9-ketospinosyn derivatives

专利摘要:

公开号:AU2004205353A1
申请号:U2004205353
申请日:2004-01-08
公开日:2004-08-05
发明作者:Michael E. Beck；Ulrich Ebbinghaus-Kintscher；Gunther Eberz；Rita Frode；Peter Jeschke；Peter Losel；Olga Malsam；Volker Mohrle；Robert Velten
申请人:Bayer CropScience AG；
IPC主号:C07D315-00

专利说明:
&1~&c) fJc~ AKTUEL TRANSLATION GROUP IN THE MATTER OF: International Patent Application PCT/EP2004/000 05 8 We the undersigned: The Aktuel Translation Group The Old Smithy 19bHart St, Henley on Thames OXON RG9 2AR, England do solemnly and sincerely Declare as follows:
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THAT our translator and proof reader is well acquainted with both the English and German languages and is a competent translator of technical and other matter written in German into English. 2. THAT the attached document is to the best of our knowledge, understanding and belief a true and correct translation made by our translator of a document supplied to us AND WE MAKE this Declaration by virtue of the Statutory Declarations Act 1835, conscientiously believing the statements contained therein to be true in every particular. )RK DECLARED this22 day of June, 2005 U RT (ONG Robin Benne , Director JVER Witnessed by Lawrence Hamblin Solicitors Concept House 9-11 Greys Road Henley on Thames Oxon. RG9 1SB Telephone 01491 411884 9-Keto Spinosyn Derivatives The present invention relates to derivatives of 9-keto spinosyns, which are 5 substituted by a =N-(O, NH or NRx)-Ry moiety in the C-9 position, methods for their manufacture, and their use for controlling animal pests. Spinosyns are known compounds; they are fermentation products, which are manufactured from the cultures of the actinomycete Saccharopolyspora spinosa. 10 Synthetic preparations for the manufacture of spinosyn derivatives were described by Martynow, J. G. and Kirst, H. A. in J. Org. Chem. 1994, 59, 1548. In this publication, both the 9,17-diketone of the spinosyn aglycone and the 17-keto derivative of the spinosyn aglycone are mentioned. The spinosyn-17-pseudoaglycone and spinosyn-9 15 pseudoaglycone are disclosed in WO 97/00265 and US-A 6,001,981. The manufacture of additional derivatives, which are obtainable with semi synthetic methods starting from natural products, is described in these texts. The spinosyn-9 pseudoaglycone derivative, which is oxidised into ketone at the C-9 position, is also known as an insecticide compound, for example, and was produced through chemical 20 derivatisation (see. WO 97/00265 and US-A 6,001,981). The object of the present invention is to provide new derivatives of 9-keto spinosyns. An additional object of the present invention is to provide methods that are suitable for the manufacture of these derivatives. 25 The present invention relates to compounds according to the general formula (I) -2 17 CH3 H H and derived salts, where X stands for 0, NH or NR 4 , 5 R' stands for hydrogen or an amino sugar, R2 stands for hydrogen or a possibly substituted alkyl, cycloalkyl, arylalkyl, hetarylalkyl, aryl or hetaryl, or for CO-R' or CS-R' if X stands for NH or 10 NR 4 , where R' stands for amino, possibly substituted alkyl, alkylamino, dialkylamino, 15 aryl, arylamino, hetarylamino, arylalkyl, hetaryl or hetarylalkyl,
R
3 stands for hydrogen or hydroxy, R4 stands for possibly substituted alkyl, or forms a 3-, 4-, 5-, 6-, 7- or 8 20 membered ring with R 2 , which can be interrupted by one or more heteroatom(s) such as 0, S, SO, SO 2 , NH or NR 5 , and is possibly substituted, ' stands for possibly substituted alkyl, cycloalkyl, arylalkyl, hetarylalkyl, aryl or hetaryl, and 25 -3 A-B stands for one of the following groups: -HC=CH-, -HC=C(CH 3 )-, -H 2
C-CH
2 or -H 2
C-CH(CH
3 )-. The following sections will explain preferred substituents or regions of the moieties 5 listed in the formulas indicated above or below. The occurrence of possibly substituted alkyl by itself or as a component of a moiety in the general formulas designates straight-chained or branched alkyl with preferably 1 to 6, particularly 1 to 4 carbon atoms. The following are mentioned as examples: 10 possibly substituted methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1,2-dimethylbutyl, 1,1-dimethylpropyl, 2,2-dimethylpropyl, 1-ethoxypropyl, hexyl, I-methylpentyl, 2 methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,3-dimethylbutyl, 1,1-dimethylbutyl, 2,2-dimethylbutyl, 3,3-dimethylbutyl, 1,1,2 15 trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethylbutyl, and 2-ethylbutyl. Preferable substances are methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert butyl. The occurrence of possibly substituted cycloalkyl by itself or as a component of a 20 moiety in the general formulas designates mono-, bi-, and tricyclic cycloalkyl, preferably with 3 to 10,-particularly with 3, 5 or 7 carbon atoms. The following are mentioned as examples: possibly substituted cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, bicyclo[2.2.1]heptyl, bicyclo[2.2.2]octyl, and adamantyl. 25 The occurrence of possibly substituted arylalkyl in the general formulas preferably designates substituted arylalkyl possibly in the aryl portion and/or alkyl portion with an aryl portion defined as described below, and with preferably 1 to 4, particularly 1 or 2 carbon atoms in the alkyl portion, and the alkyl portion can be straight-chained 30 or branched. Benzyl and phenylethyl are mentioned as examples and as preferable substances.
-4 The occurrence of possibly substituted hetarylalkyl in the general formulas preferably designates substituted hetarylalkyl possibly in the hetaryl portion and/or alkyl portion with a hetaryl portion defined as described below, and with preferably 1 to 4, 5 particularly 1 or 2 carbon atoms in the alkyl portion, and the alkyl portion can be straight-chained or branched. The occurrence of possibly substituted aryl by itself or as a component of a moiety in the general formulas designates, for example, a mononuclear, binuclear or 10 polynuclear aromatic moiety such as phenyl, naphthyl, tetrahydronaphthyl, indanyl, fluorenyl, however preferably phenyl or naphthyl, and particularly phenyl. The occurrence of possibly substituted hetaryl by itself or as a component of a moiety in the general formulas designates 5- to 7-membered rings with preferably 1 to 3, 15 particularly 1 or 2 of the same or different heteroaromates. Oxygen, sulphur or nitrogen can be heteroatoms in the heteroaromates. The following are listed as examples, and are preferred: possibly substituted furyl, thienyl, pyrazolyl, imidazolyl, 1,2,4- and 1,2,4-triazolyl, isoxazolyl, thiazolyl, isothiazolyl, 1,2,3-, 1,3,4-, 1,2,4- and 1,2,5-oxadiazolyl, azepinyl, pyrrolyl, pyridyl, piperazinyl, pyridazinyl, pyrimidinyl, 20 pyrazinyl, 1,3,5-, 