in 40 mL of trichloromethane. After the addition of 850 mg of pH 7 buffer solution (KH2PO4/Na2HPO4) and 160 mg of benzyltriethylammonium chloride, 600 mg (77%, 2.68 mmol) of m-chloroperbenzoic acid are added a little at a time between 0- 4 °C and the reaction mixture was stirred at room temperature for 24 h. 33% aqueous sodium bisulfite solution was added and the mixture is then extracted twice with dichloromethane. The combined organic phases are washed with water, dried over sodium sulfate and filtered. After removing the solvent under reduced pressure, the residue is purified by column chromatography using MPLC on RPC-18) with water/acetonitrile. 70 mg of product are produced (7.5% of theory, 95.2% purity according to LC/MS).
[000340] 13C-NMR(D6-DMSO) ppm: 164.2, 155.6, 138.3, 136.0, 129.8, 125.1, 124.2, 119.9, 117.9, 56 ,8, 49.5, 44.4, 27.0, 19.5, 16.4 Preparation Example 20: 2,4-Dimethyl-N-[1,3-oxazolidin-2-ylidene]-5-[ (2,2,2-trifluoroethyl)sulfanyl]aniline 1-(2-Chloroethyl)-3-{2,4-dimethyl-5-[(2,2,2-
[000341] 1.45 g (6.16 mmol) of 2,4-dimethyl-5-[(2,2,2-trifluoroethyl)sulfanyl]aniline are added a little at a time to a 700 mg solution (6.63 mmol) of 2-chloroethyl isocyanate in 50 ml of tert-butyl methyl ether and a catalytic portion of 1,8-diazabicyclo[5.4,0]undec-7-ene (DBU) and are subsequently stirred. at room temperature for another 18 h. Under reduced pressure, most of the solvent is removed from the mixture and the resulting white solid is filtered off with suction. 2.00 g of product are produced (88.5% of theory, 94.4% purity according to LC/MS).
(XXVI-1)[000342] 1H-NMR(D6-DMSO) ppm: 8.01(s,1H), 7.83(s,1H), 7.04(s,1H), 6.83(t,1H), 3 .77-3.69(q,2H), 3.68-3.65(m,2H), 3.45-3.40(m,2H), 2.30(s,3H), 2.14 (s,3H), Step 2: 2,4-Dimethyl-N-[1,3-oxazolidin-2-ylidene]-5-[(2,2,2-trifluoroethyl)sulfanyl]aniline (XXVI-1)
[000343] 900 mg (2.64 mmol) of 1-(2-Chloroethyl)-3-{2,4-dimethyl-5-[(2,2,2-trifluoroethyl)sulfanyl]phenyl}urea in a mixture of 15 ml of water and 20 ml of propionitrile with 4 g of potassium carbonate are heated under reflux for 18 h. Under reduced pressure, the mixture is freed from the solvent and the remaining solids sludge is acidified with dilute hydrochloric acid. The mixture is then left to stand for 18 hours and the beige precipitate is then filtered off with suction. 560 mg of crude product were produced. Purification by column chromatography using Biotage Isolera One and ethyl acetate/cyclohexane 2: 1 v/v as mobile phase yielded 130 mg of product (16.2% of theory, purity according to LC/MS 81, 5%).
(Ia-278)[000344] logP(HCOOH): 1.36 Preparation Example 21: 2-Fluoro-4-methyl-N-[1,3-thiazinan-2-ylidene]-5-[(2,2,2-trifluoroethyl) sulfanyl]aniline (Ia-279) Step 1: 2-Fluoro-4-methyl-N-[(1,3-thiazinan-2-ylidene]-5-[(2,2,2-trifluoroethyl)sulfanyl] chloride aninium (Ia-278) (Ia-278)
[000345] 1.61 g (6.72 mmol) of 2-fluoro-4-methyl-5-[(2,2,2-trifluoroethyl)sulfanyl]aniline are added a little at a time to a solution of 1 mg (7.37 mmol) of 3-chloropropyl isocyanate in 30 ml of tert-butyl methyl ether and a catalytic portion of 1,8-diazabicyclo[5.4,0]undec-7-ene (DBU) and are subsequently stirred at room temperature for a further 18 h. Under reduced pressure, the mixture is freed from the solvent. The residue that remains is a light beige oil that slowly crystallizes. 2.3 g of product are produced (91.3% of theory, 95% purity according to LC/MS).
[000346] 13C-NMR(D6-DMSO) ppm: 166.0 (broad), 156.1, 142.1, 131.7, 129.4, 126.1, 120.6, 118.6, 41, 3, 34.9, 26.6, 20.6
[000347] logP(HCOOH): 1.34 Step 2: 2-Fluoro-4-methyl-N-[1,3-thiazinan-2-ylidene]-5-[(2,2,2-trifluoroethyl)sulfanyl] aniline (Ia-279)
[000348] 2.2 g (5.87 mmol) of 2-fluoro-4-methyl-N-[(1,3-thiazinan-2-ylidene]-5-[(2,2,2-trifluoroethyl) chloride )sulfanyl]anilinium (Ia-278) are dissolved in 50 ml of water and made alkaline with ammonium hydroxide (28-30% by weight solution of NH3 in water) The mixture is repeatedly extracted with dichloromethane. separated, dried over sodium sulphate and freed from solvent under reduced pressure A residue of 1.56 g of the product is produced (68.3% of theory, 100% purity according to 1H-NMR) as bright amber crystals. 22: 2-Fluoro-4-methyl-N-[1,3-thiazolidin-2-ylidene]-5-[(2,2,2-trifluoroethyl)sulfinyl]aniline 1-(2-Chloroethyl)-3-{ 2-fluoro-4-methyl-5-[(2,2,2-
[000349] 1.9 g (7.94 mmol) of 2-fluoro-4-methyl-5-[(2,2,2-trifluoroethyl)sulfanyl]aniline are added a little at a time to a solution of 1 mg (8.22 mmol) of 2-chloroethyl isothiocyanate in 50 mL of tert-butyl methyl ether and a catalytic portion of 1,8-diazabicyclo[5.4,0]undec-7-ene (DBU) and are subsequently stirred at room temperature for a further 18 h. Under reduced pressure, most of the solvent is removed from the mixture and the resulting white solid is filtered off with suction. 2.88 g of product are produced (97.1% of theory, >100% purity according to 1H-NMR).
[000350] 1H-NMR(D6-DMSO) ppm: 7.68-7.67(m,1H), 7.43-7.40(m,1H), 4.03-3.93(m,4H) ), 3.61(t,2H), 2.41(s,3H), Step 2: 2-Fluoro-4-methyl-N-[1,3-thiazolidin-2-ylidene]-5-[(2 ,2,2-trifluoroethyl)sulfanyl]aniline (Ia-238)
[000351] 2.75 mg (7.62 mmol) of 1-(2-chloroethyl)-3-{2-fluoro-4-methyl-5-[(2,2,2-trifluoroethyl)sulfanyl]phenyl}urea in a mixture of 3 ml of water and 100 ml of propionitrile with 2 g of potassium carbonate, 3.5 g of cesium carbonate, 0.1 g of sodium hydroxide and 0.1 g of potassium iodide are heated under reflux for 48 h. Under reduced pressure, the mixture is freed from the solvent and the remaining solids sludge is neutralized with dilute hydrochloric acid. The mixture is repeatedly extracted with dichloromethane. The combined organic phases are separated, dried over magnesium sulphate and freed from solvent under reduced pressure. Yield 2.38 g of a brown oil as a crude product. Purification by column chromatography using Biotage Isolera One with a 50 g Snap cartridge and 1:1 v/v ethyl acetate/cyclohexane as mobile phase yielded 590 mg of product (23.9% of theory, purity according to with LC/MS 92.9%).
[000352] 13C-NMR(D6-DMSO) ppm: 163.3, 153.7, 134.8, 126.9(broad), 126.9, 126.0, 117.0, 45.0(broad) , 35.5, 29.8, 19.4 Step 3: 2-Fluoro-4-methyl-N-[1,3-thiazolidin-2-ylidene]-5-[(2,2,2-trifluoroethyl)sulfinyl ]aniline
[000353] At 0-4°C, 99 mg (0.305 mmol) of 2-fluoro-4-methyl-N-[1,3-thiazolidin-2-ylidene]-5-[(2,2,2-trifluoroethyl) )sulfanyl]aniline (Ia-238) are initially charged in 10 ml of trichloromethane. After the addition of 120 mg of pH 7 buffer solution (KH2PO4/Na2HPO4) and 20 mg of benzyltriethylammonium chloride, 80 mg (70%, 0.357 mmol) of m-chloroperbenzoic acid are added a little at a time between 0-4° C and the reaction mixture was stirred at room temperature for 24 h. 33% aqueous sodium bisulfite solution was added and the mixture is then extracted twice with dichloromethane. The combined organic phases are washed with water, dried over sodium sulfate and filtered. After removing the solvent under reduced pressure, the residue is purified by column chromatography using MPLC on RPC-18) with water/acetonitrile. 15 mg of product are produced (14.4% of theory, 100% purity according to LC/MS).
[000354] 13C-NMR(D6-DMSO) ppm: 165.3, 157.5, 137.2, 131.5, 125.6, 120.6, 119.5, 58.5, 46.4, 31 .3
[000355] logP(HCOOH): 0.80 Preparation Example 23: 2-Fluoro-4-methyl-N-[(2E)-1-phenylpyrrolidin-2-ylidene]-5-[(2,2,2- trifluoroethyl)sulfinyl]aniline (Ib-55) Step 1: 2-Fluoro-4-methyl-N-[(2E)-1-phenylpyrrolidin-2-ylidene]-5-[(2,2,2-trifluoroethyl)sulfanyl ]aniline
150 mg (0.63 mmol) of 2-fluoro-4-methyl-5-[(2,2,2-trifluoroethyl)sulfanyl]aniline and 202 mg (1.25 mmol) of N- are initially charged. phenyl-2-pyrrolidinone. 0.29 ml (3.14 mmol) of phosphoryl chloride are slowly added dropwise and the reaction mixture is stirred at 100 °C for 2 h. After cooling, the mixture is poured into ice water, the pH is adjusted to 8-9 with sodium hydroxide solution and the mixture is extracted three times with ethyl acetate. The combined organic phases are washed with saturated sodium chloride solution, dried over sodium sulfate, filtered and concentrated. The residue is taken up in acetonitrile, adsorbed on RP(C-18) and purified by MPLC on RP(C-18) with water/acetonitrile. Two fractions were isolated: 89 mg (98% purity, 37% of theory) and 65 mg (98% purity, 27% of theory) of the title compound.
(Ib-55)[000357] logP(HCOOH): 1.83; logP (neutral): 4.92; 1H-NMR (D6-DMSO, 400 MHz) ppm 7.85(d,2H), 7.36(dd,2H), 7.12-7.09(m,3H), 3.92-3.84 (m,4H), 2H under DMSO peak, 2.33(s,3H), 2.05-1.97(m,2H) Step 2: 2-Fluoro-4-methyl-N-[(2E) -1-phenylpyrrolidin-2-ylidene]-5-[(2,2,2-trifluoroethyl)sulfinyl]aniline (Ib-55) (Ib-55)
[000358] At 0-4 °C 89 g (0.23 mmol) of 2-fluoro-4-methyl-N-[(2E)-1-phenylpyrrolidin-2-ylidene]-5-[(2.2, 2-trifluoroethyl)sulfanyl]aniline are initially charged in 3 ml of dichloromethane and 69 g (0.28 mmol) of meta-chloroperbenzoic acid (70%) are added and the reaction mixture is stirred at room temperature for a further 2 h. A 33% sodium thiosulfate solution (peroxide test was performed) and a saturated sodium bicarbonate solution are added and the mixture is then extracted twice with dichloromethane. The combined organic phases are washed with saturated sodium bicarbonate solution, dried over sodium sulfate and filtered, and the solvent is removed under reduced pressure. The residue comprises 98 mg (94% purity, 99% of theory) of the title compound as a brown oil.
(X-2) (XXXVIII-1)[000359] logP(HCOOH): 1.27; logP (neutral): 3.47; 1H-NMR (D6-DMSO, 400 MHz) ppm 7.86(d,2H), 7.37(m,3H), 7.22(d,1H), 7.09(dd,1H), 4, 14-4.02(m,2H), 3.73(dd,2H), 2.67-2.57(m,2H), 2.33(s,3H), 2.07-1.99( m,2H) Preparation Example 24: 2-({2-Fluoro-4-methyl-5-[(2,2,2-trifluoroethyl)sulfinyl]phenyl}imino)-3-(2,2,2-trifluoroethyl) )-1,3-thiazolidin-4-one (Ib-71) Stage 1.a: 1-{2-Fluoro-4-methyl-5-[(2,2,2-trifluoroethyl)sulfanyl]phenyl}-3 - (2,2,2-trifluoroethyl)thiourea known from JP 2011-42611 (example 250) (X-2) (XXXVIII-1)
[000360] 1.00 g (4.18 mmol) of 2-fluoro-4-methyl-5-[(2,2,2-trifluoroethyl)sulfanyl]aniline is initially charged in 5 ml of dichloromethane and 0.006 ml is added (0.042 mmol) of triethylamine. After addition of 0.59 g (4.18 mmol) of 1,1,1-trifluoro-2-isothiocyanatoethane, the reaction mixture is stirred overnight. The solvent is removed under reduced pressure, the residue is triturated with a little toluene and the insoluble fraction is filtered off with suction and dried. Yield 0.31 g (100% purity, 20% of theory) of the title compound as a white solid. Under reduced pressure, the filtrate is freed from the solvent. The 1.30 g residue includes the title compound with a purity grade of 77%.
(XXXVIII-1) (Ia-175)[000361] logP(HCOOH): 3.32; logP (neutral): 3.24; 1H-NMR (D6-DMSO, 400MHz) ppm 9.62(bs,1H), 8.34(bs,1H), 7.76(d,1H), 7.26(d,1H), 4, 46-4.40(m,2H), 3.87(q,2H), 2.38(s,3H) Step 2.a: 2-({2-Fluoro-4-methyl-5-[(2 ,2,2-trifluoroethyl)sulfanyl]phenyl}imino)-3-(2,2,2-trifluoroethyl)-1,3-thiazolidin-4-one (Ia-175) (XXXVIII-1) (Ia-175)
[000362] 75 mg (97% purity, 0.19 mmol) of 1-{2-fluoro-4-methyl-5-[(2,2,2-trifluoroethyl)sulfanyl]phenyl}-3-(2, 2,2-trifluoroethyl)thiourea and 27 mg (0.19 mmol) of bromoacetic acid are initially charged in 2 ml of toluene and the mixture is stirred under reflux for 6 h. After cooling, a saturated sodium chloride solution is added to the reaction mixture and the organic phase is separated, dried over sodium sulfate and freed from solvent under reduced pressure. The residue is applied to RP(C-18) material and purified by MPLC to RP(C-18) with water/acetonitrile. 18 g (100% purity, 23% of theory) of the title compound is isolated as a white solid.
(Ia-175) (Ib-71)[000363] logP(HCOOH): 4.09; logP (neutral): 3.99; 1H-NMR (D6-DMSO, 400MHz) ppm 7.27(d,1H), 7.21(d,1H), 4.58(q,2H), 4.24(s,2H), 3, 87(q,2H), 2.39(s,3H) Step 3.a: 2-({2-Fluoro-4-methyl-5-[(2,2,2-trifluoroethyl)sulfinyl]phenyl}imino) - 3-(2,2,2-trifluoroethyl)-1,3-thiazolidin-4-one (Ib-71) (Ia-175) (Ib-71)
[000364] At 0-4 °C 136 g (0.32 mmol) of 2-({2-fluoro-4-methyl-5-[(2,2,2-trifluoroethyl)sulfanyl]phenyl}imino)-3 -(2,2,2-trifluoroethyl)-1,3-thiazolidin-4-one are initially charged in 3 ml of dichloromethane and 84 mg (0.32 mmol) of meta-chloroperbenzoic acid (70%) are added and the reaction mixture is stirred at room temperature for another 2 h. A 33% sodium thiosulfate solution (peroxide test was performed) and a saturated sodium bicarbonate solution are added and the mixture is then extracted twice with dichloromethane. The combined organic phases are washed with saturated sodium bicarbonate solution, dried over sodium sulfate and filtered, and the solvent is removed under reduced pressure. The residue comprises 136 g (100% purity, 96% of theory) of the title compound as a lightly colored oil which crystallizes to a white solid over time.
[000365] logP(HCOOH): 2.93; logP (neutral): 2.87; 1H-NMR (D6-DMSO, 400 MHz) ppm 7.51(d,1H), 7.38(d,1H), 4.62-4.57(m,2H), 4.26-4.14 (m,3H), 4.04-3.94(m,1H), 2.36(s,3H)
[000366] Alternatively, syntheses can be carried out as follows: Step 1.b: 2-Fluoro-4-methyl-5-[(2,2,2-trifluoroethyl)sulfinyl]aniline
[000367] At 0-4°C 5.00 g (0.21 mmol) of 2-fluoro-4-methyl-5-[(2,2,2-trifluoroethyl)sulfanyl]aniline are initially charged in 100 ml of dichloromethane and 6.18 g (0.25 mmol) of meta-chloroperbenzoic acid (70%) are added and the reaction mixture is stirred at room temperature for a further 2 h. A 33% sodium thiosulfate solution is then added (peroxide test was carried out) and the mixture is then extracted twice with dichloromethane. The combined organic phases are washed with saturated sodium bicarbonate solution, dried over sodium sulfate and filtered, and the solvent is removed under reduced pressure. The residue comprises 5.10 mg (90% purity, 86% of theory) of the title compound as a brown oil.
[000368] logP(HCOOH): 1.77; logP (neutral): 1.72; 1H-NMR (D6-DMSO, 400 MHz) ppm 7.26(d,1H), 7.02(d,1H), 5.45(bs,2H), 4.08-3.95(m,1H) ), 3.88-3.75(m,1H), 2.19(s,3H) Step 2.b: 1-{2-Fluoro-4-methyl-5-[(2,2,2-trifluoroethyl) )sulfinyl]phenyl}-3-(2,2,2-trifluoroethyl)thiourea
[000369] 1.00 g (3.53 mmol) of 2-fluoro-4-methyl-5-[(2,2,2-trifluoroethyl)sulfanyl]aniline (90% purity) is initially loaded into 5 ml of dichloromethane and 0.005 ml (0.035 mmol) of triethylamine are added. After adding 0.50 g (3.53 mmol) of 1,1,1-trifluoro-2-isothiocyanatoethane, the reaction mixture is stirred overnight. The insoluble fraction is removed by suction filtration and dried. Yield 0.60 g (100% purity, 43% of theory) of the title compound as a white solid. Under reduced pressure, the filtrate is freed from the solvent. The 0.81 g residue includes the title compound with a purity grade of 54%.
(XXXVII-1) (Ib-71)[000370] logP(HCOOH): 2.34; logP (neutral): 2.30; 1H-NMR (D6-DMSO, 400MHz) ppm 9.75(bs,1H), 8.50(bs,1H), 8.12(bd,1H), 7.36(d,1H), 4, 52-4.40(m,1H), 4.21-4.15(m,1H), 4.05-3.95(m,1H), 2.36(s,3H) Step 3.c: 2-({2-Fluoro-4-methyl-5-[(2,2,2-trifluoroethyl)sulfinyl]phenyl}imino)-3-(2,2,2-trifluoroethyl)-1,3-thiazolidin-4 -one (Ib-71) (XXXVII-1) (Ib-71)
Fase 1: 3,4-Dimetil-1,2,4-tiadiazol-5(4H)-ona [000371] 200 mg (0.51 mmol) of 1-{2-fluoro-4-methyl-5-[(2,2,2-trifluoroethyl)sulfanyl]phenyl}-3-(2,2,2-trifluoroethyl) )thiourea and 70 mg (0.51 mmol) of bromoacetic acid are initially charged in 2 ml of toluene and the mixture is stirred under reflux for 6 h. A saturated sodium chloride solution is added to the reaction mixture and the organic phase is separated, dried over sodium sulfate and freed from solvent under reduced pressure. The residue is applied to RP(C-18) material and purified by MPLC to RP(C-18) with water/acetonitrile. 63 g (97% purity, 28% of theory) of the title compound is isolated as a white solid. Preparation Example 25: Synthesis of 3,4-dimethyl-5-(methylsulfanyl)-1,2,4-thiadiazol-4-ium methyl sulfate Stage 1: 3,4-Dimethyl-1,2,4-thiadiazol-5(4H)-one
[000372] At 0 °C, 6.13 g (27.6 mmol) of phosphorus pentasulfide are added to a solution of 1.80 g (13.80 mmol) of 3,4-dimethyl-1.2.4 -thiadiazol-5(4H)-one (crude, prepared according to J. Chem. soc. Perkin Trans. 1 1983, 4, 687-691) in xylene and the mixture is then heated at 100°C for 4 h . After aqueous work-up and purification by chromatography, 0.60 g (30% of theory) of the title compound are obtained. Step 2: 3,4-Dimethyl-5-(methylsulfanyl)-1,2,4-thiadiazol-4-ium methylsulfate
[000373] With stirring, 0.62 g (4.52 mmol) of dimethylsulfate are added to a solution of 0.60 g (4.10 mmol) of 3,4-dimethyl-1,2,4-thiadiazol-5 (4H)-thione in acetonitrile and the mixture is then stirred under reflux for 5 h. After cooling the solvent is removed under reduced pressure and the residue obtained (1.50) is reacted with crude product. Preparation Example 26: N-(3,4-Dimethyl-1,2,4-thiadiazol-5(4H)-ylidene)-2,4-dimethyl-5-[(2,2,2-trifluoroethyl)sulfinyl] aniline (Ib-173) Step 1: N-(3,4-Dimethyl-1,2,4-thiadiazol-5(4H)-ylidene)-2,4-dimethyl-5-[(2,2,2- trifluoroethyl)sulfanyl]aniline
Abreviaturas:[000374] The preparation processes described above can be used to produce the compounds of the Formula (I), for example the following compounds of the Formula (I):
Abbreviations:
[000375] PD-F-heptyl = pentadecafluoroheptyl; DD-F-hexyl = 1,1,2,2,3,3,4,4,5,5,6,6-dodecafluorohexyl; CHF2 = difluoromethyl; Cpr = cyclopropyl; Cl = chlorine; F = fluorine.
[000376] The logP values were determined according to Annex V.A8 of the European Directive 79/831 by HPLC (high performance liquid chromatography) on reverse phase columns (C 18), using the following methods:
[000377] [a] The LC-MS determination at the acid level was carried out at pH 2.7, using 0.1% aqueous formic acid and acetonitrile (contains 0.1% formic acid) as mobile phases; linear gradient from 10% acetonitrile to 95% acetonitrile. Also referred to as logP(HCOOH).
[000378] [b] The LC-MS determination at the neutral level was carried out at pH 7.8, using 0.001 mole of aqueous solution of ammonium bicarbonate and acetonitrile as mobile phases; linear gradient from 10% acetonitrile to 95% acetonitrile. Also referred to as logP(neutral).
[000379] [c] The determination at the acid level was carried out at pH 2.3, using 0.1% aqueous phosphoric acid and acetonitrile as mobile phases; linear gradient from 10% acetonitrile to 95% acetonitrile.
[000380] Calibration was conducted using unbranched alkan-2-ones (including 3 to 16 carbon atoms) with known logP values (determination of logP values by retention periods using linear interpolation between two successive alkanones).
[000381] The maximum lambda values were determined using UV spectra from 200 nm to 400 nm and the peak values of the chromatographic signals. NMR data from selected examples
[000382] The NMR data of selected examples are indicated either in conventional form (δ values, number of hydrogen atoms, division of multiplets) or as lists of NMR peaks.
[000383] NMR peak list method:
[000384] When 1H NMR data for selected examples is indicated in the form of lists of 1H NMR peaks, the value in ppm is indicated first and then the signal strength of each peak separated by a space. The value - pairs of signal strength numbers from different signal peaks are indicated separated from each other by semicolons.
[000385] The list of peaks for an example thus takes the form of:
[000386] i intensity^ 2 intensity2;...;i intensity^...; no intensity

