1,2,4- and 1,2,3-triazinyl, 1,2,4-, 1,3,2-, 1,3,6- and 1,2,6-oxazinyl, oxepinyl, thiepinyl and 1,2,4-diazepinyl. The possibly substituted moieties in the general formulas can carry one or more, preferably 1 to 3, particularly 1 to 2 identical or different substituents. The following 25 are listed as examples of preferred substituents: Alkyl with preferably 1 to 4, particularly 1 to 2 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl; alkoxy with preferably 1 to 4, particularly 1 to 2 carbon atoms, such as methoxy, ethoxy, n-propoxy, 30 isopropoxy, n-butoxy, isobutoxy, sec-butoxy and tert-butoxy; alkylthio with preferably 1 to 4, particularly 1 to 2 carbon atoms, such as methylthio, ethylthio, n- -5 propylthio, isopropylthio, n-butylthio, isobutylthio, sec-butylthio and tert-butylthio; halogenalkyl with preferably I to 4, particularly 1 to 2 carbon atoms and preferably 1 to 4, particularly 1 to 3 halogen atoms, where the halogen atoms are identical or different and are preferably fluorine, chlorine, bromine, iodine, particularly fluorine 5 or chlorine, such as difluoromethyl, trifluoromethyl, trichloromethyl; hydroxy, halogen, preferably fluorine, chlorine, bromine, iodine, particularly fluorine and chlorine; cyano; nitro; amino; monoalkyl- and dialkylamino with preferably 1 to 4, particularly 1 or 2 carbon atoms per alkyl group, such as methylamino, methylethylamino, dimethylamino, n-propylamino, isopropylamino, methyl-n 10 butylamino; alkylcarbonyl moieties such as methylcarbonyl, alkoxycarbonyl with preferably 2 to 4, particularly 2 to 3 carbon atoms, such as methoxycarbonyl and ethoxycarbonyl; alkylsulphinyl with I to 4, particularly I to 2 carbon atoms; halogensulphinyl with I to 4, particularly 1 to 2 carbon atoms, and 1 to 5 halogen atoms such as trifluoromethylsulphinyl; sulphonyl (-S0 2 -OH); alkylsulphonyl with 15 preferably I to 4, particularly 1 or 2 carbon atoms, such as methylsulphonyl and ethylsulphonyl or halogenalkylsulphonyl with 1 to 4, particularly I to 2 carbon atoms and 1 to 5 halogen atoms such as trifluoromethanesulphonyl. Suitable cyclic amino groups can be heteroaromatic or aliphatic ring systems with 20 one or more nitrogen atoms as a heteroatom, in which the heterocycles can be saturated or unsaturated, a ring system or several condensed ring systems, and can possibly contain additional heteroatoms such as nitrogen, oxygen, and sulphur, etc. In addition, cyclic amino groups can also designate a spiro ring or a bridged ring system. The number of atoms that form cyclic amino groups is not restricted; for 25 example, they consist of from 3 to 8 atoms in the case of a single-ring system, and of from 7 to 11 atoms in the case of a triple-ring system. The following are examples of cyclic amino groups: saturated and unsaturated monocyclic ring systems with one nitrogen atom as a heteroatom, such as 30 1-azetidinyl, pyrrolidino, 2-pyrrolin-1-yl, 1-pyrrolyl, piperidino, 1,4-dihydropyridin 1-yl, 1, 2 ,5,6-tetrahydropyridin-1-yl and homopiperidino; examples of cyclic amino -6 groups are saturated and unsaturated monocyclic ring systems with two or more nitrogen atoms as heteroatoms, such as 1-imidazolidinyl, 1-imidazolyl, 1-pyrazolyl, 1-triazolyl, 1-tetrazolyl, 1-piperazinyl, 1-homopiperazinyl, 1,2-dihydropyridazin-1-yl, 1,2-dihydropyrimidin-1-yl, perhydropyrimidin-l-yl and 1,4-diazacycloheptan-1-yl; 5 examples of cyclic amino groups are saturated and unsaturated monocyclic ring systems with one to three nitrogen atoms and one to two oxygen atoms as heteroatoms, such as oxazolin-3-yl, isoxazolin-2-yl, morpholino or 2,6 dimethylmorpholino; examples of cyclic amino groups are saturated or unsaturated monocyclic ring systems with one to three nitrogen atoms and one to two sulphur 10 atoms as heteroatoms; examples of cyclic amino groups are saturated and unsaturated condensed ring systems such as indol-1-yl, 1,2-dihydro-benzimidazol-1-yl, perhydro pyrrolo[1,2]pyrazin-2-yl; examples of cyclic amino groups are spiro-cyclic ring systems such as 2-azaspiro[4,5]-decan-2-yl; examples of cyclic amino groups are bridged heterocyclic ring systems such as 2-azabicyclo [2,2,1 ]heptan-7-yl. 15 The compounds according to the invention are generally defined by formula (I). The preferred substituents and regions of the moieties listed in the formulas shown above and below are described in the following section. 20 X preferably stands for 0, NH or NMe. Ri preferably stands for hydrogen or for an amino sugar shown in the formulae la to Ig Me Me MeN SR Me H 25 la -7 Me Me MeHN,, HN RO R Me H H 1b Me HN H2N, -RO 2 R Me H 1c Mex Me 0=( O O H Me 2 N O R SR Me Me 2 N Me 1d H OH HO Me 2NC
-
*S R~ Me Me 2 N Me 1e CH 3 O yCH3 H 0 M R M e Me RO M e~ Me2NM Me H 1g -8 R2 preferably stands for possibly substituted aryl-CI-C 3 -alkyl, particularly for benzyl, 1-phenyl-ethyl, 2-phenyl-ethyl, 3-phenyl-propyl, 2-phenyl-propyl, 2 phenyl-isopropyl, 1 -methyl-2-phenyl-ethyl, hetaryl-C I-C 3 -alkyl, hetarylmethyl, I -hetaryl-ethyl, 2-hetaryl-ethyl, 3-hetaryl-propyl, 2-hetaryl 5 propyl, 2-hetaryl-isopropyl, 1-methyl-2-hetaryl-ethyl, and the substituents can be selected from the group of hydrogen, straight-chained or branched alkyl with up to 4 carbon atoms, in particular methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, halogenalkyl with up to 2 carbon atoms, in particular trifluoromethyl, difluorochloromethyl, pentafluoroethyl, alkenyl 10 with up to 3 carbon atoms, cyclic alkyl with up to 6 carbon atoms, in particular cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, hydroxy, halogen, particularly bromine, chlorine, fluorine or iodine, alkoxy, particularly methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert butoxy, cycloalkoxy, particularly cyclopropyloxy, alkenyloxy, in particular 15 allyloxy, dioxoalkylene, particularly dioxomethylene, halogenalkoxy, in particular trifluoromethoxy, alkylthio, particularly methylthio, halogenalkylthio, particularly trifluoromethylthio, alkylsulphonyl, particularly methylsulphonyl, halogenalkylsulphonyl, in particular trifluoromethyl sulphonyl, hetarylsulphonyl, particularly N-morpholinosulphonyl or N-pyra 20 zolylsulphonyl, nitro, amino, a suitable cyclic amino group, particularly N pyrrolidino, N-piperidino, N-morpholino, N-(2,6-dimethyl-morpholino),
N
methyl-piperazino, N-thiomorpholino or N-dioxothiomorpholino, alkylamino, particularly methylamino, ethylamino, propylamino, isopropylamino, butylamino, sec-butylamino, isobutylamino, tert-butylamino, alkyleneamino, 25 in particular propyleneamino, dialkylamino, particularly dimethylamino, diethylamino, carboxyl, carbamoyl, cyano, alkoxycarbonyl, particularly methoxycarbonyl, ethoxycarbonyl, propyloxycarbonyl, isopropyloxycarbonyl, butyloxycarbonyl, sec-butyloxycarbonyl, isobutyloxycarbonyl, tert butyloxycarbonyl, alkyleneoxycarbonyl, particularly propyleneoxycarbonyl, 30 N-alkoxycarbonyl-amino, particularly N-methoxycarbonylamino,
N
ethoxycarbonylamino, N-propyloxycarbonylamino, N-isopropyloxycarbonyl- -9 amino, N-butyloxycarbonyl-amino, N-sec-butyloxycarbonylamino, N isobutyloxycarbonylamino, N-tert-butyloxycarbonylamino, cyanoalkylenecar bonylamino, particularly cyanomethylenecarbonylamino, cyanoethylene carbonylamino, N-alkyleneoxycarbonylamino, in particular N 5 propyleneoxycarbonylamino, N-alkylsulphonylamino, particularly N-me thylsulphonyl-amino, N-ethylsulphonylamino, N-propylsulphonylamino, N isopropylsulphonyl-amino, N-butylsulphonylamino, N-sec-butylsulphonyl amino, N-isobutylsulphonyl-amino, N-tert-butylsulphonylamino, N-alkylen esulphonylamino, in particular N-propylenesulphonylamino, possibly 10 substituted arylsulphonylamino, particularly 4-trifluoromethyl phenylsulphonylamino, N-alkoxycarbonyl-N-alkyl-amino, particularly N methoxycarbonyl-N-methyl-amino, N-methoxy-carbonyl-N-ethyl-amino, N ethoxycarbonyl-N-methyl-amino, N-ethoxycarbonyl-N-ethyl-amino, N propyloxycarbonyl-N-methyl-amino, N-propyloxycarbonyl-N-ethyl-amino,
N
15 isopropyloxycarbonyl-N-methyl-amino, N-isopropyloxycarbonyl-N-ethyl amino, N-butyloxycarbonyl-N-methyl-amino, N-butyloxy-carbonyl-N-ethyl amino, N-sec-butyloxycarbonyl-N-methyl-amino, N-sec-butyloxycarbonyl-N ethyl-amino, N-isobutyloxy-carbonyl-N-methyl-amino, N-iso butyloxycarbonyl-N-ethyl-amino, N-tert-butyloxycarbonyl-N-methyl-amino, 20 N-tert-butyloxycarbonyl-N-methyl-amino, N-alkyleneoxycarbonyl-N-alkyl amino, particularly N-propyleneoxycarbonyl-N-methylamino, N-propylene oxycarbonyl-N-methyl-amino, N-alkylcarbonyl-N-alkylamino, in particular N-methylcarbonyl-N-methyl-amino, N-methyl-carbonyl-N-ethyl-amino, N ethyl-carbonyl-N-methyl-amino, N-ethylcarbonyl-N-ethyl-amino, N 25 cycloalkylcarbonylamino, particularly N-cyclopropyl-carbonylamino, N-1 methylcycloprop-1-yl-carbonyl-N-amino, N-cyclobutyl-amino, N-alkoxy carbonyl-N-alkylsulphonyl-amino, particularly N-methoxy-carbonyl-N methylsulphonyl-amino, N-methoxycarbonyl-N-ethyl-sulphonylamino, N ethoxy-carbonyl-N-methylsulphonyl-amino, N-ethoxy-carbonyl-N-ethyl 30 sulphonylamino, N-propyloxycarbonyl-N-methyl-sulphonyl-amino, N-propyl oxy-carbonyl-N-ethylsulphonyl-amino, N-isopropyloxycarbonyl-N-methyl- -10 sulphonyl-amino, N-isopropyloxycarbonyl-N-ethylsulphonylamino, N butyloxycarbonyl-N-methylsulphonyl-amino, N-butyloxycarbonyl-N-ethyl sulphonylamino, N-sec-butyloxycarbonyl-N-methylsulphonyl-amino, N-sec butyloxycarbonyl-N-ethyl-sulphonyl-amino, N-isobutyloxycarbonyl-N 5 methyl-sulphonyl-amino, N-isobutyloxycarbonyl-N-ethylsulphonylamino, N tert-butyloxy-carbonyl-N-methyl-sulphonylamino, N-tert-butyloxycarbonyl N-methylsulphonyl-amino, N-alkyleneoxycarbonyl-N-alkylsulphonyl-amino, in particular N-propyleneoxycarbonyl-N-methylsulphonyl-amino, N propyleneoxycarbonyl-N-methylsulphonyl-amino, N-alkylcarbonyl-N 10 alkylsulphonyl-amino, particularly N-methylcarbonyl-N-methylsulphonyl amino, N-methylcarbonyl-N-ethylsulphonyl-amino, N-ethyl-carbonyl-N methylsulphonyl-amino, N-ethylcarbonyl-N-ethyl-sulphonylamino, N cycloalkylcarbonyl-N-alkylsulphonyl-amino, particularly N-cyclopropyl carbonyl-N-methylsulphonyl-amino, N-1-methylcycloprop-1-yl-carbonyl-N 15 methylsulphonylamino, N-cyclobutyl-N-methylsulphonylamino, alkylaminocarbonylamino, in particular N-methylaminocarbonylamino, N ethylamino-carbonylamino, N,N-dialkylaminocarbonylamino, particularly N,N-dimethylaminocarbonylamino, N-alkylaminosulphonylamino, in particular N-methylaminosulphonylamino, N,N-dialkylaminosulphonylamino, 20 particularly N,N-dimethylaminosulphonylamino. If X stands for NH or NMe, then R2 continues to preferably stand for CO-R' or CS-R', 25 where R' stands for amino, possibly substituted Ci-C 4 -alkyl, CI-C 4 alkylamino, Di-Ci-C 4 -alkylamino, aryl, arylamino, hetaryl 30 amino, aryl-Ci-C 3 -alkyl, hetaryl or hetaryl-Ci-C 3 -alkyl.
- 11 R4 preferably stands for possibly substituted Ci-C 4 -alkyl or forms a 6-membered ring with R 2 , which can be interrupted by 0, S or NR , and which is substituted if necessary. 5 R 5 preferably stands for possibly substituted CI-C 4 -alkyl. X particularly preferably stands for 0 or NH. RI particularly preferably stands for hydrogen or for an amino sugar shown in the 10 formulae la, ld or le Me Me Me 2 N,, MeN SRO sR Me-'o R Me H la Me Me O O Me2N R S R .S R, Me Me2N Me 1d H OH HO Me2N _R S OC OS R, Me Me2N' Me le 15 R2 particularly preferably stands for aryl-Ci-C 3 -alkyl, in particular for benzyl, 1 phenyl-ethyl, hetaryl-Cr-C 3 -alkyl, hetarylmethyl, particularly pyridylmethyl, pyrimidylmethyl, pyridazinylmethyl, pyrazylmethyl, furylmethyl, thiazolylmethyl, pyrazolylmethyl, oxazolylmethyl, isoxazolylmethyl, - 12 thiazolylmethyl, imidazolylmethyl, triazolylmethyl, tetrazolylmethyl, dihydro dioxazinylmethyl, 1 -hetaryl-ethyl, in particular 1 -pyridylethyl, 1 pyrimidylethyl, I-pyridazinylethyl, 1-pyrazylethyl, 1-furylethyl, 1 -thia zolylethyl, 1 -pyrazolylethyl, 1 -oxazolylethyl, 1 -isoxazolylethyl, I -thia 5 zolylethyl, I-imidazolylethyl, 1-triazolylethyl, 1-tetrazolylethyl, 1-dihydro dioxazinylethyl, which can each be substituted by moieties from the group of hydrogen, straight-chained or branched alkyl with up to 4 carbon atoms, in particular methyl, ethyl, propyl, tert-butyl, halogenalkyl, in particular trifluoromethyl, hydroxy, halogen, particularly bromine, chlorine, fluorine or 10 iodine, alkoxy, particularly methoxy, ethoxy, tert-butoxy, halogenalkoxy, in particular trifluoromethoxy, alkylthio, particularly methylthio, halogenalkylthio, particularly trifluoromethylthio, alkylsulphonyl, particularly methylsulphonyl, halogenalkylsulphonyl, in particular trifluoromethylsulphonyl, nitro, amino, alkylamino, in particular methyl 15 amino, ethylamino, N-alkoxycarbonylamino, particularly N-methoxycarb onylamino, N-ethoxycarbonylamino, N-propyloxycarbonylamino, N-isopro pyloxycarbonyl-amino, N-butyloxycarbonylamino, N-sec-butyloxycarbonyl amino, N-isobutyloxycarbonylamino, N-tert-butyloxycarbonylamino,
N
alkyleneoxycarbonyl-amino, in particular N-propyleneoxycarbonylamino,
N
20 alkylsulphonylamino, particularly N-methylsulphonylamino, N-ethylsulph onylamino, N-propylsulphonylamino, N-isopropylsulphonylamino, N-butyl sulphonylamino, N-sec-butylsulphonylamino, N-isobutylsulphonyl-amino,
N
tert-butylsulphonylamino, N- N-alkoxycarbonyl-N-alkyl-amino, particularly N-methoxycarbonyl-N-methyl-amino, N-methoxy-carbonyl-N-ethyl-amino, 25 N-ethoxycarbonyl-N-methyl-amino, N-ethoxycarbonyl-N-ethyl-amino, N-pro pyloxycarbonyl-N-methyl-amino, N-propyloxycarbonyl-N-ethyl-amino,
N