[000387] The solvent in which the NMR spectrum was recorded is indicated in square brackets after the example number and before the NMR peak list or the conventional NMR interpretation list.


































































[000388] The sharp signal strength is related to the strength of the signals in a printed example of an NMR spectrum in cm and shows the true proportions of the signal strengths. In the case of wide signals, several peaks or the middle of the signal and relative intensities may be displayed compared to the most intense signal in the spectrum.
[000389] 1H NMR peak lists are similar to conventional 1H NMR prints and typically contain all peaks listed in a conventional NMR interpretation.
[000390] Furthermore, like conventional 1H NMR prints, they can show solvent signals, stereoisomer signals of the target compounds, which also form part of the subject matter of the invention, and/or impurity peaks.
[000391] In the compound signal log, in the delta range of solvents and/or water our 1H NMR peak lists show the usual solvent peaks, for example, DMSO peaks in DMSO-d6 and the water peak, which usually have a high intensity on average.
The peaks of stereoisomers of the target compounds and/or peaks of impurities usually have a lower intensity than the peaks of the target compounds (for example with a degree of purity of >90%).
[000393] These stereoisomers and/or impurities may be typical of the particular preparation process. In this case, the respective peaks can thus help to identify the reproduction of our preparation process with reference to “fingerprints of by-products”.
[000394] A specialist who calculates the target compounds by known methods (MestreC, ACD simulation, but also with predicted values evaluated empirically) can, if necessary, isolate the peaks of the target compounds, optionally using intensity filters. Isolation would be similar to the relevant peak in a conventional 1H NMR interpretation.
[000395] If, as a result of rounding the value to two decimal places, there are signals with the same value δ, the respective intensities after addition present the same image that would also be observed in the printed image of a classic NMR in the region of this value δ -
GC-MS: Massa EI (m/z): 373 (2Cl) [M]+[000396] The preparation processes described above can be used to obtain the compounds of the Formula (II), for example the following compounds of the Formula (II): N-{2-Chloro-4-fluoro-5-[ chloride (2,2,2-trifluoroethyl)sulfanyl]phenyl}-2,2,2-trifluoroethaniidoyl (II-4) GC-MS: EI Mass (m/z): 373 (2Cl) [M]+
[000397] The preparation processes described above can be used to obtain the compounds of the Formula (III), for example the following compounds of the Formula (III): 2,2,2-Trifluoro-N-{4-fluoro-2 -methyl-5-[(2,2,2-trifluoroethyl)sulfanyl]phenyl}acetamide (III-4) F
[000398] logP(HCOOH): 3.16; logP (neutral): 3.1; 1H-NMR (D6-DMSO, 400MHz) ppm 11.05(s,1H), 7.59(d,1H), 7.31(d,1H), 3.96(q,2H), 2, 17(s,3H) N-{4-Bromo-2-chloro-5-[(2,2,2-trifluoroethyl)sulfanyl]phenyl}-2,2,2-trifluoroacetamide (III-5)
[000399] logP(HCOOH): 3.78; 1H-NMR (D6-DMSO, 400 MHz) ppm 4.17-4.24(m,2H), 7.79(s,1H), 8.01(s,1H), 11.45(s,1H) ) N-{2,4-Dibromo-5-[(2,2,2-trifluoroethyl)sulfanyl]phenyl}-2,2,2-trifluoroacetamide (III-6)
[000400] logP(HCOOH): 3.81; 1H-NMR (D6-DMSO, 400MHz) ppm 11.21(s,1H), 7.90(s,1H), 7.56(s,1H), 3.99(q,2H) N-{ 2-Chloro-4-fluoro-5-[(2,2,2-trifluoroethyl)sulfanyl]phenyl}-2,2,2-trifluoroacetamide (III-7)
[000401] logP(HCOOH): 3.33; logP(neutral): 3.11; 1H-NMR (D6-DMSO, 400MHz) ppm 11.39(s,1H), 7.85(d,1H), 7.76(d,1H), 4.08(q,2H) N-{ 4-Chloro-2-fluoro-5-[(2,2,2-trifluoroethyl)sulfanyl]phenyl}-2,2,2-trifluoroacetamide (III-8)
[000402] logP(HCOOH): 3.34; logP(neutral): 3.14; 1H-NMR (D6-DMSO, 400MHz) ppm 11.47(bs,1H), 7.85(d,1H), 7.76(d,1H), 4.09(q,2H) N-{ 4-Bromo-2-chloro-5-[(2,2,2-trifluoroethyl)sulfanyl]phenyl}-2,2,2-trifluoroacetamide (III-9)
[000403] logP(HCOOH): 3.46; logP (neutral): 3.11; 1H-NMR (D6-DMSO, 400MHz) ppm 11.46(s,1H), 7.87(d,1H), 7.82(d,1H), 4.11(q,2H)
[000404] The preparation processes described above can be used to obtain the compounds of the Formula (IV), for example the following compounds of the Formula (IV): N,N'-[Disulfanediylbis(4-fluoro-6-methylbenzene- 3,1-diyl)]bis(2,2,2-trifluoroacetamide) (IV-2)
[000405] logP(HCOOH): 4.0; logP(neutral): 3.92; 1H-NMR (D6-DMSO, 400MHz) ppm 11.04(s,2H), 7.62(d,2H), 7.32(d,2H), 2.19(s,6H) N,N '-[Disulfanediylbis(4-bromo-6-chlorobenzene-3.1-diyl)]bis(2,2,2-trifluoroacetamide) (IV-3)
[000406] logP(HCOOH): 5.42 N,N'-[Disulfanediylbis(4,6-dibromobenzene-3.1-diyl)]bis(2,2,2-trifluoroacetamide) (IV-4)
[000407] logP(HCOOH): 5.62; logP(neutral): 4.49; 1H-NMR (D6-DMSO, 400 MHz) ppm 11.38(s,2H), 8.18(s,2H), 7.77(d,2H) N,N'-[Disulfanediylbis(6-chloro- 4-fluorobenzene-3.1-diyl)]bis(2,2,2-trifluoroacetamide) (IV-5)
[000408] logP(HCOOH): 4.45; logP(neutral): 3.81; 1H-NMR (D6-DMSO, 400 MHz) ppm 11.37(s,2H), 7.88(d,2H), 7.80(d,2H) N,N'-[Disulfanediylbis(4-chloro- 6-fluorobenzene-3.1-diyl)]bis(2,2,2-trifluoroacetamide) (IV-6)
[000409] logP(HCOOH): 4.60; logP(neutral): 3.82; 1H-NMR (D6-DMSO, 400 MHz) ppm 11.44(s,2H), 7.95(d,2H), 7.83(d,2H) N,N'-[Disulfanediylbis(4-bromo- 6-fluorobenzene-3.1-diyl)]bis(2,2,2-trifluoroacetamide) (IV-7)
[000410] logP(HCOOH): 4.76; logP(neutral): 4.02; 1H-NMR (D6-DMSO, 400 MHz) ppm 11.44(s,2H), 7.95-7.89 (m,4H)
[000411] The preparation processes described above can be used to obtain the compounds of the Formula (V), for example the following compounds of the Formula (V): 2-Fluoro-4-methyl-5-[(trifluoroacetyl) chloride amino]benzenesulfonyl (V-2)
[000412] 1H-NMR (D6-DMSO, 400MHz) ppm 10.98 (s,1H), 7.48 (d,1H), 7.12 (d,1H), 2.15 (s,3H) 2,4-Dibromo-5-[(trifluoroacetyl)amino]benzenesulfonyl chloride (V-3)
[000413] 1H-NMR (D6-DMSO, 400MHz) ppm 9.20(bs,1H), 8.56(s,1H), 8.36(s,1H) 4-Chloro-2-fluoro chloride -5- [(trifluoroacetyl)amino]benzenesulfonyl (V-4) F
[000414] 1H-NMR (D6-DMSO, 400 MHz) ppm 11.30(s,1H), 7.72-7.67(m,1H), 7.59-7.55(d,1H) Chloride of 2-Bromo-4-fluoro-5-[(trifluoroacetyl)amino]benzenesulfonyl (V-5) O
[000415] 1H-NMR (D6-DMsO, 400 MHz) ppm 9.38(bs,1H), 8.00-7.97(m,1H), 7.68(d,1H)
[000416] The preparation processes described above can be used to obtain the compounds of the Formula (VI), for example the following compounds of the Formula (VI): 2,2,2-Trifluoro-N-(4-fluoro-2 -methylphenyl)acetamide (VI-2)
[000417] logP(HCOOH): 2.2; logP(neutral): 2.19; 1H-NMR (D6-DMSO, 400 MHz) ppm 10.97(s,1H), 7.28-7.30(m,1H), 7.19-7.21(m,1H), 7.08 - 7.11(m,1H), 2.18(s,3H) N-(4-Bromo-2-chlorophenyl)-2,2,2-trifluoroacetamide (VI-3)
[000418] logP(HCOOH): 3.01; logP(neutral): 2.81; 1H-NMR (D6-DMSO, 400MHz) ppm 11.35 (s,1H), 7.92 (d, 1H), 7.65 (dd,1H), 7.45 (d,1H) N-( 2,4-Dibromophenyl)-2,2,2-trifluoroacetamide (VI-4)
[000419] logP(HCOOH): 3.10; logP (neutral): 2.89; 1H-NMR (D6-DMSO, 400MHz) ppm 11.36(s,1H), 8.04(d,1H), 7.69(dd,1H), 7.43(d,1H) N-( 2-Chloro-4-fluorophenyl)-2,2,2-trifluoroacetamide (VI-5)
[000420] logP(HCOOH): 2.46; logP(neutral): 2.31; 1H-NMR (D6-DMSO, 400MHz) ppm 11.29(s,1H), 7.64(dd,1H), 7.53(dd,1H), 7.35-7.30(m,1H) ) N-(4-Chloro-2-fluorophenyl)-2,2,2-trifluoroacetamide (VI-6)
[000421] logP(HCOOH): 2.53; logP(neutral): 2.40; 1H-NMR (D6-DMSO, 400MHz) ppm 11.29(s,1H), 7.62(dd,1H), 7.55(dd,1H), 7.37(dd,1H) N-( 4-Bromo-2-fluorophenyl)-2,2,2-trifluoroacetamide (VI-7)
[000422] logP(HCOOH): 2.73; logP(neutral): 2.51; 1H-NMR (D6-DMSO, 400 MHz) ppm 11.36(s,1H), 7.74(d,1H), 7.52-7.46(m,2H)
[000423] The preparation processes described above can be used to obtain the compounds of the Formula (X), for example the following compounds of the Formula (X): 4-Chloro-2-fluoro-5-[(2.2, 2-trifluoroethyl)sulfanyl]aniline (X-6)
[000424] 11.0 g (30.9 mmol) of N-{4-chloro-2-fluoro-5-[(2,2,2-trifluoroethyl)sulfanyl]phenyl}-2,2,2-trifluoroacetamide in 150 ml of dioxane are carefully added to a solution of 10.3 ml (186 mmol) of sulfuric acid (96%) in 100 ml of water. The reaction mixture is then heated under reflux overnight. After cooling, the solution is adjusted to pH 7 using a saturated solution of sodium bicarbonate and a little sodium carbonate and extracted three times with ethyl acetate. The combined organic phases are washed with saturated sodium chloride solution, dried over sodium sulfate, filtered and concentrated. The residue comprises 8.27 mg (96% purity, 99% of theory) of the title compound as an oil/black solid mixture.
[000425] logP(HCOOH): 3.02; logP(neutral): 3.00; 1H-NMR (D6-DMSO, 400MHz) ppm 7.27(d,1H), 7.04(d,1H), 5.46(bs,2H), 3.85(q,2H) 2-Chlorine -5-[(2,2,2-trifluoroethyl)sulfanyl]aniline (X-7)
[000426] logP(HCOOH): 3.00; logP(neutral): 2.95; 1H-NMR (D6-DMSO, 400 MHz) ppm 7.16(d,1H), 6.89(d,1H), 6.68-6.65(m,1H), 5.48(broad,2H) ), 3.89(q,2H); GC-MS: Mass EI (m/z): 241 (1Cl) [M]+ 2-Fluoro-5-[(2,2,2-trifluoroethyl)sulfanyl]aniline (X-8)
[000427] logP(HCOOH): 2.57; logP(neutral): 2.53; 1H-NMR (D6-DMSO, 400 MHz) ppm 7.01-6.97(m,1H), 6.92-6.89(m,1H), 6.69-6.64(m,1H) , 5.31(broad,2H), 3.82(q,2H); GC-MS: EI Mass (m/z): 225 [M]+
[000428] The preparation processes described above can be used to obtain the compounds of the Formula (XXI for example the following compounds of the Formula (XXI 1,1'-Disulfanediylbis(4-chloro-3-nitrobenzene) (XXI-2)
[000429] logP(HCOOH): 4.58; logP(neutral): 4.58; 1H-NMR (D6-DMSo, 400MHz) ppm 8.29(d,2H), 7.89-7.86(m,2H), 7.81(d,2H); GC-MS: Mass EI (m/z): 376 (2Cl) [M]+ 1,1'-Disulfanediylbis(4-fluoro-3-nitrobenzene) (XXI-3)
[000430] logP(HCOOH): 3.83; logP(neutral): 3.79; 1H-NMR (D6-DMSO, 400 MHz) ppm 8.32-8.29(m,2H), 8.03-7.97(m,2H), 7.69-7.63(m,2H) ; GC-MS: Mass EI (m/z): 344 [M]+ 1,1'-Disulfanediylbis(2,4-dichloro-5-nitrobenzene) (XXI-4)
[000431] logP(HCOOH): 5.69; logP(neutral): 5.64; 1H-NMR (D6-DMSO, 400 MHz) ppm 8.33(s,2H), 8.21(s,2H)
[000432] The preparation processes described above can be used to obtain the compounds of the Formula (XXII) for example the following compounds of the Formula (XXII): 3,3'-Disulfanediylbis(6-chloroaniline) (XXII-2)
[000433] logP(HCOOH): 3.84; logP(neutral): 3.83; 1H-NMR (D6-DMSO, 400 MHz) ppm 7.18(d,2H), 6.94(d,2H), 6.65-6.62(m,2H), 5.59(broad,4H) ); GC-MS: Mass EI (m/z): 316 (2Cl) [M]+ 3,3'-Disulfanediylbis(6-fluoroaniline) (XXII-3)
[000434] logP(HCOOH): 2.98; logP(neutral): 2.97; 1H-NMR (D6-DMSO, 400 MHz) ppm 7.02-6.95(m,2H), 6.95-6.82(m,2H), 6.62-6.57(m,2H) , 5.40(broad,4H); GC-MS: Mass EI (m/z): 284 [M]+ 3,3'-Disulfanediylbis(4,6-dichloroaniline) (XXII-4)
[000435] logP(HCOOH): 5.14; logP(neutral): 4.95; 1H-NMR (D6-DMSO, 400MHz) ppm 7.41(s,2H), 6.95(s,2H), 5.78(broad,4H); GC-MS: EI Mass (m/z): 386 (4Cl) [M]+
[000436] The preparation processes described above can be used to obtain the compounds of the Formula (XXIV) for example the following compounds of the Formula (XXIV): 1-Chloro-2-fluorocyclopropanecarboxamide (XXIV-1)
[000437] 1H-NMR(D6-DMSO) ppm: 7.84(broad,1H), 7.75(broad,1H), 5.05-4.86(m,1H), 1.89-1, 81(m,1H), 1.69-1.60(m,1H) N-(2,2,2-Trifluoroethyl)cyclopentanecarboxamide (XXIV-2)
[000438] 1H-NMR(D6-DMSO) ppm: 8.43(broad,1H), 3.92-3.83(m,2H), 3.08-3.07(m,1H), 2, 67-2.59(m,1H), 1.79-1.49(m,7H) N-(2,2-Difluoroethyl)cyclopentanecarboxamide (XXIV-3)
[000439] 1H-NMR(D6-DMSO) ppm: 8.18(t,1H), 5.97(tt,1H), 3.50-3.40(m,2H), 3.08-3, 06(m,1H), 2.64-2.57(m,1H), 1.78-1.45(m,7H) N-(1,1,1-Trifluoropropan-2-yl)cyclopropanecarboxamide (XXIV -4)
[000440] 1H-NMR(D6-DMSO) ppm: 8.62-8.60(d,1H), 4.62-4.55(m,1H), 1.63-1.59(m,1H) ), 1.24-1.23(d,3H), 0.72-0.70(m,4H) (3-Pyridyl)(4,4-difluoropiperidin-1-yl)methanone (XXIV-5)
[000441] 1H-NMR(D6-DMSO) ppm: 8.67-8.66(m,2H), 7.90-7.87(m,1H), 7.51-7.48(m,1H) ), 3.73(m,2H), 3.42(m,2H), 2.06(m,4H) (2-Chlorophenyl)(4,4-difluoropiperidin-1-yl)methanone (XXIV-6)
[000442] 1H-NMR(D6-DMSO) ppm: 7.56-7.53(m,1H), 7.49-7.41(m,3H), 3.90-3.84(m,1H) ), 3.70-3.64(m,1H), 3.34-3.22(m,2H), 2.15-1.90(m,4H) Examples of Use Test with Phaedon (spray treatment) PHAECO)
[000443] Solvents: 78.0 parts by weight of acetone 1.5 parts by weight of N,N-dimethylformamide
[000444] Emulsifier: 0.5 parts by weight of polyglycolic alkylaryl ether
[000445] To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the indicated amounts of solvent and emulsifier and the concentrate is diluted with water containing emulsifier to the desired concentration. Chinese cabbage (Brassica pekinensis) leaves are sprayed with the preparation of the active compound at the desired concentration and, after drying, are colonized with mustard beetle larvae (Phaedon cochleariae).
[000446] After 7 days the effect in % is determined. 100% means that all the beetle larvae have been killed; 0 % means that none of the beetle's larvae were killed.
[000447] In this tests, for example, the following compounds in the preparation examples show a level of effectiveness of
[000448] 100% at an application rate of 500 g/ha: Ia-02, Ia-04, Ia-05, Ia-13, Ia-14, Ia-15, Ia-18, Ia-19,
[000449] Ib-02, Ib-10, Ib-11, Ib-14, Ib-16 Test with Tetranychus, resistance to organophosphates (TETRUR spray treatment) Solvents: 78.0 parts by weight of acetone 1.5 parts in weight of N,N-dimethylformamide Emulsifier: 0.5 parts by weight of polyglycolic alkylaryl ether
[000450] To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the indicated amounts of solvent and emulsifier and the concentrate is diluted with water containing emulsifier to the desired concentration. Bean (Phaseolus vulgaris) leaf discs that have been infested with all stages of the greenhouse spider mite (Tetranychus urticae) are sprayed with a preparation of the active compound at the desired concentration.
[000451] After 6 days the effect in % is determined. 100% means all mites have been killed; 0% means that none of the mites were killed.
[000452] In these tests, for example, the following compounds of the preparation examples show an efficacy level of 80% at an application rate of 500 g/ha.Ia-09, Ia-17, Ib-04, Ib- 05
[000453] In these tests, for example, the following compounds in the preparation examples show an efficacy level of 100% at an application rate of 500 g/ha.Ia-02, Ia-03, Ia-05, Ia- 07, la-12, la-13, la-15, la-18,
[000454] Ia-23, Ia-26, Ib-02, Ib-03, Ib-06, Ib-07, Ib-08, Ib-09, Ib-12, Ib-13, Ib-15 Test with Meloidogyne incognita (MELGIN) Solvents: 80.0 parts by weight of acetone
[000455] To prepare a suitable preparation of the active compound, 1 part by weight of the active compound is mixed with the stated amounts of solvent and the concentrate is diluted with water to obtain the desired concentration.
The containers are filled with sand, active compound solution, egg/larvae suspension of Meloidogyne incognita and lettuce seeds. Lettuce seeds germinate and plants develop. Galls form at the roots.
[000457] After 14 days, the effectiveness of the nematicide is determined in % of gall formation. 100% means no galls were found; 0% means that the number of galls on the treated plants corresponds to the untreated control.
[000458] In this tests, for example, the following composite of the preparation examples shows a level of effectiveness of
[000459] 90% at an application rate of 20 ppm: Ia-07
[000460] In this tests, for example, the following composite of the preparation examples shows a level of effectiveness of
[000461] 100% at an application rate of 20 ppm: Ib-02 Lucilia cuprina (48h) Solvent: Dimethyl sulfoxide
[000462] 10 mg of the active compound are dissolved in 0.5 ml of dimethyl sulfoxide. To prepare a suitable formulation, the active compound solution is diluted with water to the desired concentration in each case. About 20 Lucilla cuprina larvae are introduced into a test tube containing about 1 cm3 of horse meat and 0.5 ml of the preparation of the active compound to be tested. After 48 hours the efficacy of the preparation of the active compound in % of larval mortality was determined.
[000463] In this test, for example, the following compounds from the preparation examples show an effect level of 100% at an application rate of 100 ppm: Ia-21, Ib-11 Test with Boophilus microplus (BOOPMI injection) Solvent : Dimethyl sulfoxide
[000464] To produce a suitable preparation of the active compound, 10 mg of the active compound is mixed with 0.5 ml of solvent and the concentrate is diluted with solvent to the desired concentration. The active compound solution is injected into the abdomen (Boophilus microplus) and the animals are transferred to dishes and kept in a climate-controlled room. Activity is assessed by laying fertile eggs.
[000465] After 7 days the effect in % is determined. 100% means none of the ticks laid fertile eggs.
[000466] In this tests, for example, the following composite of the preparation examples shows a level of effectiveness of
[000467] 80% at an application rate of 20 μg/animal: Ia-04
[000468] In these tests, for example, the following compounds from the preparation examples show an efficacy level of 100% at an application rate of 20 μg/animal.Ia-01, Ia-21, Ia-22, Ib- 01, Ib-10, Ib-11, Ib-14, Ib-16
[000469] Unless otherwise indicated, the test solution in the examples below was prepared as follows:
[000470] 1 part by weight of the active compound is mixed with the stated amounts of a mixture of solvent and emulsifier (3 parts by weight of dimethylformamide as solvent and 1 part by weight of polyoxyethylene alkylphenyl ether as emulsifier) and the solution is diluted with water in the desired concentration. Test with mites (Tetranychus urticae)
[000471] 50 to 100 adult mites are placed on leaves of common bean in the bifoliar stage, planted in a pot of 6 cm in diameter.
[000472] After one day, using a spray gun, the plant is sprayed with a sufficient amount of the active compound preparation in the desired concentration and placed in an oven. After 7 days, the % acaricide effect is determined. 100% means all mites have been killed; 0% means that none of the mites were killed.
[000473] In these tests, for example, the following compounds in the preparation examples show an efficacy level of 100% at an active compound concentration of 100 ppm:
[000474] Ia-21, Ia-01, Ib-11, Ib-01, Ia-06, Ia-14, Ia-15, Ib-14, Ia-20, Ia-25, Ia-19, Ib-16 and Ib-10 Test with cucurbit leaf beetle (Aulacophora femoralis)
[000475] The cucumber leaves are dipped into an experimental solution at the appropriate concentration and then allowed to air dry. The leaves are then inserted into a plastic dish filled with sterile soil and five Aulacophora femoralis larvae in the second larval stage. The plates are placed in an acclimatized room at 25 °C.
[000476] After 7 days, the effect in % is determined. 100% means that all the beetle larvae have been killed; 0 % means that none of the beetle's larvae were killed.
[000477] In these tests, for example, the following compounds in the preparation examples show an efficacy level of 100% at an active compound concentration of 500 ppm:
[000478] Ia-21, Ib-11, Ib-01, Ib-14, Ib-16 and Ib-10
[000479] Immersion test with Boophilus microplus (BOOPMI bath)
[000480] Experimental animals: cattle tick (Boophilus microplus) Parkhurst strain, resistant to pyrethroids
[000481] Solvent: Dimethyl sulfoxide
[000482] 10 mg of the active compound are dissolved in 0.5 ml of dimethyl sulfoxide. To prepare a suitable formulation, the active compound solution is diluted with water to the desired concentration in each case.
[000483] This preparation of active compound is pipetted into test tubes. 8-10 engorged adult female cattle ticks (Boophilus microplus) are transferred to another perforated tube. The tube is immersed in an active compound formulation and all ticks are thoroughly wetted. After draining the liquid, the ticks are transferred on filter discs to plastic plates and stored in a climate-controlled room.
[000484] Activity is determined after 7 days with the deposition of fertile eggs. Eggs whose fertility is not visible from the outside are kept in climate-controlled compartments until the larvae hatch after about 42 days. 100% effectiveness means that none of the ticks laid fertile eggs; 0% means all eggs were fertile.
[000485] In these tests, for example, the following compounds in the preparation examples show an efficacy level of 100% at an application rate of 100 ppm: Ia-189, Ib-115, Ib-33
[000486] Injection test with Boophilus microplus (BOOPMI injection)
[000487] Solvent: Dimethyl sulfoxide
[000488] To produce a suitable preparation of the active compound, 10 mg of the active compound is mixed with 0.5 ml of solvent and the concentrate is diluted with solvent to the desired concentration.
[000489] 1 μl of the active compound solution is injected into the abdomen of 5 engorged adult females of the cattle tick (Boophilus microplus). The animals are transferred to dishes and kept in an air-conditioned room.
[000490] Activity is determined after 7 days with the deposition of fertile eggs. Eggs whose fertility is not visible from the outside are kept in climate-controlled compartments until the larvae hatch after about 42 days. 100% effectiveness means that none of the ticks laid fertile eggs; 0% means all eggs were fertile.
[000491] In this test, for example, the following compounds from the preparation examples show an effectiveness level of 100% at an application rate of 20 µg/animal. la-01, la-115, la-116, la-118, la-120, la-13, la-189, la-206, la-21, la-22, la-27, la-34, la- 39, Ia-44, Ia-50, Ia-66, Ia-80, Ib-01, Ib-02, Ib-03, Ib-07, Ib-10, Ib-108, Ib-11, Ib-115, Ib-12, Ib-14, Ib-14, Ib-16, Ib-17, Ib-18, Ib-19, Ib-20, Ib-33, Ib-35, Ib-38, Ib-40, Ib- 47, Ib-48, Ib-58, Ib-59, Ib-68, Ib-85
[000492] In this test, for example, the following compounds from the preparation examples show an efficacy level of 90% at an application rate of 20 µg/animal. Ib-44
[000493] In this test, for example, the following compounds from the preparation examples show an efficacy level of 80% at an application rate of 20 µg/animal. Ia-04, Ib-24, Ib-89 Test with Cooperia curticei (COOPCU)
[000494] Solvent: Dimethyl sulfoxide
[000495] To produce a suitable preparation of the active compound, 10 mg of the active compound is mixed with 0.5 ml of dimethyl sulfoxide and the concentrate is diluted with Ringer's solution to the desired concentration.
[000496] Containers containing the preparation of the active compound in the desired concentration are colonized with about 40 nematode larvae (Cooperia curticei).
[000497] After 5 days, mortality in % is determined. 100% means all larvae have been killed; 0% means that none of the larvae were killed.
[000498] In these tests, for example, the following compounds in the preparation examples show an efficacy level of 100% at an application rate of 100 ppm: Ia-220 Test with Lucilia cuprina (LUCICU)
[000499] Solvent: Dimethyl sulfoxide
[000500] To produce a suitable preparation of the active compound, 10 mg of the active compound is mixed with 0.5 ml of dimethyl sulfoxide and the concentrate is diluted with water to the desired concentration.
[000501] About 20 L1 larvae of the blowfly (Lucilia cuprina) are transferred to an experimental container containing minced horse meat and the preparation of the active compound in the desired concentration.
[000502] After 2 days, mortality in % is determined. 100% means all larvae have been killed; 0% means that none of the larvae were killed.
[000503] In this tests, for example, the following compounds in the preparation examples show an efficacy level of 100% at an application rate of 100 ppm: Ia-21, Ib-11
[000504] In these tests, for example, the following compounds in the preparation examples show an effectiveness level of 90% at an application rate of 100 ppm. ia-13
[000505] In these tests, for example, the following compounds in the preparation examples show an efficacy level of 80% at an application rate of 100 ppm. Ib-02 Myzus persicae - active spray test (MYZUPE), 1 part by weight of active compound is mixed with the indicated amounts of solvent and emulsifier and the concentrate is diluted with water containing emulsifier to the desired concentration. Myzus persicae - spray test (MYZUPE)
[000506] Solvents: 78 parts by weight of acetone 1.5 parts by weight of dimethylformamide
[000507] Emulsifier: 0.5 parts by weight of polyglycolic alkylaryl ether
[000508] To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the indicated amounts of solvent and emulsifier and the concentrate is diluted with water containing emulsifier to the desired concentration.
[000509] Chinese cabbage (Brassica pekinensis) leaves infested with all stages of the green peach louse (Myzus persicae) are sprayed with a preparation of the active compound in the desired concentration.
[000510] After 6 days the effect in % is determined. 100% means all aphids have been killed; 0% means none of the aphids were killed.
[000511] In this test, for example, the following compounds from the preparation examples show an effect level of 100% at an application rate of 500 g/ha: Ia-206, Ia-228, Ib-44
[000512] In this test, for example, the following compounds from the preparation examples show an efficiency of 90% at an application rate of 500 g/ha: Ia-34, Ia-116, Ib-123
[000513] In this test, for example, the following compounds in the preparation examples show an efficiency of 80% at an application rate of 500 g/ha: Ib-42 Phaedon cochleariae - Spray test (PHAECO)
[000514] Solvents: 78.0 parts by weight of acetone a. 1.5 parts by weight of dimethylformamide
[000515] Emulsifier: 0.5 parts by weight of polyglycolic alkylaryl ether
[000516] To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the indicated amounts of solvent and emulsifier and the concentrate is diluted with water containing emulsifier to the desired concentration.
[000517] Chinese cabbage leaves (Brassica pekinensis) are sprayed with the preparation of the active compound in the desired concentration and, after drying, are colonized with larvae of the mustard beetle (Phaedon cochleariae).
[000518] After 7 days, the effect in % is determined. 100% means that all the beetle larvae have been killed; 0 % means that none of the beetle's larvae were killed.
[000519] In this test, for example, the following compounds from the preparation examples show an effect level of 100% at an application rate of 500 g/ha: Ia-02, Ia-04, Ia-05, Ia- 13, la-14, la-15, la-18, la-19, la-27, la-28, la-29, la-31, la-35, la-36, la-38, la-45, la-78, la-79, la-115, la-118, la-121, la-135, la-139, la-149, la-162, la-191, la-202, la-209, la- 229, Ib-02, Ib-10, Ib-11, Ib-14, Ib-16, Ib-17, Ib-20, Ib-20, Ib-27, Ib-39, Ib-43, Ib-44, Ib-56, Ib-57, Ib-68, Ib-78, Ib-83, Ib-101, Ib-110, Ib-111, Ib-115
[000520] In this test, for example, the following compounds of the preparation examples show an efficiency of 83% at an application rate of 500 g/ha: Ia-33, Ia-92, Ia-130, Ia-134, Ia -171, Ia-204, Ia-207, Ia-210, Ib-18, Ib-30, Ib-108, Ib-137, Ib-143 Tetranychus urticae - spray test, resistant to organophosphates (TETRUR)
[000521] Solvents: 78.0 parts by weight of acetone b. 1.5 parts by weight of dimethylformamide
[000522] Emulsifier: 0.5 parts by weight of polyglycolic alkylaryl ether
[000523] To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the indicated amounts of solvent and emulsifier and the concentrate is diluted with water containing emulsifier to the desired concentration.
Discs of bean leaves (Phaseolus vulgaris) which have been infested with all stages of the greenhouse spider mite (Tetranychus urticae) are sprayed with a preparation of the active compound in the desired concentration.
[000525] After 6 days the effect in % is determined. 100% means all mites have been killed; 0% means that none of the mites were killed.
[000526] In these tests, for example, the following compounds in the preparation examples show an effectiveness level of 100% at an application rate of 500 g/ha. Ia-01, Ia-02, Ia-03, Ia-04, Ia-05, Ia-06, Ia-07, Ia-08, Ia-11, Ia-12, Ia-13, Ia-14, Ia- 15, la-16, la-18, la-19, la-20, la-21, la-22, la-23, la-25, la-26, la-27, la-28, la-29, la-30, la-31, la-32, la-33, la-34, la-35, la-36, la-37, la-38, la-39, la-40, la-41, la- 42, la-43, la-44, la-46, la-47, la-48, la-49, la-50, la-51, la-52, la-53, la-54, la-55, la-56, la-57, la-60, la-61, la-64, la-65, la-66, la-67, la-69, la-70, la-71, la-72, la- 73, la-74, la-75, la-76, la-77, la-78, la-79, la-80, la-81, la-82, la-83, la-84, la-85, la-86, la-87, la-89, la-93, la-94, la-95, la-96, la-97, la-98, la-99, la-100, la-115, la- 116, la-119, la-120, la-121, la-122, la-123, la-124, la-125, la-126, la-127, la-129, la-130, la-131, la-132, la-133, la-134, la-135, la-136, la-138, la-139, la-140, la-141, la-141, la-275, la-276, la- 02, Ib-03, Ib-06, Ib-07, Ib-08, Ib-09, Ib-10, Ib-11, Ib-12, Ib-13, Ib-14, Ib-15, Ib-16, Ib-17, Ib-19, Ib-20, Ib-21, Ib-22, Ib-24, Ib-25, Ib-26, Ib-27, Ib-28, Ib-29, Ib-30, Ib- 3 1, Ib-32, Ib-33, Ib-34, Ib-35, Ib-36, Ib-37, Ib-38, Ib-39, Ib-40, Ib-42, Ib-43, Ib-45, Ib-46, Ib-47, Ib-48, Ib-49, Ib-50, Ib-51, Ib-52, Ib-53, Ib-56, Ib-57, Ib-58, Ib-59, Ib- 61, Ib-62, Ib-63, Ib-64, Ib-65, Ib-68, Ib-69, Ib-71, Ib-72, Ib-75, Ib-76, Ib-78, Ib-79, Ib-80, Ib-81, Ib-82, Ib-83, Ib-84, Ib-85, Ib-86, Ib-87, Ib-88, Ib-89, Ib-90, Ib-92, Ib- 93, Ib-94, Ib-95, Ib-97, Ib-98, Ib-99, Ib-100, Ib-108, Ib-109, Ib-110, Ib-
[000527] In these tests, for example, the following compounds in the preparation examples show an effectiveness level of 90% at an application rate of 500 g/ha. la-59, la-62, la-63, la-68, la-83, la-88, la-91, la-92, la-101, la-102, la-103, la-104, la- 105, la-106, la-107, la-117, la-118, la-128, la-149, la-155, la-159, la-160, la-167, la-168, la-278, Ib-01, Ib-23, Ib-41, Ib-54, Ib-60, Ib-66, Ib-67, Ib-73, Ib-74, Ib-77, Ib 91, Ib-96, Ib-101 , Ib-102, Ib-103, Ib-104, Ib-111, Ib-116, Ib-122, Ib-124, Ib-128, Ib-133, Ib-134, Ib-136, Ib-142, Ib -143, Ib-144, Ib-145, Ib-146, Ib-147, Ib-149, Ib-150, Ib-152, Ib-153, Ib-154, Ib-155, Ib-156, Ib-157 , Ib-158, Ib-166, Ib-167, Ib-172
[000528] In these tests, for example, the following compounds in the preparation examples show an efficiency level of 80% at an application rate of 500 g/ha. Ia-09, Ia-17, Ia-45, Ia-90, Ia-108, Ia-109, Ib-04, Ib-05, Ib-18.
[000529] In these tests, for example, the following compounds in the preparation examples show an effectiveness level of 100% at an application rate of 100 g/ha. ia-58
[000530] In these tests, for example, the following compounds in the preparation examples show an efficiency level of 90% at an application rate of 100 g/ha. la-181. Tetranychus urticae - spray test, resistant to organophosphates (TETRUR) Solvents: 7 parts by weight of dimethylformamide Emulsifier: 2 parts by weight of polyglycolic alkylaryl ether
[000531] To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the indicated amounts of solvent and emulsifier and the concentrate is diluted with water containing emulsifier to the desired concentration. If the addition of ammonium salts or/and penetrants is necessary, these are added, in each case, in a concentration of 1000 ppm to the preparation solution.
Beans (Phaseolus vulgaris) which have been heavily infested with all stages of the greenhouse spider mite (Tetranychus urticae) are treated by spraying with the preparation of the active compound in the desired concentration.
[000533] After 7 days the effect in % is determined. 100% means all mites have been killed; 0% means that none of the mites were killed.
[000534] In these tests, for example, the following compounds in the preparation examples show an effectiveness level of 90% at an application rate of 100 ppm. Ib-44
[000535] In this test, for example, the following compounds in the preparation examples show an effectiveness level of 100% at an application rate of 20 ppm. Ib-168
[000536] In this test, for example, the following compounds in the preparation examples show an efficacy level of 80% at an application rate of 20 ppm. Ib-159.