isopropyloxycarbonyl-N-methyl-amino, N-isopropyloxycarbonyl-N-ethyl amino, N-butyloxy-carbonyl-N-methyl-amino, N-butyloxy-carbonyl-N-ethyl amino, N-sec-butyloxycarbonyl-N-methyl-amino, N-sec-butyloxycarbonyl-N 30 ethyl-amino, N-isobutyloxy-carbonyl-N-methyl-amino, N-isobutyloxy carbonyl-N-ethyl-amino, N-tert-butyloxycarbonyl-N-methyl-amino, N-tert- - 13 butyloxycarbonyl-N-methyl-amino, N-alkyleneoxycarbonyl-N-alkyl-amino, particularly N-propyleneoxycarbonyl-N-methylamino, N-propyleneoxycarb onyl-N-methyl-amino, N-alkylcarbonyl-N-alkylamino, particularly N-methyl carbonyl-N-methyl-amino, N-methylcarbonyl-N-ethyl-amino, N-ethyl 5 carbonyl-N-methyl-amino, N-ethylcarbonyl-N-ethyl-amino, N-cycloalkylcarb onylamino, in particular N-cyclopropylcarbonylamino, N-1-methylcycloprop 1 -yi-carbonyl-N-amino, N-cyclobutylamino, N-alkoxy-carbonyl-N alkylsulphonyl-amino, particularly N-methoxycarbonyl-N-methylsulphonyl amino, N-methoxycarbonyl-N-ethyl-sulphonylamino, N-ethoxy-carbonyl-N 10 methylsulphonyl-amino, N-ethoxy-carbonyl-N-ethylsulphonyl-amino,
N
propyloxycarbonyl-N-methyl-sulphonyl-amino, N-propyloxycarbonyl-N ethylsulphonyl-amino, N-isopropyloxycarbonyl-N-methylsulphonyl-amino, N-isopropyloxycarbonyl-N-ethylsulphonyl-amino, N-butyloxycarbonyl-N methyl-sulphonylamino, N-butyloxycarbonyl-N-ethyl-sulphonylamino, N-sec 15 butyloxy-carbonyl-N-methylsulphonyl-amino, N-sec-butyloxycarbonyl-N ethylsulphonyl-amino, N-isobutyloxycarbonyl-N-methyl-sulphonyl-amino,
N
isobutyloxy-carbonyl-N-ethylsulphonyl-amino, N-tert-butyloxy-carbonyl-N methylsulphonyl-amino, N-tert-butyloxycarbonyl-N-methylsulphonyl-amino, N-alkyleneoxycarbonyl-N-alkylsulphonyl-amino, particularly N 20 propyleneoxy-carbonyl-N-methylsulphonyl-amino, N-propyleneoxycarbonyl N-methylsulphonyl-amino, N-alkylcarbonyl-N-alkylsulphonyl-amino, particularly N-methylcarbonyl-N-methylsulphonyl-amino, N-methylcarbonyl N-ethylsulphonyl-amino, N-ethyl-carbonyl-N-methylsulphonyl-amino,
N
ethylcarbonyl-N-ethyl-sulphonyl-amino, N-cycloalkylcarbonyl-N-alkyl 25 sulphonyl-amino, in particular N-cyclopropyl-carbonyl-N-methylsulphonyl amino, N-1-methylcycloprop-1-yl-carbonyl-N-methylsulphonylamino,
N
cyclobutyl-N-methylsulphonylamino, alkylamino-carbonylamino, particularly N-methylaminocarbonylamino, N-ethyl-aminocarbonylamino, N,N-dialkyl aminocarbonylamino, particularly N,N-dimethylaminocarbonylamino, N 30 alkylaminosulphonylamino, in particular N-methylaminosulphonylamino, - 14 N,N-dialkylaminosulphonylamino, in particular N,N-dimethylamino sulphonylamino. If X stands for NH or Nme, then 5 R2 particularly preferably continues to stand for CO-R' or CS-R', where 10 R' stands for amino, arylamino, particularly trifluoromethoxy phenylamino, trifluoromethylphenylamino, chlorophenylamino, hetarylamino, particularly bromopyridylamino or trifluoromethylpyridylamino. 15 X particularly preferably stands for 0. RI quite particularly preferably stands for hydrogen or for an amino sugar as shown in the formulae la and le Me Me Me 2 N, 2 RO Me. S R Me H la H OH HO Me2N R S R Me Me 2 N '0Me 20 1e R2 quite particularly preferably stands for benzyl, 1-phenyl-ethyl, hetarylmethyl, particularly pyridylmethyl, pyridazinylmethyl, thiazolylmethyl, pyrazolyl- - 15 methyl, isoxazolylmethyl, imidazolylmethyl, dihydro-dioxazinylmethyl, 1 pyridylethyl, 1-thiazolylethyl, 1-dihydro-dioxazinylethyl, which can be possibly substituted by moieties from the group consisting of hydrogen, methyl, tert-butyl, trifluoromethyl, bromine, chlorine, fluorine, methoxy, 5 trifluoromethoxy, nitro, amino, methylamino, ethylamino, N methoxycarbonylamino, N-ethoxycarbonylamino, N-propyloxycarbonyl amino, N-isopropyloxycarbonyl-amino, N-tert-butyloxycarbonylamino, N propyleneoxycarbonylamino, N-methylsulphonylamino, N-ethylsulphonyl amino, N-methoxycarbonyl-N-methyl-amino, N-ethoxycarbonyl-N-methyl 10 amino, N-isopropyloxycarbonyl-N-methyl-amino, N-tert-butyloxycarbonyl-N methyl-amino, N-propyleneoxy-carbonyl-N-methylamino, N-cyclopropyl carbonylamino, N-1-methylcycloprop-1-yl-carbonyl-N-amino, N-methoxy carbonyl-N-methylsulphonyl-amino, N-methoxycarbonyl-N-ethyl sulphonylamino, N-isobutyloxycarbonyl-N-methyl-sulphonyl-amino, N-tert 15 butyloxycarbonyl-N-methylsulphonyl-amino, N-tert-butyloxycarbonyl-N methylsulphonyl-amino, N-propyleneoxycarbonyl-N-methylsulphonyl-amino, N-cyclopropylcarbonyl-N-methyl-sulphonyl-amino, N-1-methylcycloprop-1 yl-carbonyl-N-methyl-sulphonyl-amino, N,N-dialkylaminocarbonyl-amino, N-methylaminosulphonyl-amino and N,N-dialkylaminosulphonyl-amino. 20 A-B preferably stands for one of the following groups: -HC=CH- or -H 2
C-CH
2 -. According to the invention, the compounds according to formula () are preferred, in which a combination of the previously listed preferred substances occur. 25 According to the invention, the compounds according to formula (I) are particularly preferred, in which a combination of the previously listed particularly preferred substances occur.
-16 According to the invention, the compounds according to formula (I) are quite particularly preferred, in which a combination of the previously listed quite particularly preferred substances occur. 5 The 9-keto spinosyn derivatives according to the invention and their acid addition salts and metal complexes according to the general formula (I) possess strongly pronounced biological properties and are suitable first and foremost for controlling animal pests, in particular insects, arachnids and nematodes, which occur in the agricultural industry, forests, the areas of material and stock protection and in the 10 hygiene sector. The general definitions of moieties above and the preferred definitions of moieties or explanations apply to the end products, and to the initial and intermediate products respectively. These moieties can be combined with each other in any manner, i.e. 15 among the respective preferred substances. The 9-keto spinosyn derivatives according to the invention according to the general formula (I) and their salts can exist in stereoisomer forms, which either behave as an object and a mirror image of that object (enantiomers), or not as an object and a 20 mirror image of that object (diastereomers). The enantiomers and the diastereomers, and their corresponding mixtures are all subjects of the present invention. The racemic forms can be separated into stereomers with uniform components according to a known method, as can the diastereomers. If necessary, the isomers can be converted into one another using methods known in their own right. 25 However, the optically active, stereoisomer forms of the compounds according to the general formula (I) and their salts are preferably formed and utilised, according to the invention. 30 The invention therefore relates to both the pure enantiomers and diastereomers, and their mixtures for use as plant protection agents.
- 17 The compounds according to the invention, in which R' stands for an amino sugar shown in the formulae I a to If, and/or R3 stands for a basic moiety, can form salts. Suitable salts of the 9-keto spinosyn derivatives according to the general formula (I) 5 can be customary non-toxic salts, i.e. salts with various bases, and salts with additional acids. Examples of preferable salts are those with inorganic bases, such as alkali metal salts, for example sodium, potassium, or caesium salts, earth alkali metal salts, for example calcium or magnesium salts, ammonium salts, salts with organic bases as well as with inorganic amines, for example triethylammonium, 10 dicyclohexylammonium, N,N'-dibenzylethylenediammonium, pyridinium, picolinium or ethanol ammonium salts, salts with inorganic acids, for example hydrochlorides, hydrobromides, dihydrosulphates, trihydrosulphates, or phosphates, salts with organic carboxylic acids or organic sulphonic acids, for example formiates, acetates, trifluoroacetates, maleates, tartrates, methanesulphonates, 15 benzolsulphonates or para-toluene sulphonates, salts with basic amino acids, for example arginates, aspartates or glutamates, and similar salts. Salts are formed according to the standard method for salt production. For example, the compounds according to the invention are neutralised with corresponding acids, 20 in order to form acid addition salts. Representative usable acid addition salts are salts, which are formed, for example, through reaction with other inorganic acids, such as, for example, sulphuric acid, hydrochloric acid, hydrobromic acid, phosphoric acid, or organic carboxylic acids such as acetic acid, trifluoroacetic acid, citric acid, succinic acid, lactic acid, formic acid, maleic acid, camphoric acid, 25 phthalic acid, glycolic acid, glutaric acid, stearic acid, salicylic acid, sorbinic acid, cinnamic acid, picric acid, benzoic acid, or organic sulphonic acids such as methane sulphonic acids and para-toluene sulphonic acids, or with basic amino acids such as asparagine acid, glutaminic acid, arginine or similar acids. 30 Examples of the new 9-keto spinosyn derivatives according to the invention according to the general formula (I) are listed below in Groups 1 to 94: - 18 Group 1 R O 17 CH3 0 .-- No R2 21 x R3 H A--B H and derived salts, 5 Compounds of Group 1 correspond to the general formula (I), in which A-B stands for the group -HC=CH-, R' and R 3 stand for hydrogen, X stands for 0 and R 2 stands for a moiety listed in Table 1 as follows: Table 1 10 Comp. R2 Comp. R No. No. 1 4-NH 2 -phenyl-CH 2
-CH
2 - 36 4-Boc-NH-phenyl-CH 2
-CH
2 2 4-Cpr-CO-NH-phenyl-CH 2 - 37 4-Boc-NMe-phenyl-CH 2
-CH
2 CH 2 3 4-Cpr-CO-NMe-phenyl-CH 2 - 38 3-Boc-NH-phenyl-CH 2
-CH
2 CH 2 4 4-Cpr-CO-NEt-phenyl-CH 2 - 39 3-Boc-NMe-phenyl-CH 2
-CH
2 CH 2 5 3-NH 2 -phenyl-CH 2
-CH
2 - 40 4-iPrCO-NH-phenyl-CH 2
-CH
2 6 3-Cpr-CO-NH-phenyl-CH 2 - 41 4-iPrCO-NMe-phenyl-CH 2 CH 2 - CH 2 7 3-Cpr-CO-NMe-phenyl-CH 2 - 42 2-iPrCO-NH-phenyl-CH 2
-CH
2 CH 2
-
- 19 Comp. R 2 Comp. R 2 No. No. 8 3-Cpr-CO-NEt-phenyl-CH 2 - 43 2-iPrCO-NMe-phenyl-CH 2 CH 2 - CH 2 9 4-MCpr-CO-NH-phenyl-CH 2 - 44 4-MeOOC-NH-phenyl-CH 2 CH 2 - CH 2 10 4-MCpr-CO-NMe-phenyl-CH 2 - 45 4-MeOOC-NMe-phenyl-CH 2 CH 2 - CH 2 11 4-MCpr-CO-NEt-phenyl-CH 2 - 46 4-EtSO 2 -NH-phenyl-CH 2
-CH
2 CH 2 12 4-Ph-O-phenyl-CH 2
-CH
2 - 47 3-EtSO 2 -NH-phenyl-CH 2
-CH
2 13 4-MeSO 2 -NH-phenyl-CH 2 - 48 4-NH 2 -phenyl-CH(Me)
CH
2 14 3-MeS 0 2 -NH-phenyl-C1 2 - 49 3-NH 2 -phenyl-CH(Me)
CH
2 15 2-chloro-pyrid-5-yl-CH 2 - 50 4-NH 2 -phenyl-CH(Me)-CH 2 16 2-chloro-pyrid-5-yl-CH 2
-CH
2 - 51 3-NH 2 -phenyl-CH(Me)-CH 2 17 4-EtSO 2 -N(COOMe)-phenyl- 52 4-EtSO 2 -N(COOEt)-phenyl
CH
2
-CH
2 - CH 2
-CH
2 18 4-MeSO 2 -N(COOtBu)-phenyl- 53 4-MeSO 2 -N(COOiPr)-phenyl
CH
2
-CH
2 - CH 2
-CH
2 19 4-Me 2 NCO-NH-phenyl-CH 2 - 54 4-Me 2 NCO-NH-phenyl-CH 2 CH 2 20 4-H 2 C=CHOCO-NMe-phenyl- 55 4-H 2 C=CHOCO-NH-phenyl
CH
2
-CH
2 - CH 2
-CH
2 21 4-NC-CH 2 -CS-NH-phenyl- 56 4-NC-CH 2 -CO-NH-phenyl
CH
2
-CH
2 - CH 2
-CH
2 22 4-NC-CH 2 -CO-NMe-phenyl- 57 4-NC-CH 2
-CH
2 -CO-NMe
CH
2
-CH
2 - phenyl-CH 2
-CH
2
-
- 20 Comp. R 2 Comp. R 2 No. No. 23 4-Cbu-CO-NH-phenyl-CH 2 - 58 4-Cbu-CO-NMe-phenyl-CH 2 CH 2
-
CH
2 24 4-MeNHCO-NH-phenyl-CH 2 - 59 4-MeNHCS-NH-phenyl-CH 2 CH 2
-
CH
2 25 4-NC-CH 2
-CH
2 -O-CO-NEt- 60 4-NC-CH 2
-CH
2 -O-CO-NEt phenyl-CH 2
-CH
2
-
phenyl-CH 2
-CH
2 26 3-Br-pyrid-5-yi-CH 2 - 61 3-Br-pyrid-5-yl-CH 2
-CH
2 27 2-CI-thiazol-5-yl-CH 2 - 62 2-Cl-thiazol-5-yl-CHMe 28 4-Cbu-CO-N(S O 2 Me)-phenyl- 63 4-Cbu-CO-N(SO 2 Et)-phenyl
CH
2
-CH
2
-
CH
2
-CH
2 29 4-Cbu-CO-N(S O 2 Me)-phenyl- 64 4-ChxNHCO-NH-phenyl-CH 2 CH 2
-CH
2
-
C2 30 4-iPrCO-N(SO 2 Me)-phenyl- 65 4-iPrCO-N(SO 2 Et)-phenyl
CH
2
-CH
2
-
CH
2
-CH
2 31 4-sec-BuCO-NH-phenyl-CH 2 - 66 4-sec-BuCO-NMe-phenyl
CH
2
-
CH
2
-CH
2 32 4-MCpr-CO-N(SO 2 Me)- 67 4-MCpr-CO-N(SO 2 Et)-phenyl phenyl-CH 2
-CH
2
-
CH
2
-CH
2 33 4-MCpr-CO-N(COOMe)- 68 4-MCpr-CO-N(SO 2 iPr) phenyl-CH 2
-CH
2
-
phenyl-CH 2
-CH
2 34 4-MCpr-CO-N(COOiPr)- 69 4-MCpr-CO-N(COOPr) phenyl-CH 2
-CH
2
-
phenyl-CH 2
-CH
2 35 2-NH 2 -pyrid-5-yl-CH 2 - 70 2-CprNH-pyrid-5-yl-CH 2 Boc =tert-Butyloxycarbonyl, Cpr =Cyclopropyl, Cbu = Cyclobutyl, Chx Cyclohexyl, MCpr = I1-methyl-cycloprop-1I-yl, Ph = Phenyl 5 -21 Group 2 Compounds of Group 2 correspond to the general formula (I), in which A-B stands for the group -HC=C(CH 3 )-, R' and R 3 stand for hydrogen, X stands for 0 and R 2 has one of the meanings listed in Table 1. 5 Group 3 Compounds of Group 3 correspond to the general formula (I), in which A-B stands for the group -H 2
C-CH
2 -, R1 and R 3 stand for hydrogen, X stands for 0 and R 2 has one of the meanings listed in Table 1. 10 Group 4 Compounds of Group 4 correspond to the general formula (I), in which A-B stands for the group -H 2
C-CH(CH
3 )-, RI and R 3 stand for hydrogen, X stands for 0 and R 2 has one of the meanings listed in Table 1. 15 Group 5 Compounds of Group 5 correspond to the general formula (I), in which A-B stands for the group -HC=CH-, R' stands for hydrogen, R 3 stands for hydroxy, X stands for o and R2 has one of the meanings listed in Table 1. 20 Group 6 Compounds of Group 6 correspond to the general formula (I), in which A-B stands for the group -HC=C(CH 3 )-, R' stands for hydrogen, R 3 stands for hydroxy, X stands for 0 and R2 has one of the meanings listed in Table 1. 25 Group 7 Compounds of Group 7 correspond to the general formula (I), in which A-B stands for the group -H 2
C-CH