权利要求:
Claims (13)
[0001]
na qual n representa o número 0 ou 1, X1, X2, X3, X4, independentemente uns dos outros, representam hidrogênio, flúor, cloro, bromo, iodo, (C1-C4)-alquila, (C1- C4)-haloalquila, ou (C1-C4)-alcoxi, R3 representa (C1-C4)-alcoxi-(C1-C4)-alquila, ou representa um anel de 3 membros, saturado que é opcionalmente mono- ou trissubstituído por substituintes idênticos ou diferentes do grupo consistindo em flúor, cloro, bromo, iodo, ou representa fenila que é mono- ou trissubstituída por substituintes idênticos ou diferentes do grupo consistindo em flúor, cloro, bromo, iodo, ciano, (C1-C4)-haloalquila, ou representa um anel de 6 membros aromático que contém um a dois N, R1 e R2, independentemente um do outro, representam hidrogênio, ciano, (C1-C4)-alquila, (C1-C4)-haloalquila, (C1-C4)-alcoxi, (C1-C4)-cianoalquila, (C1-C4)-hidroxialquila, (C1-C4)-alcoxi-(C1-C4)- alquila, (C2-C4)-alcenila, (C2-C4)-alcinila, ou representam (C1-C4)-alquilacarbonila, (C1-C5)- alcoxicarbonila, arilcarbonila, tiofenilcarbonila, piridilcarbonila, pirimidilcarbonila, tiazolilcarbonila, pirazolilcarbonila, (C1-C4)- alquilsulfinila, (C1-C4)-haloalquilsulfinila, arilsulfinila, aril-(C1-C4)- alquilsulfinila, hetarilsulfinila, hetaril-(C1-C4)-alquilsulfinila, (C1-C4)- alquilsulfonila, (C1-C4)-haloalquilsulfonila, arilsulfonila, aril-(C1-C4)- alquilsulfonila, hetarilsulfonila, hetaril-(C1-C4)-alquilsulfonila opcionalmente mono- a trissubstituída, independentemente uns dos outros, por substituintes do grupo consistindo em flúor, cloro, bromo, ciano, nitro, (C1-C4)-alquila, (C1-C4)-haloalquila, (C2-C4)-alcenila, (C2- C4)-haloalcenila, (C2-C4)-alcinila, (C1-C4)-alcoxi, (C1-C4)-haloalcoxi, (C1- C4)-alquiltio, (C1-C4)-alquilsulfinila, (C1-C4)-alquilsulfonila, (C1-C4)- alquilamino, di-(C1-C4)-alquilamino, ou representam um anel de 3 a 6 membros, saturado ou aromático que pode conter opcionalmente um a dois heteroátomos do grupo consistindo em O, S e N, que pode ser opcionalmente interrompido uma vez ou duas vezes por C=O e que é opcionalmente mono- ou trissubstituído por substituintes idênticos ou diferentes do grupo consistindo em flúor, cloro, bromo, ciano, nitro, (C1-C4)-alquila, (C1-C4)-haloalquila, (C2-C4)-alcenila, (C2-C4)-alcinila, (C1-C4)-alcoxi, (C1- C4)-haloalcoxi ou (C3-C6)-cicloalquila, ou representam -(CH2)m-R6, -(CH2)m-O-R6, onde R6 representa um anel de 3 a 6 membros, saturado, parcialmente saturado ou aromático que pode conter opcionalmente um a dois heteroátomos do grupo consistindo em O, S e N, que pode ser opcionalmente interrompido uma vez ou duas vezes por C=O e que é opcionalmente mono- ou trissubstituído por substituintes idênticos ou diferentes do grupo consistindo em flúor, cloro, bromo, ciano, nitro, (C1-C4)-alquila, (C1-C4)-haloalquila, (C2-C4)-alcenila, (C2-C4)-alcinila, (C1-C4)-alcoxi, (C1- C4)-haloalcoxi ou (C3-C6)-cicloalquila, onde m representa o número 1 ou 2, ou R1 e R2 conjuntamente com o átomo de nitrogênio ao qual estão ligados podem formar um anel de 3 a 6 membros, saturado ou insaturado que é opcionalmente mono- ou tetrassubstituído por flúor, cloro, (C1-C4)-alquila, (C1-C4)-alcoxi, (C1-C4)-haloalquila e que pode conter opcionalmente mais um heteroátomo do grupo consistindo em enxofre, oxigênio e nitrogênio e/ou pelo menos um grupo carbonila, ou R1 e R3 conjuntamente com os átomos aos quais eles estão ligados podem formar um anel de 5 membros saturado que contém mais um átomo de enxofre e um grupo carbonila.1. N-arylamidine-substituted trifluoroethyl sulfide derivatives, characterized by the fact that they have the Formula (I), in which n represents the number 0 or 1, X1, X2, X3, X4, independently of each other, represent hydrogen, fluorine, chlorine, bromine, iodine, (C1-C4)-alkyl, (C1-C4)-haloalkyl, or (C1-C4)-alkoxy, R3 represents (C1-C4)-alkoxy-(C1-C4)-alkyl, or represents a 3-membered, saturated ring which is optionally mono- or trisubstituted by identical or different substituents from the group consisting of fluorine, chlorine, bromine, iodine, or represents phenyl which is mono- or trisubstituted by identical or different substituents from the group consisting of fluorine, chlorine, bromine, iodine, cyano, (C1-C4)-haloalkyl, or represents a ring A 6-membered aromatic containing one to two N, R1 and R2, independently of one another, represent hydrogen, cyano, (C1-C4)-alkyl, (C1-C4)-haloalkyl, (C1-C4)-alkoxy, ( C1-C4)-cyanoalkyl, (C1-C4)-hydroxyalkyl, (C1-C4)-alkoxy-(C1-C4)-alkyl, (C2-C4)-alkenyl, (C2-C4)-alkynyl, or represent ( C1-C4)-alkylcarbonyl, (C1-C5)-alkoxycarbonyl, arylcarbonyl, thiophenyl rbonyl, pyridylcarbonyl, pyrimidylcarbonyl, thiazolylcarbonyl, pyrazolylcarbonyl, (C1-C4)-alkylsulfinyl, (C1-C4)-haloalkylsulfinyl, arylsulfinyl, aryl-(C1-C4)-alkylsulfinyl, hetarylsulfinyl, hetaryl-(C1-C4)-alkylsulfinyl, (C1-C4)-alkylsulfonyl, (C1-C4)-haloalkylsulfonyl, arylsulfonyl, aryl(C1-C4)-alkylsulfonyl, hetarylsulfonyl, hetaryl-(C1-C4)-alkylsulfonyl optionally mono- to trisubstituted, independently of each other, by substituents from the group consisting of fluorine, chlorine, bromine, cyano, nitro, (C1-C4)-alkyl, (C1-C4)-haloalkyl, (C2-C4)-alkenyl, (C2-C4)-haloalkenyl, (C2 -C4)-alkynyl, (C1-C4)-alkoxy, (C1-C4)-haloalkoxy, (C1-C4)-alkylthio, (C1-C4)-alkylsulfinyl, (C1-C4)-alkylsulfonyl, (C1-C4 )-alkylamino, di-(C1-C4)-alkylamino, or represent a 3- to 6-membered, saturated or aromatic ring which may optionally contain one to two heteroatoms from the group consisting of O, S and N, which may optionally be interrupted once or twice by C=O and which is optionally mono- or trisubstituted by identical or different substituents from the group consisting of fluorine, chlorine, bromine, cyano, nitro, (C1-C4)-alkyl, (C1-C4)-haloalkyl, (C2- C4)-alkenyl, (C2-C4)-alkynyl, (C1-C4)-alkoxy, (C1-C4)-haloalkoxy or (C3-C6)-cycloalkyl, or represent -(CH2)m-R6, -(CH2 )mO-R6, where R6 represents a 3- to 6-membered, saturated, partially saturated or aromatic ring which may optionally contain one to two heteroatoms from the group consisting of O, S and N, which may optionally be interrupted once or twice by C=O and which is optionally mono- or trisubstituted by identical or different substituents from the group consisting of fluorine, chlorine, bromine, cyano, nitro, (C1-C4)-alkyl, (C1-C4)-haloalkyl, (C2- C4)-alkenyl, (C2-C4)-alkynyl, (C1-C4)-alkoxy, (C1-C4)-haloalkoxy or (C3-C6)-cycloalkyl, where m represents the number 1 or 2, or R1 and R2 together with the nitrogen atom to which they are attached can form a 3 to 6 m ring bromides, saturated or unsaturated which is optionally mono- or tetra-substituted by fluorine, chlorine, (C1-C4)-alkyl, (C1-C4)-alkoxy, (C1-C4)-haloalkyl and which may optionally contain one more heteroatom from the group consisting of sulfur, oxygen and nitrogen and/or at least one carbonyl group, or R1 and R3 together with the atoms to which they are attached can form a 5-membered saturated ring which contains one more sulfur atom and one carbonyl group.
[0002]
nos quais o átomo de nitrogênio, ao qual R1 e R2 são ligados, representa o ciclo e a seta aponta para o resto da molécula, que pode ser opcionalmente mono- ou dissubstituída por metila, etila, metoxi, etoxi, flúor, cloro, bromo, trifluorometila, difluorometila.2. Compounds of the General Formula (I), according to claim 1, characterized in that: n represents the number 0 or 1, X1 and X3 represent hydrogen, X2 and X4, independently of each other, represent hydrogen, fluorine , chlorine, bromine, methyl, ethyl, trifluoromethyl, difluoromethyl, methoxy, ethoxy, especially, X2 and X4 represent the following combinations X2/X4: F/F, Cl/Cl, F/Cl, Cl/F, Br/Br, Br/Cl, Cl/Br, Br/F, F/Br, methyl/methyl, methyl/F, F/methyl, methyl/Cl, Cl/methyl, methyl/Br, Br/methyl, ethyl/ethyl, ethyl/ F, F/ethyl, ethyl/Cl, Cl/ethyl, ethyl/Br, Br/ethyl, methoxy/methyl, methyl/methoxy, methyl/H, ethyl/H, chlorine/H, bromine/H, fluorine/H, methoxy/H, H/chlorine, H/fluorine, H/bromine, H/methyl, H/methoxy, H/ethyl R3 represents methoxymethyl, methoxyethyl, or represents a saturated 3-membered ring which is optionally mono- or disubstituted by identical or different substituents from the group consisting of fluorine, chlorine, bromine, or represents phenyl which is mono- or disubstituted by su identical or different substituents from the group consisting of fluorine, chlorine, bromine, cyano, trifluoromethyl, or represents a 6-membered aromatic ring containing one to two N, R1 represents cyano, cyanomethyl, methylcarbonyl, ethylcarbonyl, propylcarbonyl, isopropylcarbonyl, methoxycarbonyl, ethoxycarbonyl , represents arylcarbonyl, pyridylcarbonyl, pyrimidylcarbonyl, thiazolylcarbonyl, pyrazolylcarbonyl, methylsulfinyl, trifluoromethylsulfinyl, methylsulfonyl, trifluoromethylsulfonyl optionally mono- or disubstituted, independently of one another, by fluorine, chlorine, bromine, cyano, nitro, methyl, methyl, trifluoromethyl, butyl , trifluoromethoxy, methylthio, methylsulfinyl, methylsulfonyl, methylamino, dimethylamino, or represents oxetanyl, thietanyl, trimethylenesulfonyl, trimethylenesulfinyl, oxanyl or thianyl which may be optionally mono- or polysubstituted by identical or different substituents from the group consisting of fluorine, chlorine, bromine , nitro, methyl a, ethyl, trifluoromethyl, vinyl, ethynyl, methoxy, ethoxy, difluoromethoxy, trifluoromethoxy, trifluoroethoxy and cyclopropyl, or represents cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl which are optionally mono- or polysubstituted by identical or different substituents from the group consisting of fluorine, chlorine , bromine, cyano, nitro, methyl, ethyl, trifluoromethyl, vinyl, ethynyl, methoxy, ethoxy, difluoromethoxy, trifluoromethoxy, trifluoroethoxy and cyclopropyl, R2 represents hydrogen, methyl or ethyl, or R1 and R2 together with the nitrogen atom to which they are attached can form a 3 to 6 membered, saturated or unsaturated ring which is optionally mono-, di-, tri- or tetra-substituted by methyl, ethyl, methoxy, ethoxy, fluorine, chlorine, bromine, trifluoromethyl, difluoromethyl and which contains one or two more heteroatoms from the group consisting of sulfur and nitrogen, or together with the nitrogen atom to which they are attached can form a 4-membered saturated or unsaturated ring. which is optionally mono-, di-, tri- or tetra-substituted by methyl, ethyl, methoxy, ethoxy, fluorine, chlorine, bromine, trifluoromethyl, difluoromethyl and which optionally contains one more heteroatom from the group consisting of oxygen, sulfur and nitrogen, especially following rings are explicitly mentioned: in which the nitrogen atom to which R1 and R2 are attached represents the cycle and the arrow points to the rest of the molecule, which may optionally be mono- or disubstituted by methyl, ethyl, methoxy, ethoxy, fluorine, chlorine, bromine , trifluoromethyl, difluoromethyl.
[0003]