2 -, R' stands for hydrogen, R 3 stands for hydroxy, X stands for 0 and R2 has one of the meanings listed in Table 1. 30 - 22 Group 8 Compounds of Group 8 correspond to the general formula (I), in which A-B stands for the group -H 2
C-CH(CH
3 )-, R1 stands for hydrogen, R 3 stands for hydroxy, X stands for 0 and R 2 is one the compounds listed in Table 1. 5 Group 9 Compounds of Group 9 correspond to the general formula (I), in which A-B stands for the group -HC=CH-, R1 stands for an amino sugar shown in formula la Me Me Me N, Me S R R Me H la 10 R 3 stands for hydrogen, X stands for 0 and R 2 has one of the meanings listed in Table 1. Group 10 Compounds of Group 10 correspond to the general formula (1), in which A-B stands 15 for the group -HC=C(CH 3 )-, R' stands for an amino sugar shown in formula 1 a Me Me Me 2 N, Me R R Me H la R3 stands for hydrogen, X stands for 0 and R2 has one of the meanings listed in Table 1. 20 Group 11 Compounds of Group 11 correspond to the general formula (I), in which A-B stands for the group -H 2
C-CH
2 -, RI stands for an amino sugar shown in formula la -23 Me Me Me N, MeN oS R Me H la R3 stands for hydrogen, X stands for 0 and R2 has one of the meanings listed in Table 1. 5 Group 12 Compounds of Group 12 correspond to the general formula (I), in which A-B stands for the group -H 2
C-CH(CH
3 )-, RI stands for an amino sugar shown in formula 1 a Me Me Me N, 1 2 " RO Me S R Me H 1a R3 stands for hydrogen, X stands for 0 and R2 has one of the meanings listed in 10 Table 1. Group 13 Compounds of Group 13 correspond to the general formula (I), in which A-B stands for the group -HC=CH-, R' stands for an amino sugar shown in formula lb Me Me MeHN,,, HNI R 0 0 R Me H 15 1b
R
3 stands for hydrogen, X stands for 0 and R 2 has one of the meanings listed in Table 1. 20 - 24 Group 14 Compounds of Group 14 correspond to the general formula (I), in which A-B stands for the group -HC=C(CH 3 )-, RI stands for an amino sugar shown in formula lb Me Me MeHN,, HNIH, R 0 H N, SR o R Me H 1b 5 R3 stands for hydrogen, X stands for 0 and R2 has one of the meanings listed in Table 1. Group 15 Compounds of Group 15 correspond to the general formula (I), in which A-B stands 10 for the group -H 2
C-CH
2 -, R' stands for an amino sugar shown in formula lb Me Me MeHN,, R HN S:R o R Me H 1b R3 stands for hydrogen, X stands for 0 and R2 has one of the meanings listed in Table 1. 15 Group 16 Compounds of Group 16 correspond to the general formula (I), in which A-B stands for the group -H 2
C-CH(CH
3 )-, R' stands for an amino sugar shown in formula lb Me Me MeHN,, 0 H N SRR 0 R Me H 1b R3 stands for hydrogen, X stands for 0 and R2 has one of the meanings listed in 20 Table 1.
- 25 Group 17 Compounds of Group 17 correspond to the general formula (I), in which A-B stands for the group -HC=CH-, R' stands for an amino sugar shown in formula Ic Me H 2 N H 2N , S R 0 o R Me H 5 1c
R
3 stands for hydrogen, X stands for 0 and R 2 has one of the meanings shown in Table 1. Group 18 10 Compounds of Group 18 correspond to the general formula (I), in which A-B stands for the group -H 2
C-CH(CH
3 )-, R' stands for an amino sugar shown in formula Ic Me
H
2 N,- R 0 H N,/ S R Me H 1c
R
3 stands for hydrogen, X stands for 0 and R 2 has one of the meanings listed in Table 1. 15 Group 19 Compounds of Group 19 correspond to the general formula (I), in which A-B stands for the group -H 2
C-CH
2 -, R' stands for an amino sugar shown in formula lc Me
H
2 N,, -, R0 H2N H2N,''S RR Me H 1c -26
R
3 stands for hydrogen, X stands for 0 and R 2 has one of the meanings listed in Table 1. Group 20 5 Compounds of Group 20 correspond to the general formula (I), in which A-B stands for the group -H 2
C-CH(CH
3 )-, RI stands for an amino sugar shown in formula Ic Me H N,,,
H
2 N 2N, S R R 2
-
R Me H 1c R3 stands for hydrogen, X stands for 0 and R2 has one of the meanings listed in Table 1. 10 Group 21 Compounds of Group 21 correspond to the general formula (I), in which A-B stands for a group -HC=CH-, RI stands for an amino sugar shown in formula 1 d Me Me o O Me 2 N 0 S R Me Me 2 N Me 1d 15 R3 stands for hydrogen, X stands for 0 and R2 has one of the meanings listed in Table 1. Group 22 Compounds of Group 22 correspond to the general formula (I), in which A-B stands 20 for the group -HC=C(CH 3 )-, R' stands-for an amino sugar shown in formula Id - 27 Me Me 0 0 2 RS Me2N R .S R, Me Me 2 N Me 1d R3 stands for hydrogen, X stands for 0 and R 2 has one of the meanings listed in Table 1. 5 Group 23 Compounds of Group 23 correspond to the general formula (I), in which A-B stands for the group -H 2
C-CH
2 -, R 1 stands for an amino sugar shown in formula 1 d Mes Me 0 H M e2N
-
S = .S R~ Me Me2N'' 'Me 1d
R
3 stands for hydrogen, X stands for 0 and R 2 has one of the meanings listed in 10 Table 1. Group 24 Compounds of Group 24 correspond to the general formula (I), in which A-B stands for the group -H 2
C-CH(CH
3 )-, R 1 stands for an amino sugar shown in formula Id Me Me S0 H 0 0 Me2N 0RS O .NSRO Me Me2N Me 15 1d -28 R3 stands for hydrogen, X stands for 0 and R2 has one of the meanings listed in Table 1. Group 25 5 Compounds of Group 25 correspond to the general formula (I), in which A-B stands for the group -HC=CH-, R stands for an amino sugar shown in formula le H OH HO RS Me2N Z S R, Me Me 2 N Me 1e R3 stands for hydrogen, X stands for 0 and R2 has one of the meanings listed in Table 1. 10 Group 26 Compounds of Group 26 correspond to the general formula (I), in which A-B stands for the group -HC=C(CH 3 )-, R stands for an amino sugar shown in formula le H OH HO Me 2 N RS __O R Me Me 2 N Me le 15 R3 stands for hydrogen, X stands for 0 and R2 has one of the meanings listed in Table 1. Group 27 Compounds of Group 27 correspond to the general formula (1), in which A-B stands 20 for the group -H 2
C-CH
2 -, R' stands for an amino sugar shown in formula le - 29 H OH HO Me2 _R S O SS R, Me Me 2 N 'Me 1e R3 stands for hydrogen, X stands for 0 and R2 has one of the meanings listed in Table 1. 5 Group 28 Compounds of Group 28 correspond to the general formula (I), in which A-B stands for the group -H 2
C-CH(CH
3 )-, R' stands for an amino sugar shown in formula le H OH HO RS OS R, Me Me 2 N Me 1e R3 stands for hydrogen, X stands for 0 and R2 has one of the meanings listed in 10 Table 1. Group 29 Compounds of Group 29 correspond to the general formula (I), in which A-B stands for the group -HC=CH-, R' stands for an amino sugar shown in formula If O=< 3 O CH 3 H O 0 Me 2 N RS O 7T:: , S R," Me Me 2 N , Me 15 1f R3 stands for hydrogen, X stands for 0 and R2 has one of the meanings listed in Table 1.
- 30 Group 30 Compounds of Group 30 correspond to the general formula (I), in which A-B stands for the group -HC=C(CH 3 )-, R' stands for an amino sugar shown in formula If O H 3 O
CH
3 O O Me2N-' R S RO zi~o S R," Me Me 2 N Me 1f 5 R 3 stands for hydrogen, X stands for O and R 2 has one of the meanings listed in Table 1. Group 31 Compounds of Group 31 correspond to the general formula (I), in which A-B stands 10 for the group -H 2
C-CH
2 -, R' stands for an amino sugar shown in formula If CH Me2N o O R S O ,S R. Me Me2N Me 1f R3 stands for hydrogen, X stands for 0 and R2 has one of the meanings listed in Table 1. 15 Group 32 Compounds of Group 32 correspond to the general formula (I), in which A-B stands for the group -H 2
C-CH(CH
3 )-, R' stands for an amino sugar shown in formula If O= 3 O CH3 H Me 2 N O O RS Me Me 2 N Me if -31 R3 stands for hydrogen, X stands for 0 and R2 has one of the meanings listed in Table 1. Group 33 5 Compounds of Group 33 correspond to the general formula (I), in which A-B stands for the group -HC=CH-, R' stands for an amino sugar shown in formula Ig o Me M Me-+ Me Me sRO Me 0 - R Me H 1g R3 stands for hydrogen, X stands for 0 and R2 has one of the meanings listed in Table 1. 10 Group 34 Compounds of Group 34 correspond to the general formula (I), in which A-B stands for the group -HC=C(CH 3 )-, R' stands for an amino sugar shown in formula lg o Me O- Me- Me /N+ Me S R Me 0O Me H 1g 15 R 3 stands for hydrogen, X stands for 0 and R 2 has one of the meanings listed in Table 1. Group 35 Compounds of Group 35 correspond to the general formula (I), in which A-B stands 20 for the group -H 2
C-CH
2 -, R 1 stands for an amino sugar shown in formula lg - 32 0 Me 0- Me- + Me'N Me sRO Me 0 R Me H 1g R3 stands for hydrogen, X stands for 0 and R2 has one of the meanings listed in Table 1. 5 Group 36 Compounds of Group 36 correspond to the general formula (I), in which A-B stands for the group -H 2
C-CH(CH
3 )-, R 1 stands for an amino sugar shown in formula Ig o Me O Me + RO Me 0 Me R Me H 1g
R
3 stands for hydrogen, X stands for O and R 2 has one of the meanings listed in 10 Table 1. Group 37 17 CH3 O HH N 2 21 x 3 H (I) and derived salts, 15 Compounds of Group 37 correspond to the general formula (I), in which A-B stands for the group -HC=CH-, Rand R 3 stand for hydrogen, X stands for NH and R2 stands for a moiety as listed in Table 2 below: - 33 Table 2 Comp. R 2 Comp. R 2 No. No. 4-NH 2 -phenyl-CH 2
-CH
2 - 17 H 2 N-CS 2 4-Cpr-CO-NH-phenyl-CH 2 - 18 Me-HN-CS
CH
2 3 4-Cpr-CO-NMe-phenyl-CH 2 - 19 4-CF 3 O-phenyl-NH-CO
CH
2 4 4-Cpr-CO-NEt-phenyl-CH 2 - 20 4-CF 3 -phenyl-NH-CO
CH
2 5 3-NH 2 -phenyl-CH 2
-CH
2 - 21 4-CI-phenyl-NH-CO 6 3-Cpr-CO-NH-phenyl-CH 2 -' 22 3-CF 3 O-phenyl-NH-CO
CH
2 7 4-Cbu-CO-NMe-phenyl-CH 2 - 23 3-CF 3 -phenyl-NH-CO
CH
2 8 3-Cpr-CO-NEt-phenyl-CH 2 - 24 2-chloro-pyrid-5-yl-CHMe
CH
2 9 4-MCpr-CO-NH-phenyl-CH 2 - 25 4-Boc-NH-phenyl-CH 2
-CH
2 CH 2 10 4-MCpr-CO-NMe-phenyl- 26 4-Boc-NMe-phenyl-CH 2 -C1 2 CH 2
-CH
2 11 4-MCpr-CO-NEt-phenyl-CH 2 - 27 3-Boc-NH-phenyl-CH 2
-CH
2 CH 2 12 4-Ph-O-phenyl-CH 2
-CH
2 - 28 3-Boc-NMe-phenyl-CH 2
-CH
2 13 4-MeSO 2 -NH-phenyl-CH 2 - 29 4-iPrCO-NH-phenyl-CH 2
-CH
2 CH 2
-
__ 14 3-MeS 0 2 -NH-phenyl-CH 2 - 30 4-iPrCO-NMe-phenyl-CH 2 CH 2
-
CH
2 15 2-chloro-pyrid-5-yl-CH 2 - 31 4-iPrCO-NH-phenyl-CH 2 16 2-chloro-pyrid-5-yl-CH 2
-CH
2 - 33 4-iPrCO-NMe-phenyl-CH 2 Boc =ter-t-Butyloxycarbonyl, Cpr = Cyclopropyl, Cbu = Cyclobutyl, MCpr =1 methyl-cycloprop-1-yl, Ph = Phenyl - 34 Group 38 Compounds of Group 38 correspond to the general formula (I), in which A-B stands for the group -HC=C(CH 3 )-, R' and R 3 stand for hydrogen, X stands for NH and R 2 5 has one of the meanings listed in Table 2. Group 39 Compounds of Group 39 correspond to the general formula (I), in which A-B stands for the group -H 2 C-CH2-, R' and R 3 stand for hydrogen, X stands for NH and R2 has 10 one of the meanings listed in Table 2. Group 40 Compounds of Group 40 correspond to the general formula (I), in which A-B stands for the group -H 2
C-CH(CH
3 )-, R' and R 3 stand for hydrogen, X stands for NH and R 2 15 has one of the meanings listed in Table 2. Group 41 Compounds of Group 41 correspond to the general formula (I), in which A-B stands for the group -HC=CH-, R' and R 3 stand for hydrogen, X stands for NEt and R2 has 20 one of the meanings listed in Table 2. Group 42 Compounds of Group 42 correspond to the general formula (I), in which A-B stands for the group -HC=C(CH 3 )-, RI and R3 stand for hydrogen, X stands for NEt and R2 25 has one of the meanings listed in Table 2. Group 43 Compounds of Group 43 correspond to the general formula (I), in which A-B stands for the group -H 2
C-CH
2 -, R' and R3 stand for hydrogen, X stands for NEt and R2 has 30 one of the meanings listed in Table 2.