nos quais o átomo de nitrogênio ao qual R1 e R2 são ligados representa o ciclo e a seta aponta para o resto da molécula, que pode ser opcionalmente mono- ou dissubstituída por metila, etila, metoxi, etoxi, flúor, cloro, bromo, trifluorometila, difluorometila.3. Compounds of the General Formula (I), according to claim 1, characterized in that: n represents the number 0 or 1, X1 and X3 represent hydrogen, X2 and X4, independently of each other, represent hydrogen, fluorine , chlorine, bromine, methyl, ethyl, trifluoromethyl, difluoromethyl, methoxy, ethoxy, especially, X2 and X4 represent the following combinations X2/X4: F/F, Cl/Cl, F/Cl, Cl/F, Br/Br, Br/Cl, Cl/Br, Br/F, F/Br, methyl/methyl, methyl/F, F/methyl, methyl/Cl, Cl/methyl, methyl/Br, Br/methyl, ethyl/ethyl, ethyl/ F, F/ethyl, ethyl/Cl, Cl/ethyl, ethyl/Br, Br/ethyl, methoxy/methyl, methyl/methoxy, methyl/H, ethyl/H, chlorine/H, bromine/H, fluorine/H, methoxy/H, H/chlorine, H/fluorine, H/bromine, H/methyl, H/methoxy, H/ethyl R3 represents methoxymethyl, methoxyethyl, or represents phenyl, which is mono- or polysubstituted by identical or different substituents from the group consisting of fluorine, chlorine, bromine, cyano, trifluoromethyl, R1 and R2, independently of each other, represent hydrogen, cyano , methyl, ethyl, propyl, butyl, sec-butyl, isopropyl, tert-butyl, (2,2,2)-trifluoroethyl, (2,2)-difluoromethyl, methoxy, ethoxy, cyanomethyl, methoxymethyl, methoxyethyl, allyl, butenyl , propynyl, methylcarbonyl, ethylcarbonyl, propylcarbonyl, isopropylcarbonyl, methoxycarbonyl, ethoxycarbonyl, represent arylcarbonyl, pyridylcarbonyl, pyrimidylcarbonyl, thiazolylcarbonyl, pyrazolylcarbonyl, methylsulfinyl, trifluoromethylsulfinyl, methylsulfonyl, trifluoromethylsulfonyl, optionally mono- or unsubstituted bromo-substituted by one or more , cyano, nitro, methyl, trifluoromethyl, allyl, butenyl, methoxy, trifluoromethoxy, methylthio, methylsulfinyl, methylsulfonyl, methylamino, dimethylamino, or represent a 3 to 6 membered, saturated or aromatic ring which may optionally contain one to two heteroatoms of the group consisting of O, S and N, which may optionally be interrupted once, twice or three times by C=O and which may optionally be mon o- or trisubstituted by identical or different substituents from the group consisting of fluorine, chlorine, bromine, cyano, nitro, methyl, ethyl, trifluoromethyl, vinyl, ethynyl, methoxy, ethoxy, difluoromethoxy, trifluoromethoxy, trifluoroethoxy and cyclopropyl, especially the following rings are explicitly mentioned: cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, oxetane, phenyl, thienyl and pyridyl which may be optionally substituted by the substituents mentioned as more particularly preferred, or represent -(CH2)m-R6, where R6 represents a ring of 3 to 6 membered, saturated, partially saturated or aromatic which may optionally contain one to two heteroatoms from the group consisting of O, S and N, may optionally be interrupted once or twice by C=O and which may optionally be mono-, di- or trisubstituted by identical or different substituents from the group consisting of fluorine, chlorine, bromine, cyano, nitro, methyl, ethyl, trifluoromethyl, vinyl, ethynyl, meth xi, ethoxy, difluoromethoxy, trifluoromethoxy, trifluoroethoxy and cyclopropyl, where m represents the number 1, especially the following R6 are explicitly mentioned: cyclopropyl, phenyl and pyridyl which may be optionally substituted by the substituents mentioned as more particularly preferred, or R1 and R2 together with the nitrogen atom to which they are attached can form a 3 to 6 membered, saturated or unsaturated ring which is optionally mono-, di-, tri- or tetra-substituted by methyl, ethyl, methoxy, ethoxy, fluorine, chlorine, bromine, trifluoromethyl, difluoromethyl, which may optionally contain one or two more heteroatoms from the group consisting of sulfur, oxygen and nitrogen (where oxygen atoms must not be directly adjacent to each other) and/or at least one CH2 group is replaced by a carbonyl group , especially the following rings are explicitly mentioned: in which the nitrogen atom to which R1 and R2 are attached represents the cycle and the arrow points to the rest of the molecule, which may optionally be mono- or disubstituted by methyl, ethyl, methoxy, ethoxy, fluorine, chlorine, bromine, trifluoromethyl , difluoromethyl.
[0004]
nos quais o átomo de nitrogênio ao qual R1 e R2 são ligados representa o ciclo e a seta aponta para o resto da molécula, que pode ser opcionalmente mono- ou dissubstituída por metila, etila, metoxi, etoxi, flúor, cloro, bromo, trifluorometila, difluorometila, ou R1 e R3 conjuntamente com os átomos aos quais eles estão ligados podem formar um anel de 5 membros saturado que contém mais um átomo de enxofre e um grupo carbonila, especialmente R1 e R3 conjuntamente com os átomos aos quais eles estão ligados representam o seguinte grupo, no qual a seta aponta para o resto da molécula.4. Compounds of the General Formula (I), according to claim 1, characterized in that: N represents the number 0 or 1, X1 and X3 represent hydrogen, X2 and X4 represent the following combinations X2/X4: methoxy/ H, H/methoxy, ethoxy/H, H/ethoxy, methoxy/methyl, methyl/methoxy, ethoxy/methyl, methyl/ethoxy, methoxy/F, F/methoxy, ethoxy/F, F/ethoxy, methoxy/Cl, Cl/methoxy, ethoxy/Cl, Cl/ethoxy, R3 represents methoxymethyl, methoxyethyl, or represents a saturated 3-membered ring which is optionally mono- or disubstituted by identical or different substituents from the group consisting of fluorine, chlorine, bromine, or represents phenyl which is mono- or disubstituted by identical or different substituents from the group consisting of fluorine, chlorine, bromine, cyano, trifluoromethyl, or represents an aromatic 6-membered ring which contains one to two N, R1 and R2, independently of one another, represent hydrogen, cyano, methyl, ethyl, propyl, butyl, sec-butyl, isopropyl, tert-butyl, (2,2,2)-trifluoroethyl a,(2,2)-difluoromethyl, methoxy, ethoxy, cyanomethyl, methoxymethyl, methoxyethyl, allyl, butenyl, propynyl, methylcarbonyl, ethylcarbonyl, propylcarbonyl, isopropylcarbonyl, methoxycarbonyl, ethoxycarbonyl, or represent arylcarbonyl, pyridylcarbonyl, pyrimidylcarbonyl, pyrazolylcarbonyl, thiazolyl methylsulfinyl, trifluoromethylsulfinyl, methylsulfonyl, trifluoromethylsulfonyl optionally mono- or disubstituted, independently of one another, by fluorine, chlorine, bromine, cyano, nitro, methyl, trifluoromethyl, allyl, butenyl, methoxy, trifluoromethoxy, methylthio, methylamino, methylsulfonyl , or represent a 3 to 6 membered, saturated or aromatic ring which may optionally contain one to two heteroatoms from the group consisting of O, S and N, which may optionally be interrupted once, twice or three times by C=O and which may be optionally mono- or tri-substituted by identical or different substituents from the group consisting of fl. fluorine, chlorine, bromine, cyano, nitro, methyl, ethyl, trifluoromethyl, vinyl, ethynyl, methoxy, ethoxy, difluoromethoxy, trifluoromethoxy, trifluoroethoxy and cyclopropyl, especially the following rings are explicitly mentioned: cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, oxetane, phenyl, thienyl and pyridyl which may be optionally substituted by the substituents mentioned as more particularly preferred, or represent -(CH2)m-R6, where R6 represents a 3 to 6 membered, saturated, partially saturated or aromatic ring which may optionally contain a to two heteroatoms from the group consisting of O, S and N, may optionally be interrupted once or twice by C=O and which may optionally be mono-, di- or trisubstituted by identical or different substituents from the group consisting of fluorine, chlorine , bromine, cyano, nitro, methyl, ethyl, trifluoromethyl, vinyl, ethynyl, methoxy, ethoxy, difluoromethoxy, trifluoromethoxy, trifluoroethoxy and cyclopropyl, where m represents ta the number 1, especially the following R6 are explicitly mentioned: cyclopropyl, phenyl and pyridyl which may be optionally substituted by the substituents mentioned as more particularly preferred, or R1 and R2 together with the nitrogen atom to which they are attached may form a ring of 3 to 6 membered, saturated or unsaturated which is optionally mono-, di-, tri- or tetra-substituted by methyl, ethyl, methoxy, ethoxy, fluorine, chlorine, bromine, trifluoromethyl, difluoromethyl, which may optionally contain one or two more heteroatoms of the group consisting of sulfur, oxygen and nitrogen (where oxygen atoms must not be directly adjacent to each other) and/or at least one CH2 group is replaced by a carbonyl group, especially the following rings are explicitly mentioned: in which the nitrogen atom to which R1 and R2 are attached represents the cycle and the arrow points to the rest of the molecule, which may optionally be mono- or disubstituted by methyl, ethyl, methoxy, ethoxy, fluorine, chlorine, bromine, trifluoromethyl , difluoromethyl, or R1 and R3 together with the atoms to which they are attached can form a 5-membered saturated ring which contains a further sulfur atom and a carbonyl group, especially R1 and R3 together with the atoms to which they are attached represent the following group, in which the arrow points to the rest of the molecule.
[0005]
no qual a seta aponta para o resto da molécula, R2 representa ciano, (2,2,2)-trifluoroetila, (2,2)-difluorometila, 2-cloro-(2,2)-difluoroetila, (2,2)-dicloro-2-fluoroetila, (2,2,2)-tricloroetila, pentafluoroetila, 2-clorotetrafluoroetila, alila, butenila, propinila, metilsulfinila, trifluorometilsulfinila, metilsulfonila, trifluorometilsulfonila, ou representa um anel de 3 a 6 membros, saturado ou aromático que pode conter opcionalmente um a dois heteroátomos do grupo consistindo em O, S e N, que pode ser opcionalmente interrompido uma vez, duas vezes ou três vezes por C=O e que é opcionalmente mono- ou trissubstituído por substituintes idênticos ou diferentes do grupo consistindo em flúor, cloro, bromo, ciano, nitro, metila, etila, trifluorometila, vinila, etinila, metoxi, etoxi, difluorometoxi, trifluorometoxi, trifluoroetoxi e ciclopropila, especialmente os seguintes anéis são explicitamente mencionados: ciclopropila, ciclobutila, ciclopentila, ciclohexila, oxetano, fenila, tienila e piridila que podem ser opcionalmente substituídas pelos substituintes mencionados como mais particularmente preferidos, ou representa -(CH2)m-R6, onde R6 representa um anel de 3 a 6 membros, saturado, parcialmente saturado ou aromático que pode conter opcionalmente um a dois heteroátomos do grupo consistindo em O, S e N, pode ser opcionalmente interrompido uma vez ou duas vezes por C=O e que é opcionalmente mono-, di- ou trissubstituído por substituintes idênticos ou diferentes do grupo consistindo em flúor, cloro, bromo, ciano, nitro, metila, etila, trifluorometila, vinila, etinila, metoxi, etoxi, difluorometoxi, trifluorometoxi, trifluoroetoxi e ciclopropila, onde m representa o número 1, especialmente os seguintes R6 são explicitamente mencionados: ciclopropila, ciclobutila, ciclopentila, ciclohexila, fenila e piridila que podem ser opcionalmente substituídas pelos substituintes mencionados como mais particularmente preferidos.5. Compounds of the General Formula (I), according to claim 1, characterized in that: n represents the number 0 or 1, X1 and X3 represent hydrogen, X2 and X4, independently of each other, represent hydrogen, fluorine , chlorine, bromine, methyl, ethyl, trifluoromethyl, difluoromethyl, methoxy, ethoxy, especially, X2 and X4 represent the following combinations X2/X4: F/F, Cl/Cl, F/Cl, Cl/F, Br/Br, Br/Cl, Cl/Br, Br/F, F/Br, methyl/methyl, methyl/F, F/methyl, methyl/Cl, Cl/methyl, methyl/Br, Br/methyl, ethyl/ethyl, ethyl/ F, F/ethyl, ethyl/Cl, Cl/ethyl, ethyl/Br, Br/ethyl, methoxy/methyl, methyl/methoxy, methyl/H, ethyl/H, chlorine/H, bromine/H, fluorine/H, methoxy/H, H/chlorine, H/fluorine, H/bromine, H/methyl, H/methoxy, H/ethyl. R1 and R3 together with the atoms to which they are attached can form a saturated 5-membered ring which contains a further sulfur atom and a carbonyl group, especially R1 and R3 together with the atoms to which they are attached represent the following group, in which the arrow points to the rest of the molecule, R2 represents cyano, (2,2,2)-trifluoroethyl, (2,2)-difluoromethyl, 2-chloro-(2,2)-difluoroethyl, (2,2) -dichloro-2-fluoroethyl, (2,2,2)-trichloroethyl, pentafluoroethyl, 2-chlorotetrafluoroethyl, allyl, butenyl, propynyl, methylsulfinyl, trifluoromethylsulfinyl, methylsulfonyl, trifluoromethylsulfonyl, or represents a saturated or aromatic 3- to 6-membered ring which may optionally contain one to two heteroatoms from the group consisting of O, S and N, which may optionally be interrupted once, twice or three times by C=O and which is optionally mono- or trisubstituted by identical or different substituents from the group consisting of fluorine, chlorine, bromine, cyano, nitro, methyl, ethyl, trifluoromethyl, vinyl, ethynyl, methoxy, ethoxy, difluoromethoxy, trifluoromethoxy, trifluoroethoxy and cyclopropyl, especially the following rings are explicitly mentioned: cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, oxetane, phenyl, thienyl and pyridyl which may be optionally substituted by the substituents mentioned as more particularly preferred, or represents -(CH2)m -R6, where R6 represents a saturated, partially saturated or aromatic 3 to 6 membered ring which may optionally contain one to two heteroatoms from the group consisting of O, S and N, may optionally be interrupted once or twice by C=O and which is optionally mono-, di- or trisubstituted by identical or different substituents from the group consisting of fluorine, chlorine, bromine, cyano , nitro, methyl, ethyl, trifluoromethyl, vinyl, ethynyl, methoxy, ethoxy, difluoromethoxy, trifluoromethoxy, trifluoroethoxy and cyclopropyl, where m represents the number 1, especially the following R6 are explicitly mentioned: cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, phenyl and pyridyl which may be optionally substituted by the substituents mentioned as more particularly preferred.
[0006]

[0007]
são convertidas na presença de ácidos, anidridos de ácido ou cloretos de ácido da Fórmula (VIII), na qual AG representa um grupo de partida, em anilidas da Fórmula Geral (VI), (B) anilidos da Fórmula (VI) são convertidos por clorossulfonação com ácido clorossulfônico em cloretos de sulfonila da Fórmula Geral (V), (C) cloretos de sulfonila da Fórmula (V) são convertidos por redução com ferro em ácido clorídrico ou iodeto em dissulfuretos da Fórmula Geral (IV), (D) dissulfuretos da eletrófilos trifluoretila da Fórmula (IX), na qual AG representa um grupo de partida tal como cloro, bromo, tosilato, mesilato ou triflato, em sulfuretos da Fórmula Geral (III), (E) os compostos da Fórmula (III) são convertidos com clorofosfato difenila ou pentacloreto de fósforo em cloretos de imidoíla da Fórmula Geral (II), (F) os compostos da Fórmula Geral (II) são convertidos com aminas em amidinas da Fórmula Geral (Ia), (G) os compostos da Fórmula (IA) são convertidos com agentes oxidantes em sulfóxidos da Fórmula Geral (Ib), na qual X1, X2, X3, X4, R1, R2 e R3 são como definidos em qualquer uma das reivindicações 1 a 6.7. Process for preparing compounds of Formula (I), as defined in any one of claims 1 to 6, characterized in that: (A) anilines of Formula (VII), are converted in the presence of acids, acid anhydrides or acid chlorides of Formula (VIII), in which AG represents a leaving group, in anilides of General Formula (VI), (B) anilides of Formula (VI) are converted by chlorosulfonation with chlorosulfonic acid to sulfonyl chlorides of General Formula (V), (C) sulfonyl chlorides of Formula (V) are converted by reduction with iron in hydrochloric acid or iodide to disulfides of General Formula (IV), (D) trifluoroethyl electrophile disulfides of Formula (IX), in which AG represents a leaving group such as chlorine, bromine, tosylate, mesylate or triflate, in sulfides of the General Formula (III), (E) compounds of Formula (III) are converted with diphenyl chlorophosphate or phosphorus pentachloride to imidoyl chlorides of General Formula (II), (F) compounds of General Formula (II) are converted with amines to amidines of General Formula (Ia), (G) compounds of Formula (IA) are converted with oxidizing agents to sulfoxides of General Formula (Ib), in which X1, X2, X3, X4, R1, R2 and R3 are as defined in any one of claims 1 to 6.
[0008]
opcionalmente na presença de uma de um solvente orgânico, em compostos da Fórmula (XXXVIII), (B) compostos da Fórmula (XXXVIII) são opcionalmente convertidos por cicloacilação em compostos da Fórmula Geral (Ia-g), (C) estes compostos da Fórmula (Ia-g) são oxidados em compostos da Fórmula (Ib-g), na qual A representa oxigênio ou enxofre, e X1, X2, X3, X4 e R2 são como definidos em qualquer uma das reivindicações 1 a 6.8. Process for preparing compounds of Formula (I), as defined in any one of claims 1 to 6, characterized in that: (A) anilines of Formula (X), optionally in the presence of an organic solvent, in compounds of Formula (XXXVIII), (B) compounds of Formula (XXXVIII) are optionally converted by cycloacylation to compounds of General Formula (Ia-g), (C) these compounds of Formula (Ia-g) are oxidized to compounds of Formula (Ib-g), in which A represents oxygen or sulfur, and X1, X2, X3, X4 and R2 are as defined in any one of claims 1 to 6.
[0009]
9. Active compound composition, characterized in that it comprises at least one compound of the General Formula (I), as defined in any one of claims 1 to 6, and at least one more insecticide, acaricide or nematicidally active compound, selected from group consisting of: (1) Inhibitors of acetylcholinesterase (AChE), such as, for example: carbamates, for example, alanicarb, aldicarb, bendiocarb, benfuracarb, butocarboxim, butoxycarboxim, carbaryl, carbofuran, carbosulfan, ethiofencarb, fenobucarb, furmetacarb, formetacarb , isoprocarb, methiocarb, methomyl, metolcarb, oxamyl, pirimicarb, propoxur, thiodicarb, thiophanox, triazamate, trimetacarb, XMC and xylylcarb; or organophosphates, e.g. acephate, azamethiphos, azinphos-ethyl, azinphos-methyl, cadusaphos, chloroxyphos, chlorfenvinphos, chlormephos, chlorpyrifos, chlorpyrifos-methyl, coumaphos, cyanophos, demeton-S-methyl, dicrovophos/VP, dichlor , dimethylvinphos, disulfotone, EPN, ethion, etoprophos, famfur, fenamiphos, fenitrothion, phenthion, phosthiazate, heptenophos, imicyaphos, isofenphos, isopropyl O-(methoxyaminothiophosphoryl)salicylate, isoxation, malathion, metaphothion, mecarbam naled, omethoate, oxidemeton-methyl, parathion, parathion-methyl, phentoate, phorate, phosalone, fosmet, phosphamidone, foxim, pirimiphos-methyl, profenophos, propetamphos, prothiophos, pyraclophos, pyridaphenthione, quilfos, sulfoephos, terbu tebu tetrachlorvinphos, thiomethone, triazophos, trichlorphon and vamidothione; (2) GABA-mediated chlorine channel antagonists such as, for example: cyclodiene organochlorines, for example, chlordane and endosulfan; or phenylpyrazoles (fiprols), for example ethiprole and fipronil; (3) Sodium channel modulators/voltage dependent sodium channel blockers such as, for example, pyrethroids, eg, acrinathrin, allethrin, d-cis-trans allethrin, d-trans allethrin, bifenthrin, bioallethrin, bioallethrin isomer S-cyclopentenyl, bioresmethrin, cycloprothrin, cyfluthrin, beta-cyfluthrin, cyhalothrin, lambda-cyhalothrin, gamma-cyhalothrin, cypermethrin, alpha-cypermethrin, beta-cypermethrin, theta-cypermethrin, zeta-cypermethrin, cyphenotrin [1R-transisomers ], deltamethrin, empentrin [isomers (EZ)- (1R)), esfenvalerate, etofenprox, fenpropathrin, fenvalerate, flucitrinate, flumethrin, tau-fluvalinate, halfenprox, imiprotrin, kadetrin, permethrin, phenotrin [isomer (1R)-trans pralethrin, pyrethrin (pyrethrum), resmethrin, silafluofen, tefluthrin, tetramethrin, tetramethrin [isomers (1R))], tralomethrin and transfluthrin; or DDT; or methoxychlor; (4) Acetylcholine nicotinergic receptor (nAChR) agonists, such as, for example: neonicotinoids, for example, acetamiprid, clothianidin, dinotefuran, imidacloprid, nitenpyram, thiacloprid and thiamethoxam; or nicotine; (5) Allosteric activators of the nicotinergic acetylcholine receptor (nAChR), such as, for example: spinosyns, for example, spinetoram and spinosad; (6) Chlorine channel activators such as, for example: avermectins/milbemycins, for example abamectin, emamectin benzoate, lepimectin and milbemectin; (7) Juvenile hormone mimetics, such as, for example: juvenile hormone analogues, for example, hydroprene, quinoprene and methoprene; or fenoxycarb; or pyriproxyfen; (8) Active compounds with unknown or non-specific mechanisms of action, such as, for example: alkyl halides, for example, methyl bromide and other alkyl halides; or chloropicrin; or sulphoryl fluoride; or borax; or tartar emetic; (9) Selective antinutrients, eg, pymetrozine; or flonicamid; (10) Inhibitors of the growth of mites, for example, clofentezine, hethiazox and diflovidazine; or etoxazole; (11) Microbial disruptors of the digestive membranes of insects, for example, Bacillus turingiensis subspecies israelensis, Bacillus sphaericus, Bacillus turingiensis subspecies aizawai, Bacillus turingiensis subspecies kurstaki, Bacillus turingiensis subspecies tenebrionis, and plant proteins Cri1 Crib1 BT: , mCri3A, Cri3Ab, Cri3Bb, Cri34/35Ab1; (12) Inhibitors of oxidative phosphorylation, ATP disruptors such as, for example, diafenthiuron; or organotin compounds, for example azocyclotin, cyhexatin, fenbutatin oxide; or propargite; or tetradiphone; (13) Oxidative phosphorylation uncouplers that act by disrupting the H-proton gradient, such as, for example, chlorfenapyr, DNOC and sulfluramide; (14) Nicotinergic acetylcholine receptor antagonists, such as, for example,bensultape, cartape hydrochloride, thiocyclam and thiosultapesodium; (15) Chitin biosynthesis inhibitors, type 0, such as, for example, bistrifluron, chlorfluazuron, diflubenzuron, flucicloxuron, flufenoxuron, hexaflumuron, lufenuron, novaluron, noviflumuron, teflubenzuron and triflumuron; (16) Chitin biosynthesis inhibitors, type 1, such as, for example, buprofezin; (17) Moult disruptors, dipterans, such as, for example, cyromazine; (18) Ecdysone receptor agonists such as, for example, chromafenozide, halofenozide, methoxyfenozide and tebufenozide; (19) Octopaminergic antagonists such as, for example, amitraz; (20) Complex III electron transport inhibitors, such as, for example, hydramethylnon or acequinocil or fluacripyrime; (21) Complex I electron transport inhibitors, for example: METI acaricides, for example, fenazaquin, fenpyroximate, pyrimidifen, pyridaben, tebufenpyrad and tolfenpyrad; or rotenone (Derris); (22) Voltage-dependent sodium channel blockers, eg, indoxacarb; or metaflumizone; (23) Acetyl-CoA carboxylase inhibitors, such as, for example: tetronic and tetramic acid derivatives, for example, spirodiclofen, spiromesifen and spirotetramat; (24) Inhibitors of complex IV electron transport, such as, for example: phosphines, for example, aluminum phosphide, calcium phosphide, phosphine and zinc phosphide; or cyanide; (25) Complex II electron transport inhibitors, such as, for example, cyenopyrafen; (28) Effectors of Rianodine receptors, such as, for example; diamides, for example chlorantraniliprole and flubendiamide; other active compounds with unknown mechanism of action, such as, for example, amidoflumet, azadirachtin, benclothiaz, benzximate, biphenazate, bromopropylate, cinometionat, cryolite, cyantraniliprol (Ciazipir), ciflumetofen, dicofol, diflovidazine, fluensulfone, fluphenerim, flufenerim fufenozide, imidaclotiz, iprodione, meperfluthrin, pyridalyl, pyrifluquinazone, tetramethylfluthrin and iodomethane and additionally preparations based on Bacillus firmus (particularly CNCM strain I-1582, eg VOTiVO™, BioNem), and the following known active compounds: 3-Bromo -N-{2-bromo-4-chloro-6-[(1-cyclopropylethyl)carbamoyl]phenyl}-1-(3-chloropyridin-2-yl)-1H-pyrazol-5-carboxamide, 4-{[( 6-bromopyrid-3-yl)methyl](2-fluoroethyl)amino}furan-2(5H)-one (known from WO 2007/115644), 4-{[(6-fluoropyrid-3-yl)methyl]( 2,2-difluoroethyl)amino}furan-2(5H)-one (known from WO 2007/115644), 4-{[(2-chloro-1,3-thiazol-5-yl)methyl](2-fluoroethyl) )amino}furan-2(5H)-one (known from WO 2007/11564 4), 4-{[(6-chloropyrid-3-yl)methyl](2-fluoroethyl)amino}furan-2(5H)-one (known from WO 2007/115644), flupyradifurone, 4-{[(6 -chloro-5-fluoropyrid-3-yl)methyl](methyl)amino}furan-2(5H)-one (known from WO 2007/115643), 4-{[(5,6-dichloropyrid-3-yl) methyl](2-fluoroethyl)amino}furan-2(5H)-one (known from WO 2007/115646), 4-{[(6-chloro-5-fluoropyrid-3-yl)methyl](cyclopropyl)amino} furan-2(5H)-one (known from WO 2007/115643), 4-{[(6-chloropyrid-3-yl)methyl](cyclopropyl)amino}furan-2(5H)-one (known from EP- A-0 539 588), 4-{[(6-chloropyrid-3-yl)methyl](methyl)amino}furan-2(5H)-one (known from EP-A-0 539 588), {[1 -(6-chloropyridin-3-yl)ethyl](methyl)oxido-À4-sulfanylidene}cyanamide (known from WO 2007/149134) and diastereoisomers thereof {[(1R)-1-(6-chloropyridin-3-yl) ethyl](methyl)oxide-À4-sulfanylidene}cyanamide (A) and {[(1S)-1-(6-chloropyridin-3-yl)ethyl](methyl)oxide-À4-sulfanylidene}cyanamide (B) (also known from WO 2007/149134) and also sulfoxaflor and diastereoisomers of these [(R)-methyl(oxid) o){(1R)-1-[6-(trifluoromethyl)pyridin-3-yl]ethyl}-À4-sulfanilidene]cyanamide (A1) and [(S)-methyl(oxide){(1S)-1- [6-(trifluoromethyl)pyridin-3-yl]ethyl}-À±4-sulfanylidene]cyanamide (A2), identified as group A diastereoisomer (known from WO 2010/074747, WO 2010/074751), [(R)-methyl( oxide){(1S)-1-[6-(trifluoromethyl)pyridin-3-yl]ethyl}-À4-sulfanylidene]cyanamide (B1) and [(S)-methyl(oxide){(1R)-1- [6-(trifluoromethyl)pyridin-3-yl]ethyl}-À4-sulfanylidene]cyanamide (B2), identified as group B diastereoisomer (also known from WO 2010/074747, WO 2010/074751) and 11-(4-chloro -2,6-dimethylphenyl)-12-hydroxy-1,4-dioxa-9-azadispiro[4.2.4.2]tetradec-11-en-10-one (known from WO 2006/089633), 3-(4'- fluoro-2,4-dimethylbiphenyl-3-yl)-4-hydroxy-8-oxa-1-azaspiro[4.5]dec-3-en-2-one (known from WO 2008/067911), 1-{2- fluoro-4-methyl-5-[(2,2,2-trifluoroethyl)sulfinyl]phenyl}-3-(trifluoromethyl)-1H-1,2,4-triazol-5-amine (known from WO 2006/043635) , [(3S,4aR,12R,12aS,12bS)-3-[(cyclopropylcarbonyl) oxy]-6,12-dihydroxy-4,12b-dimethyl-11-oxo-9-(pyridin-3-yl)-1,3,4,4a,5,6,6a,12,12a,12b-decahydro -2H,11H-benzo[f]pyrano[4,3-b]chromen-4-yl]methylcyclopropanecarboxylate (known from WO 2008/066153), 2-cyano-3-(difluoromethoxy)-N,N-dimethylbenzenesulfonamide (known from WO 2006/056433), 2-cyano-3-(difluoromethoxy)-N-methylbenzenesulfonamide (known from WO 2006/100288), 2-cyano-3-(difluoromethoxy)-N-ethylbenzenesulfonamide (known from WO 2005/035486) , 4-(difluoromethoxy)-N-ethyl-N-methyl-1,2-benzothiazol-3-amine 1,1-dioxide (known from WO 2007/057407), N-[1-(2,3-dimethylphenyl) -2-(3,5-dimethylphenyl)ethyl]-4,5-dihydro-1,3-thiazol-2-amine (known from WO 2008/104503), {1'-[(2E)-3-(4 -chlorophenyl)prop-2-en-1-yl]-5-fluorospiro[indole-3,4'-piperidin]-1(2H)-yl}(2-chloropyridin-4-yl)methanone (known from WO 2003 /106457), 3-(2,5-dimethylphenyl)-4-hydroxy-8-methoxy-1,8-diazaspiro[4.5]dec-3-en-2-one (known from WO 2009/049851), 3- (2,5-dimethylphenyl)-8-methoxy-2-oxo-1,8-diazaspiro[4.5]dec-3-en-4-yl ethyl carbonate (known from WO 2009/049851), 4-(but-2-yn-1-yloxy)-6-(3,5-dimethylpiperidin-1-yl)-5-fluoropyrimidine (known from WO 2004/099160) , (2,2,3,3,4,4,5,5-octafluoropentyl)(3,3,3-trifluoropropyl)malononitrile (known from WO 2005/063094), (2,2,3,3,4, 4,5,5-octafluoropentyl)(3,3,4,4,4-pentafluorobutyl)malononitrile (known from WO 2005/063094), 8-[2-(cyclopropylmethoxy)-4-(trifluoromethyl)phenoxy]-3- [6-(trifluoromethyl)pyridazin-3-yl]-3-azabicyclo[3.2.1]octane (known from WO 2007/040280), flometoquin, PF1364 (CAS Reg. No. 1204776-60-2) (known from JP2010) /018586), 5-[5-(3,5-dichlorophenyl)-5-(trifluoromethyl)-4,5-dihydro-1,2-oxazol-3-yl]-2-(1H-1,2,4 -triazol-1-yl)benzonitrile (known from WO2007/075459), 5-[5-(2-chloropyridin-4-yl)-5-(trifluoromethyl)-4,5-dihydro-1,2-oxazol-3 -yl]-2-(1H-1,2,4-triazol-1-yl)benzonitrile (known from WO2007/075459), 4-[5-(3,5-dichlorophenyl)-5-(trifluoromethyl)-4 ,5-dihydro-1,2-oxazol-3-yl]-2-methyl-N-{2-oxo-2-[(2,2,2-trifluoroethyl)amino]ethyl}benz amide (known from WO2005/085216), 4-{[(6-chloropyridin-3-yl)methyl](cyclopropyl)amino}-1,3-oxazol-2(5H)-one, 4-{[(6- chloropyridin-3-yl)methyl](2,2-difluoroethyl)amino}-1,3-oxazol-2(5H)-one, 4-{[(6-chloropyridin-3-yl)methyl](ethyl)amino }-1,3-oxazol-2(5H)-one, 4-{[(6-chloropyridin-3-yl)methyl](methyl)amino}-1,3-oxazol-2(5H)-one (all known from WO2010/005692), NNI-0711 (known from WO2002/096882), 1-acetyl-N-[4-(1,1,1,3,3,3-hexafluoro-2-methoxypropan-2-yl) -3-isobutylphenyl]-N-isobutyryl-3,5-dimethyl-1H-pyrazole-4-carboxamide (known from WO2002/096882), methyl 2-[2-({[3-bromo-1-(3-chloropyridine) -2-yl)-1H-pyrazol-5-yl]carbonyl}amino)-5-chloro-3-methylbenzoyl]-2-methylhydrazinecarboxylate (known from WO2005/085216), methyl 2-[2-({[3- bromo-1-(3-chloropyridin-2-yl)-1H-pyrazol-5-yl]carbonyl}amino)-5-cyano-3-methylbenzoyl]-2-ethylhydrazinecarboxylate (known from WO2005/085216), methyl 2- [2-({[3-bromo-1-(3-chloropyridin-2-yl)-1H-pyrazol-5-yl]carbonyl}amino)-5-cyano-3-methylbenzoyl]-2-methylhydrazineac carboxylate (known from WO2005/085216), methyl 2-[3,5-dibromo-2-({[3-bromo-1-(3-chloropyridin-2-yl)-1H-pyrazol-5-yl]carbonyl} amino)benzoyl]-1,2-diethylhydrazinecarboxylate (known from WO2005/085216), 2-[3,5-dibromo-2-({[3-bromo-1-(3-chloropyridin-2-yl)-1H- methyl pyrazol-5-yl]carbonyl}amino)benzoyl]-2-ethylhydrazinecarboxylate (known from WO2005/085216), (5RS,7RS;5RS,7SR)-1-(6-chloro-3-pyridylmethyl)-1, 2,3,5,6,7-hexahydro-7-methyl-8-nitro-5-propoxyimidazo[1,2-a]pyridine (known from WO2007/101369), 2-{6-[2-(5- fluoropyridin-3-yl)-1,3-thiazol-5-yl]pyridin-2-yl}pyrimidine (known from WO2010/006713), 2-{6-[2-(pyridin-3-yl)-1, 3-thiazol-5-yl]pyridin-2-yl}pyrimidine (known from WO2010/006713), 1-(3-chloropyridin-2-yl)-N-[4-cyano-2-methyl-6-(methylcarbamoyl) )phenyl]-3-{[5-(trifluoromethyl)-1H-tetrazol-1-yl]methyl}-1H-pyrazole-5-carboxamide (known from WO2010/069502), 1-(3-chloropyridin-2-yl )-N-[4-cyano-2-methyl-6-(methylcarbamoyl)phenyl]-3-{[5-(trifluoromethyl)-2H-tetrazol-2-yl]methyl}-1H-pyra zol-5-carboxamide (known from WO2010/069502), N-[2-(tert-butylcarbamoyl)-4-cyano-6-methylphenyl]-1-(3-chloropyridin-2-yl)-3-{[5 -(trifluoromethyl)-1H-tetrazol-1-yl]methyl}-1H-pyrazole-5-carboxamide (known from WO2010/069502), N-[2-(tert-butylcarbamoyl)-4-cyano-6-methylphenyl] -1-(3-chloropyridin-2-yl)-3-{[5-(trifluoromethyl)-2H-tetrazol-2-yl]methyl}-1H-pyrazol-5-carboxamide (known from WO2010/069502), ( 1E)-N-[(6-chloropyridin-3-yl)methyl]-N'-cyano-N-(2,2-difluoroethyl)ethanimidamide (known from WO2008/009360), N-[2-(5-amino -1,3,4-thiadiazol-2-yl)-4-chloro-6-methylphenyl]-3-bromo-1-(3-chloropyridin-2-yl)-1H-pyrazole-5-carboxamide (known from CN102057925 ) and 2-[3,5-dibromo-2-({[3-bromo-1-(3-chloropyridin-2-yl)-1H-pyrazol-5-yl]carbonyl}amino)benzoyl]-2-ethyl methyl -1-methylhydrazinecarboxylate (known from WO2011/049233), and/or at least one more fungicidally active compound, selected from the group consisting of: (1) Inhibitors of ergosterol biosynthesis, such as, for example, (1.1) aldimor f (1704-28-5), (1.2) azaconazole (60207-31-0), (1.3) bitertanol (55179-31-2), (1.4) bromuconazole (116255-48-2), (1.5) cyproconazole ( 113096-99-4), (1.6) diclobutrazol (75736-33-3), (1.7) difenoconazole (119446-68-3), (1.8) diniconazole (83657-24-3), (1.9) diniconazol-M ( 83657-18-5), (1.10) dodemorph (1593-77-7), (1.11) dodemorph acetate (31717-87-0), (1.12) epoxiconazole (106325-08-0), (1.13) etaconazole ( 60207-93-4), (1.14) fenarimol (60168-88-9), (1.15) fenbuconazole (114369-43-6), (1.16) fenhexamid (126833-17-8), (1.17) fenpropidin (67306- 00-7), (1.18) fenpropimorph (67306-03-0), (1.19) fluquinconazole (136426-54-5), (1.20) flurprimidol (56425-91-3), (1.21) flusilazol (85509-19- 9), (1.22) flutriafol (76674-21-0), (1.23) furconazole (112839-33-5), (1.24) furconazole-cis (112839-32-4), (1.25) hexaconazole (79983-71- 4), (1.26) imazalyl (60534-80-7), (1.27) imazalyl sulfate (58594-72-2), (1.28) imibenconazole (86598-92-7), (1.29) ipconazol (125225-28-7) ), (1.30) metconazole (125116-23-6), (1.31) micl obutanil (88671-89-0), (1.32) naftifin (65472-88-0), (1.33) nuarimol (63284-71-9), (1.34) oxpoconazole (174212-12-5), (1.35) paclobutrazol ( 76738-62-0), (1.36) pefurazoate (101903-30-4), (1.37) penconazol (66246-88-6), (1.38) piperalin (3478-94-2), (1.39) prochloraz (67747- 09-5), (1.40) propiconazole (60207-90-1), (1.41) prothioconazole (178928-70-6), (1.42) piributicarb (88678-67-5), (1.43) pyrifenox (88283-41- 4), (1.44) quinconazole (103970-75-8), (1.45) simeconazole (149508-90-7), (1.46) spiroxamine (118134-30-8), (1.47) tebuconazole (107534-96-3) , (1.48) terbinafin (91161-71-6), (1.49) tetraconazole (112281-77-3), (1.50) triadimefon (43121-43-3), (1.51) triadimenol (89482-17-7), ( 1.52) tridemorph (81412-43-3), (1.53) triflumizole (68694-11-1), (1.54) triforine (26644-46-2), (1.55) triticonazole (131983-72-7), (1.56) uniconazole (83657-22-1), (1.57) uniconazole-p (83657-17-4), (1.58) viniconazole (77174-66-4), (1.59) voriconazole (137234-62-9), (1.60) 1-(4-chlorophenyl)-2-(1H-1,2,4-triazol-1-yl)cyc loheptanol (129586-32-9), (1.61) methyl 1-(2,2-dimethyl-2,3-dihydro-1H-inden-1-yl)-1H-imidazol-5-carboxylate (11032395-0), (1.62) N'-{5-(difluoromethyl)-2-methyl-4-[3-(trimethylsilyl)propoxy]phenyl}-N-ethyl-N-methylimidoformamide, (1.63) N-ethyl-N-methyl-N '-{2-methyl-5-(trifluoromethyl)-4-[3-(trimethylsilyl)propoxy]phenyl}imidoformamide and (1.64) O-[1-(4-methoxyphenoxy)-3,3-dimethylbutan-2-yl ] 1H-imidazol-1-carbothioate (111226-71-2); (2) Respiratory inhibitors (respiratory chain inhibitors), such as, for example, (2.1) bixafen (581809-46-3), (2.2) boscalid (188425-85-6), (2.3) carboxin (5234-68 -4), (2.4) diflumethorim (13033907-0), (2.5) fenfuram (24691-80-3), (2.6) fluopiram (658066-35-4), (2.7) flutolanil (66332-96-5), (2.8) fluxapiroxad (907204-31-3), (2.9) furametpyr (123572-88-3), (2.10) furmeciclox (60568-05-0), (2.11) mixture of isopyrazam from syn-epimeric racemate 1RS,4SR ,9RS and the 1RS,4SR,9SR anti-epimeric racemate (881685-58-1), (2.12) isopyrazam (anti-epimeric racemate), (2.13) isopyrazam (1R,4S,9S anti-epimeric enantiomer), (2.14 ) isopyrazam (1S,4R,9R anti-epimeric enantiomer), (2.15) isopyrazam (1RS,4SR,9RS syn-epimeric racemate), (2.16) isopyrazam (1R,4S,9R syn-epimeric enantiomer), (2.17) isopyrazam (1S,4R,9S syn-epimeric enantiomer), (2.18) mepronil (55814-41-0), (2.19) oxycarboxin (5259-88-1), (2.20) penflufen (494793-67-8), (2.21 ) penthiopyrad (183675-82-3), (2.22) sedaxane (87496 7-67-6), (2.23) tifluzamid (130000-40-7), (2.24) 1-methyl-N-[2-(1,1,2,2-tetrafluoroethoxy)phenyl]-3-(trifluoromethyl) -1H-pyrazole-4-carboxamide, (2.25) 3-(difluoromethyl)-1-methyl-N-[2-(1,1,2,2-tetrafluoroethoxy)phenyl]-1H-pyrazole-4-carboxamide, ( 2.26) 3-(difluoromethyl)-N-[4-fluoro-2-(1,1,2,3,3,3-hexafluoropropoxy)phenyl]-1-methyl-1H-pyrazole-4-carboxamide, (2.27) N-[1-(2,4-dichlorophenyl)-1-methoxypropan-2-yl]-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxamide (1092400-95-7), (2.28) 5,8-difluoro-N-[2-(2-fluoro-4-{[4-(trifluoromethyl)pyridin-2-yl]oxy}phenyl)ethyl]quinazoline-4-amine (1210070-84-0) ( known from WO2010025451), (2.29) N-[9-(dichloromethylene)-1,2,3,4-tetrahydro-1,4-methanonaphthalen-5-yl]-3-(difluoromethyl)-1-methyl-1H- pyrazole-4-carboxamide, (2.30) N-[(1S,4R)-9-(dichloromethylene)-1,2,3,4-tetrahydro-1,4-methanonaphthalen-5-yl]-3-(difluoromethyl) -1-methyl-1H-pyrazole-4-carboxamide and (2.31) N-[(1R,4S)-9-(dichloromethylene-1,2,3,4-tetrahydro-1,4-methanonaphthalen-5-yl] -3-(difluoromethyl)-1-methyl-1H-p irazol-4-carboxamide; (3) Respiratory inhibitors (respiratory chain inhibitors) that act on complex III of the respiratory chain, such as, for example, (3.1) ametoctradin (865318-97-4), (3.2) amisulbrom (34863587-0), (3.3 ) azoxystrobin (131860-33-8), (3.4) cyazofamid (120116-883), (3.5) coumethoxystrobin (850881-30-0), (3.6) coumoxystrobin (850881-70-8), (3.5) dimoxystrobin (141600 -52-4), (3.6) enestroburin (238410-11-2) (known from WO 2004/058723), (3.9) famoxadone (131807-57-3) (known from WO 2004/058723), (3.10) fenamidone (161326-34-7) (known from WO 2004/058723), (3.11) phenoxystrobin (918162-02-4), (3.12) fluoxastrobin (361377-29-9) (known from WO 2004/058723), (3.13 ) kresoxim-methyl (143390-89-0) (known from WO 2004/058723), (3.14) metominostrobin (133408-50-1) (known from WO 2004/058723), (3.15) orisastrobin (189892-69-1 ) (known from WO 2004/058723), (316) picoxystrobin (117428-22-5) (known from WO 2004/058723), (317) pyraclostrobin (175013-18-0) (known from WO 2 004/058723), (318) pyramethostrobin (915410-70-7) (known from WO 2004/058723), (3.19) pyraoxystrobin (862588-11-2) (known from WO 2004/058723), (3.20) pyribencarb ( 799247-52-2) (known from WO 2004/058723), (3.21) triclopyricarb (902760-40-1), (3.22) trifloxystrobin (141517-21-7) (known from WO 2004/058723), (3.23) (2E)-2-(2-{[6-(3-chloro-2-methylphenoxy)-5-fluoropyrimidin-4-yl]oxy}phenyl)-2-(methoxyimino)-N-methylethanamide (known from WO 2004 /058723), (3.24) (2E)-2-(methoxyimino)-N-methyl-2-(2-{[({(1E)-1-[3-(trifluoromethyl)phenyl]ethylidene}amino)oxy] methyl}phenyl)ethanamide (known from WO 2004/058723), (3.25) (2E)-2-(methoxyimino)-N-methyl-2-{2-[(E)-({1-[3-(trifluoromethyl) )phenyl]ethoxy}imino)methyl]phenyl}ethanamide (158169-73-4), (3.26) (2E)-2-{2-[({[(1E)-1-(3-{[(E) -1-fluoro-2-phenylethenyl]oxy}phenyl)ethylidene]amino}oxy)methyl]phenyl}-2-(methoxyimino)-N-methylethanamide (326896-28-0), (3.27) (2E)-2- {2-[({[(2E,3E)-4-(2,6-dichlorophenyl)but-3-en-2-ylidene]amino}oxy)methyl]phenyl}-2-(methoxyimino) -N-methylethanamide, (3.28) 2-chloro-N-(1,1,3-trimethyl-2,3-dihydro-1H-inden-4-yl)pyridine-3-carboxamide (119899-14-8) (3.29) 5-methoxy-2-methyl-4-(2-{[({(1E)-1-[3-(trifluoromethyl)phenyl]ethylidene}amino)oxy]methyl}phenyl)-2,4-dihydro -3H-1,2,4-triazol-3-one, (3.30) (2E)-2-{2-[({cyclopropyl[(4-methoxyphenyl)imino]methyl}sulfanyl)methyl]phenyl}-3- methyl methoxyprop-2-enoate (149601-03-6), (3.31) N-(3-ethyl-3,5,5-trimethylcyclohexyl)-3-(formylamino)-2-hydroxybenzamide (226551-21-9) , (3.32) 2-{2-[(2,5-dimethylphenoxy)methyl]phenyl}-2-methoxy-N-methylacetamide (173662-97-0) and (3.33) (2R)-2-{2-[ (2,5-dimethylphenoxy)methyl]phenyl}-2-methoxy-N-methylacetamide (394657-24-0); (4) Inhibitors of mitosis and cell division, such as, for example, (4.1) benomyl (17804-35-2), (4.2) carbendazim (10605-21-7), (4.3) chlorphenazol (3574-96-7) ), (4.4) dietofencarb (87130-20-9), (4.5) ethaboxam (162650-77-3), (4.6) fluopicolid (239110-15-7), (4.7) fuberidazole (3878-19-1), (4.8) pencycuron (66063-05-6), (4.9) thiabendazole (148-79-8), (4.10) thiophanate-methyl (23564-05-8), (4.11) thiophanate (23564-06-9), (4.12) zoxamide (156052-68-5), (4.13) 5-chloro-7-(4-methylpiperidin-1-yl)-6-(2,4,6-trifluorophenyl)[1,2,4]triazole [1,5-a]pyrimidine (214706-53-3) and (4.14) 3-chloro-5-(6-chloropyridin-3-yl)-6-methyl-4-(2,4,6-trifluorophenyl) pyridazine (1002756-87-7); (5) Compounds with multisite activity, such as, for example, (5.1) Bordeaux mixture (8011-63-0), (5.2)captafol (242506-1), (5.3)captan (133-06-2) ( known from WO 02/12172), (5.4) chlorothalonil (1897-45-6), (5.5) copper-based preparations such as copper hydroxide (20427-59-2), (5.6) copper naphthenate (1338 -02-9), (5.7) copper oxide (1317-39-1), (5.8) copper oxychloride (1332-40-7), (5.9) copper sulfate (7758-98-7), (5.10 ) dichlofluanid (1085-98-9), (5.11) dithionone (3347-22-6), (5.12) dodine (2439-10-3), (5.13) dodine free base, (5.14) ferbam (14484-64- 1), (5.15) fluorofolpet (719-96-0), (5.16) folpet (133-07-3), (5.17) guazatine (108173-90-6), (5.18) guazatine acetate, (5.19) iminoctadine ( 13516-27-3), (5.20) iminoctadine albesylate (169202-06-6), (5.21) iminoctadine triacetate (5752017-9), (5.22) mancopper (53988-93-5), (5.23) mancozeb ( 8018-01-7), (5.24) maneb (12427-38-2), (5.25) methiram (9006-42-2), (5.26) zinc methiram (9006-42-2), (5.27) oxina- copper (10380-28-6), (5.28) propamidine (104-32-5), (5.29) propineb (12071-83-9), (5.30) sulfur and sulfur-based preparations such as, for example, polysulfide of calcium (7704-34-9), (5.31) tiram (137-26-8), (5.32) tolylfluanid (731-271), (5.33) zineb (12122-67-7) and (5.34) ziram (137 -30-4); (6) Resistance inducers, such as, for example, (6.1) acibenzolar-S-methyl (135158-54-2), (6.2) isotianil (224049-04-1), (6.3) probenazol (27605-76- 1) and (6.4) tiadinil (223580-51-6); (7) Inhibitors of amino acid and protein biosynthesis, such as, for example, (7.1) andoprim (23951-85-1), (7.2) blasticidin-S (2079-00-7), (7.3) cyprodinil (121552 -61-2), (7.4) kasugamycin (6980-18-3), (7.5) kasugamycin hydrochloride hydrate (19408-46-9), (7.6) mepanipyrim (110235-47-7), (7.7) pyrimethanil ( 53112-28-0) and (7.8) 3-(5-fluoro-3,3,4,4-tetramethyl-3,4-dihydroisoquinolin-1-yl)quinoline (861647-32-7) (known from WO2005070917) ; (8) Inhibitors of ATP production, such as, for example, (8.1) fentin acetate (900-95-8), (8.2) fentin chloride (639-58-7), (8.3) fentin hydroxide ( 76-87-9) and (8.4) silthiofam (175217-20-6); (9) Inhibitors of cell wall synthesis, such as, for example, (9.1) bentiavalcarb (177406-68-7), (9.2) dimethomorph (11048870-5), (9.3) flumorph (211867-47-9), (9.4) iprovalicarb (140923-17-7), (9.5) mandipropamide (374726-62-2), (9.6) polyoxins (11113-80-7), (9.7) polyoxorim (22976-86-9), (9.8 ) validamycin A (37248-47-8) and (9.9) valifenalate (283159-94-4; 283159-90-0); (10) Inhibitors of lipid and membrane synthesis, such as, for example, (10.1) biphenyl (92-52-4), (10.2) chlorneb (2675-776), (10.3) dichloran (99-30-9 ), (10.4) edifenfos (17109-49-8), (10.5) etridiazole (2593-15-9), (10.6) iodocarb (55406-53-6), (10.7) iprobenfos (26087-47-8) (10.8) isoprothiolane (50512-35-1), (10.9) propamocarb (25606-41-1), (10.10) propamocarb hydrochloride (25606-41-1), (10.11) prothiocarb (19622-08-3), (10.12) pyrazolophos (13457-18-6), (10.13) quintazene (82-68-8), (10.14) technazene (117-18-0) and (10.15) tolclophos-methyl (57018-04-9); (11) Inhibitors of melanin biosynthesis, such as, for example, (11.1) carpropamid (104030-54-8), (11.2) diclocimet (13992032-4), (11.3) fenoxanil (115852-48-7), ( 11.4) phthalide (27355-22-2), (11.5) pyroquilone (57369-32-1), (11.6) tricyclazole (41814-78-2) and (11.7) (3-methyl-1-[(4-methylbenzoyl) 2,2,2-trifluoroethyl)amino]butan-2-yl}carbamate (851524-22-6) (known from WO2005042474); (12) Inhibitors of nucleic acid synthesis, such as, for example, (12.1) benalaxyl (71626-11-4), (12.2) benalaxyl-M (kiralaxyl) (98243-83-5), (12.3) bupirimate ( 41483-43-6), (12.4) clozilacon (6793285-8), (12.5) dimethirimol (5221-53-4), (12.6) ethirimol (23947-60-6), (12.7) furalaxyl (57646-30- 7), (12.8) hyhexazol (10004-44-1), (12.9) metalaxyl (57837-19-1), (12.10) metalaxyl-M (mefenoxam) (70630-17-0), (12.11) ofurace (58810 -48-3), (12.12) oxadixyl (77732-09-3) and (12.13) oxolinic acid (14698-29-4); (13) Inhibitors of signal transduction, such as, for example, (13.1) chlozolinate (84332-86-5), (13.2) fenpiclonil (74738-173), (13.3) fludioxonil (131341-86-1), ( 13.4) iprodione (36734-19-7), (13.5) procymidone (32809-16-8), (13.6) quinoxyphen (124495-18-7) and (13.7) vinclozoline (50471-44-8); (14) Uncouplings, such as, for example, (14.1) binapacril (485-31-4), (14.2) dinocap (131-72-6), (14.3) ferimzone (89269-64-7), (14.4) fluazinam (79622-59-6) and (14.5) meptidinocap (131-72-6); (15) Other compounds, such as, for example, (15.1) bethiazole (21564-17-0), (15.2) betoxazine (163269-30-5), (15.3) capsimycin (70694-08-5), (15.4 ) carvone (99-49-0), (15.5) cynomethionate (2439-01-2), (15.6) pyriophenone (clazafenone) (68804661-9), (15.7) cufraneb (11096-18-7), (15.8) ciflufenamid (180409-60-3), (15.9) cymoxanil (57966-95-7), (15.10) cyprosulfamide (221667-31-8), (15.11) dazomet (533-74-4), (15.12) debacarb ( 62732-91-6), (15.13) dichlorophen (97-23-4), (15.14) diclomezine (62865-36-5), (15.15) difenzoquat (49866-87-7), (15.16) difenzoquat methylsulfate ( 4322248-6), (15.17) diphenylamine (122-39-4), (15.18) EcoMato, (15.19) fenpyrazamine (473798-59-3), (15.20) flumetover (154025-04-4), (15.21) fluoromide (41205-21-4), (15.22) flusulfamide (106917-52-6), (15.23) fluthianil (304900-25-2), (15.24) fosetyl-aluminum (39148-24-8), (15.25) fosetyl -calcium, (15.26) fosetyl-sodium (39148-16-8), (15.27) hexachlorobenzene (118-74-1), (15.28) irumamycin (81604-73-1), (15.29) metasulf ocarb (66952-49-6), (15.30) methyl isothiocyanate (556-61-6), (15.31) metrafenone (220899-03-6), (15.32) mildiomycin (67527-71-3), (15.33) natamycin (7681-93-8), (15.34) nickel dimethyldithiocarbamate (15521-65-0), (15.35) nitrothal-isopropyl (10552-74-6), (15.36) octylinone (26530-20-1), ( 15.37) oxamocarb (917242-12-7), (15.38) oxyfenthin (34407-87-9), (15.39) pentachlorophenol and its salts (87-86-5), (15.40) fenothrin, (15.41) phosphoric acid and its salts salts (13598-36-2), (15.42) propamocarb-fosetylate, (15.43) propanosine sodium (88498-02-6), (15.44) proquinazid (189278-12-4), (15.45) pyrimorph (868390-90 -3), (15.45e) (2E)-3-(4-tert-butylphenyl)-3-(2-chloropyridin-4-yl)-1-(morpholin-4-yl)prop-2-en-1 -one (1231776-28-5), (15.45z) (2Z)-3-(4-tert-butylphenyl)-3-(2-chloropyridin-4-yl)-1-(morpholin-4-yl)prop -2-en-1-one (1231776-29-6), (15.46) pyrrolnitrine (1018-71-9) (known from EP-A 1 559 320), (15.47) tebufloquine (376645-78-2), (15.48) teclophthalam (76280-91-6), (15.49) tolnifanide (304911-98 -6), (15.50) triazoxide (72459-58-6), (15.51) triclamide (70193-21-4), (15.52) zarilamid (8452751-5), (15.53) (3S,6S,) 2-methylpropanoate 7R,8R)-8-benzyl-3-[({3-[(isobutyryloxy)methoxy]-4-methoxypyridin-2-yl}carbonyl)amino]-6-methyl-4,9-dioxo-1,5- dioxonan-7-yl (517875-34-2) (known from WO2003035617), (15.54) 1-(4-{4-[(5R)-5-(2,6-difluorophenyl)-4,5-dihydro- 1,2-oxazol-3-yl]-1,3-thiazol-2-yl}piperidin-1-yl)-2-[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]ethanone (1003319-79-6), (15.55) 1-(4-{4-[(5S)-5-(2,6-difluorophenyl)-4,5-dihydro-1,2-oxazol-3-yl] -1,3-thiazol-2-yl}piperidin-1-yl)-2-[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]ethanone (1003319-80-9), (15.56 ) 1-(4-{4-[5-(2,6-difluorophenyl)-4,5-dihydro-1,2-oxazol-3-yl]-1,3-thiazol-2-yl}piperidin-1 -yl)-2-[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]ethanone (1003318-67-9), (15.57) 1-(4-Imidazol-1-carboxylate) methoxyphenoxy)-3,3-dimethylbutan-2-yl (111227-17-9), (15.58) 2,3,5,6-tetrachloro-4-(methylsulfonyl)pyridine (13108-52-6), (15.59) 2,3-dibutyl-6-chlorothieno[2,3-d]pyrimidin-4(3H)-one (221451-58-7), (15.60) 2,6-dimethyl-1H,5H-[1,4] dithiino[2,3-c:5,6-c']dipyrrole-1,3,5,7(2H,6H)-tetrone, (15.61) 2-[5-methyl-3-(trifluoromethyl)-1H- pyrazol-1-yl]-1-(4-{4-[(5R)-5-phenyl-4,5-dihydro-1,2-oxazol-3-yl]-1,3-thiazol-2-yl }piperidin-1-yl)ethanone (100331653-7), (15.62) 2-[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]-1-(4-{4-[(5S) )-5-phenyl-4,5-dihydro-1,2-oxazol-3-yl]-1,3-thiazol-2-yl}piperidin-1-yl)ethanone (1003316-54-8), (15.63 ) 2-[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]-1-{4-[4-(5-phenyl-4,5-dihydro-1,2-oxazol-3- yl)-1,3-thiazol-2-yl]piperidin-1-yl}ethanone (1003316-51-5), (15,64) 2-butoxy-6-iodo-3-propyl-4H-chromen-4-one , (15.65) 2-chloro-5-[2-chloro-1-(2,6-difluoro-4-methoxyphenyl)-4-methyl-1H-imidazol-5-yl]pyridine, (15.66) 2-phenylphenol and its salts (90-43-7), (15.67) 3-(4,4,5-trifluoro-3,3-dimethyl-3,4-dihydroisoquinolin-1-yl)quinoline (861647-85-0) (known of WO2005070917 ), (15.68) 3,4,5-trichloropyridine-2,6-dicarbonitrile (178 24-85-0), (15.69) 3-[5-(4-chlorophenyl)-2,3-dimethyl-1,2-oxazolidin-3-yl]pyridine, (15.70) 3-chloro-5-(4- - chlorophenyl)-4-(2,6-difluorophenyl)-6-methylpyridazine, (15.71) 4-(4-chlorophenyl)-5-(2,6-difluorophenyl)-3,6-dimethylpyridazine, (15.72) 5- amino-1,3,4-thiadiazol-2-thiol, (15.73) 5-chloro-N'-phenyl-N'-(prop-2-yn-1-yl)thiophene-2-sulfonohydrazide (134-31- 6), (15.74) 5-fluoro-2-[(4-fluorobenzyl)oxy]pyrimidine-4-amine (1174376-11-4) (known from WO2009094442), (15.75) 5-fluoro-2-[(4 -methylbenzyl)oxy]pyrimidine-4-amine (1174376-25-0) (known from WO2009094442), (15.76) 5-methyl-6-octyl[1,2,4]triazolo[1,5-a]pyrimidine- 7-amine, (15.77) ethyl-(2Z)-3-amino-2-cyano-3-phenylprop-2-enoate, (15.78) N'-(4-{[3-(4-chlorobenzyl)-1, 2,4-thiadiazol-5-yl]oxy}-2,5-dimethylphenyl)-N-ethyl-N-methylimidoformamide, (15.79) N-(4-chlorobenzyl)-3-[3-methoxy-4-(prop -2-yn-1-yloxy)phenyl]propanamide, (15.80) N-[(4-chlorophenyl)(cyano)methyl]-3-[3-methoxy-4-(prop-2-yn-1-yloxy) phenyl]propanamide, (15.81) N-[(5-bromo-3-chloropyridin-2-yl )methyl]-2,4-dichloropyridine-3-carboxamide, (15.82) N-[1-(5-bromo-3-chloropyridin-2-yl)ethyl]-2,4-dichloropyridine-3-carboxamide, (15.83) ) N-[1-(5-bromo-3-chloropyridin-2-yl)ethyl]-2-fluoro-4-iodopyridine-3-carboxamide, (15.84) N-{(E)-[(cyclopropylmethoxy)imino] [6-(difluoromethoxy)-2,3-difluorophenyl]methyl}-2-phenylacetamide (221201-92-9), (15.85) N-{(Z)-[(cyclopropylmethoxy)imino][6-(difluoromethoxy)- 2,3-difluorophenyl]methyl}-2-phenylacetamide (221201-92-9), (15.86) N'-{4-[(3-tert-butyl-4-cyano-1,2-thiazol-5-yl) )oxy]-2-chloro-5-methylphenyl}-N-ethyl-N-methylimidoformamide, (15.87) N-methyl-2-(1-{[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1 - yl]acetyl}piperidin-4-yl)-N-(1,2,3,4-tetrahydronaphthalen-1-yl)-1,3-thiazole-4-carboxamide (922514-49-6), (15.88) N-methyl-2-(1-{[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]acetyl}piperidin-4-yl)-N-[(1R)-1,2,3 ,4-tetrahydronaphthalen-1-yl]-1,3-thiazole-4-carboxamide (922514-07-6), (15.89) N-methyl-2-(1-{[5-methyl-3-(trifluoromethyl) -1H-pyrazol-1-yl]acetyl}piperidin-4-yl)-N-[( 1S)-1,2,3,4-tetrahydronaphthalen-1-yl]-1,3-thiazole-4-carboxamide (922514-48-5), (15.90) pentyl-{6-[({[(1- methyl-1H-tetrazol-5-yl)(phenyl)methylidene]amino}oxy)methyl]pyridin-2-yl}carbamate, (15.91) phenazine-1-carboxylic acid, (15.92) quinolin-8-ol (134- 31-6), (15.93) quinolin-8-ol sulfate (2:1) (134-31-6) and (15.94) {6-[({[(1-methyl-1H-tetrazol-5-yl) tert-butyl (phenyl)methylene]amino}oxy)methyl]pyridin-2-yl}carbamate; (16) Other compounds, such as, for example, (16.1) 1-methyl-3-(trifluoromethyl)-N-[2'-(trifluoromethyl)biphenyl-2-yl]-1H-pyrazole-4-carboxamide, ( 16.2) N-(4'-chlorobiphenyl-2-yl)-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxamide, (16.3) N-(2',4'-dichlorobiphenyl-2-yl )-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxamide, (16.4) 3-(difluoromethyl)-1-methyl-N-[4'-(trifluoromethyl)biphenyl-2-yl]-1H -pyrazole-4-carboxamide, (16.5) N-(2',5'-difluorobiphenyl-2-yl)-1-methyl-3-(trifluoromethyl)-1H-pyrazole-4-carboxamide, (16.6) 3-( difluoromethyl)-1-methyl-N-[4'-(prop-1-in-1-yl)biphenyl-2-yl]-1H-pyrazole-4-carboxamide, (16.7) 5-fluoro-1,3- dimethyl-N-[4'-(prop-1-yn-1-yl)biphenyl-2-yl]-1H-pyrazole-4-carboxamide, (16.8) 2-chloro-N-[4'-(prop- 1-yn-1-yl)biphenyl-2-yl]pyridine-3-carboxamide, (16.9) 3-(difluoromethyl)-N-[4'-(3,3-dimethylbut-1-yn-1-yl) biphenyl-2-yl]-1-methyl-1H-pyrazole-4-carboxamide, (16.10) N-[4'-(3,3-dimethylbut-1-yn-1-yl)biphenyl-2-yl]- 5-fluoro-1,3-dimethyl-1H-pyrazole-4-carboxamide, (16.11) 3-(difluorom) ethyl)-N-(4'-ethynylbiphenyl-2-yl)-1-methyl-1H-pyrazole-4-carboxamide, (16.12) N-(4'-ethynylbiphenyl-2-yl)-5-fluoro-1, 3-dimethyl-1H-pyrazole-4-carboxamide, (16.13) 2-chloro-N-(4'-ethynylbiphenyl-2-yl)pyridine-3-carboxamide, (16.14) 2-chloro-N-[4'- (3,3-dimethylbut-1-yn-1-yl)biphenyl-2-yl]pyridine-3-carboxamide (known from EP-A 1 559 320), (16.15) 4-(difluoromethyl)-2-methyl- N-[4'-(trifluoromethyl)biphenyl-2-yl]-1,3-thiazol-5-carboxamide, (16.16) 5-fluoro-N-[4'-(3-hydroxy-3-methylbut-1- n-1-yl)biphenyl-2-yl]-1,3-dimethyl-1H-pyrazole-4-carboxamide, (16,17) 2-chloro-N-[4'-(3-hydroxy-3-methylbut-1 -yn-1-yl)biphenyl-2-yl]pyridine-3-carboxamide, (16.18) 3-(difluoromethyl)-N-[4'-(3-methoxy-3-methylbut-1-yn-1-yl )biphenyl-2-yl]-1-methyl-1H-pyrazole-4-carboxamide, (16.19) 5-fluoro-N-[4'-(3-methoxy-3-methylbut-1-yn-1-yl) biphenyl-2-yl]-1,3-dimethyl-1H-pyrazole-4-carboxamide, (16.20) 2-chloro-N-[4'-(3-methoxy-3-methylbut-1-yn-1-yl )biphenyl-2-yl]pyridine-3-carboxamide, (16.21) (5-bromo-2-methoxy-4-methylpyridin-3-yl)(2,3,4-trimethox i-6-methylphenyl)methanone, (16.22) N-[2-(4-{[3-(4-chlorophenyl)prop-2-yn-1-yl]oxy}-3-methoxyphenyl)ethyl]-N2- (methylsulfonyl)valinamide (220706-93-4), (16.23) 4-oxo-4-[(2-phenylethyl)amino]butanoic acid and (16.24) {6-[({[(Z)-(1-methyl) but-3-yn-1-yl -1H-tetrazol-5-yl)(phenyl)methylene]amino}oxy)methyl]pyridin-2-yl}carbamate.
[0010]
10. Agrochemical compositions, characterized in that they comprise at least one compound of Formula (I), as defined in any one of claims 1 to 6, or a composition, as defined in claim 9, and further diluents and/or surfactants.
[0011]
11. Process for the preparation of agrochemical compositions, characterized in that compounds of Formula (I), as defined in any one of claims 1 to 6, or a composition as defined in claim 9, is (are) mixed ) with thinners and/or surfactants.
[0012]
12. A method for controlling animal pests, characterized in that compounds of Formula (I), as defined in any one of claims 1 to 6, or a composition as defined in claim 9, is (are) left act on animal pests and/or their habitat, excluding methods for surgical or therapeutic treatment of the human or animal body and diagnostic methods performed on the human or animal body.
[0013]
13. Use of compounds of Formula (I), as defined in any one of claims 1 to 6, or of a composition, as defined in claim 9, characterized in that it is for the control of animal pests in crop protection, in protection of materials and/or in the veterinary sector, excluding uses in methods for surgical or therapeutic treatment of the human or animal body and diagnostic methods performed on the human or animal body.

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法律状态:
2018-03-27| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|

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2019-01-08| B07A| Application suspended after technical examination (opinion) [chapter 7.1 patent gazette]|

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2020-08-11| B06A| Patent application procedure suspended [chapter 6.1 patent gazette]|

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2020-12-08| B06A| Patent application procedure suspended [chapter 6.1 patent gazette]|

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2021-04-06| B06A| Patent application procedure suspended [chapter 6.1 patent gazette]|

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2021-06-08| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

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2021-07-20| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 12/12/2012, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

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申请号 | 申请日 | 专利标题

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EP11194855.0A|EP2606726A1|2011-12-21|2011-12-21|N-Arylamidine-substituted trifluoroethylsulfide derivatives as acaricides and insecticides|

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PCT/EP2012/075269|WO2013092350A1|2011-12-21|2012-12-12|N-arylamidine-substituted trifluoroethyl sulfide derivatives as acaricides and insecticides|

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