- 35 Group 44 Compounds of Group 44 correspond to the general formula (I), in which A-B stands for the group -H 2
C-CH(CH
3 )-, R' stands for hydrogen, R 3 stands for hydroxy, X stands for NEt and R 2 has one of the meanings listed in Table 2. 5 Group 45 Compounds of Group 45 correspond to the general formula (I), in which A-B stands for the group -HC=CH-, R' stands for an amino sugar shown in formula I a Me Me Me2N, I R" RO MeN S RR Me H 1a 10 R3 stands for hydrogen, X stands for NH and R2 has one of the meanings listed in Table 2. Group 46 Compounds of Group 46 correspond to the general formula (I), in which A-B stands 15 for the group -HC=C(CH 3 )-, R stands for an amino sugar shown in formula la Me Me MeN,, I R MeNN SRR Me H 1a R3 stands for hydrogen, X stands for NH and R2 has one of the meanings listed in Table 2. 20 Group 47 Compounds of Group 47 correspond to the general formula (I), in which A-B stands for the group -H 2
C-CH
2 -, R1 stands for an amino sugar shown in formula Ia - 36 Me Me Me2N,, I 2" RO MeN R R Me H 1a R3 stands for hydrogen, X stands for NH and R2 has one of the meanings listed in Table 2. 5 Group 48 Compounds of Group 48 correspond to the general formula (I), in which A-B stands for the group -H 2
C-CH(CH
3 )-, R1 stands for an amino sugar shown in formula la Me Me Me2N,, MeN R Me H 1a R3 stands for hydrogen, X stands for NH and R2 has one of the meanings listed in 10 Table 2. Group 49 Compounds of Group 49 correspond to the general formula (I), in which A-B stands for the group -HC=CH-, R1 stands for an amino sugar shown in formula lb Me Me MeHN,, HN SRR Me H 15 lb R3 stands for hydrogen, X stands for NH and R2 has one of the meanings listed in Table 2.
- 37 Group 50 Compounds of Group 50 correspond to the general formula (I), in which A-B stands for the group -HC=C(CH 3 )-, R' stands for an amino sugar shown in formula lb Me Me MeHN,, I sR H N SRR Me H lb 5 R 3 stands for hydrogen, X stands for NH and R 2 has one of the meanings listed in Table 2. Group 51 Compounds of Group 51 correspond to the general formula (I), in which A-B stands 10 for the group -H 2
C-CH
2 -, R' stands for an amino sugar shown in formula lb Me Me MeHN,, R I (: R H NJ S RR Me H 1b
R
3 stands for hydrogen, X stands for NH and R 2 has one of the meanings listed in Table 2. 15 Group 52 Compounds of Group 52 correspond to the general formula (I), in which A-B stands for the group -H 2
C-CH(CH
3 )-, R' stands for an amino sugar shown in formula lb Me Me MeHN,, HNS: R R Me H 1b R3 stands for hydrogen, X stands for NH and R2 has one of the meanings listed in 20 Table 2.
- 38 Group 53 Compounds of Group 53 correspond to the general formula (I), in which A-B stands for the group -HC=CH-, R' stands for an amino sugar shown in formula ic Me
H
2 N H2N, RO o RI Me H 5 1C R3 stands for hydrogen, X stands for NH and R2 has one of the meanings listed in Table 2. Group 54 10 Compounds of Group 54 correspond to the general formula (I), in which A-B stands for the group -H 2
C-CH(CH
3 )-, R I stands for an amino sugar shown in formula Ic Me 2HN H R Me H 1C R3 stands for hydrogen, X stands for NH and R2 has one of the meanings listed in Table 2. 15 Group 55 Compounds of Group 55 correspond to the general formula (I), in which A-B stands for the group -HC=CH-, R' stands for an amino sugar shown in formula Id - 39 Me Me 0 0 O U M e 2 N R - R , 7 O 'S R Me Me 2 N Me 1d
R
3 stands for hydrogen, X stands for NH and R 2 has one of the meanings listed in Table 2. 5 Group 56 Compounds of Group 56 correspond to the general formula (I), in which A-B stands for the group -HC=C(CH 3 )-, R' stands for an amino sugar shown in formula Id Me Me
O
0 Me 2 N R S S R Me Me 2 N Me 1d
R
3 stands for hydrogen, X stands for NH and R 2 has one of the meanings listed in 10 Table 2. Group 57 Compounds of Group 57 correspond to the general formula (I), in which A-B stands for the group -H 2
C-CH
2 -, RI stands for an amino sugar shown in formula Id Me Me O H 0 o Me20N R S 0 SR Me Me 2 N %'Me 15 1d - 40 R 3 stands for hydrogen, X stands for NH and R 2 has one of the meanings listed in Table 2. Group 58 5 Compounds of Group 58 correspond to the general formula (I), in which A-B stands for the group -H 2
C-CH(CH
3 )-, R' stands for an amino sugar shown in formula Id Me Me O 00 0 0 Me2N- R CR 11- --- RSO0 zo S R, Me Me 2 N Me 1d R3 stands for hydrogen, X stands for NH and R2 has one of the meanings listed in Table 2. 10 Group 59 Compounds of Group 59 correspond to the general formula (I), in which A-B stands for the group -HC=CH-, R stands for an amino sugar shown in formula le H OH HO M e2 N RS RO Me Me 2 N 'Me le 15 R3 stands for hydrogen, X stands for NH and R2 has one of the meanings listed in Table 2. Group 60 Compounds of Group 60 correspond to the general formula (I), in which A-B stands 20 for the group -HC=C(CH 3 )-, R' stands for an amino sugar shown in formula le -41 H Me N OH HO Me 2 --- R S O 0 ,S R . Me Me 2 N R Me le R3 stands for hydrogen, X stands for NH and R 2 has one of the meanings listed in Table 2. 5 Group 61 Compounds of Group 61 correspond to the general formula (I), in which A-B stands for the group -H 2
C-CH
2 -, R' stands for an amino sugar shown in formula le H OH HO 2 N- RS O Me Me 2 N Me 1e
R
3 stands for hydrogen, X stands for NH and R 2 has one of the meanings listed in 10 Table 2. Group 62 Compounds of Group 62 correspond to the general formula (I), in which A-B stands for the group -H 2
C-CH(CH
3 )-, R' stands for an amino sugar shown in formula le H OH HO Me2N -RS O O;--- , S R, Me Me 2N" 'Me 15 1e R3 stands for hydrogen, X stands for NH and R2 has one of the meanings listed in Table 2.
-42 Group 63 Compounds of Group 63 correspond to the general formula (I), in which A-B stands for the group -HC=CH-, R1 stands for an amino sugar shown in formula lf O H 3 O CH3 o 6 Me2N
--
C SOR '1'o.S R, Me Me2N Me 1f 5 R3 stands for hydrogen, X stands for NH and R 2 has one of the meanings listed in Table 2. Group 64 Compounds of Group 64 correspond to the general formula (I), in which A-B stands 10 for the group -HC=C(CH 3 )-, R stands for an amino sugar shown in formula If O (CH0 CH O H 3 O CH, Me2N 0 R S Me Me 2 N 'Me 1f
R
3 stands for hydrogen, X stands for NH and R 2 has one of the meanings listed in Table 2. 15 Group 65 Compounds of Group 65 correspond to the general formula (I), in which A-B stands for the group -HC=CH-, R' stands for an amino sugar shown in formula Ig 0 Me 0 Me4+ Me4+ Me/ 'sR O MeOMe R MeM Me H 1g - 43 343 R3 stands for hydrogen, X stands for NH and R 2 has one of the meanings listed in Table 2. Group 66 5 Compounds of Group 66 correspond to the general formula (I), in which A-B stands for the group -HC=CH-, R I and R 3 stand for hydrogen, X stands for NMe and R 2 has one of the meanings listed in Table 2. Group 67 10 Compounds of Group 67 correspond to the general formula (I), in which A-B stands for the group -HC=C(CH 3 )-, R' and R3 stand for hydrogen, X stands for NMe and R2 has one of the meanings listed in Table 2. Group 68 15 Compounds of Group 68 correspond to the general formula (I), in which A-B stands for the group -H 2
C-CH
2 -, R1 and R3 stand for hydrogen, X stands for NMe and R2 has one of the meanings listed in Table 2. Group 69 20 Compounds of Group 69 correspond to the general formula (I), in which A-B stands for the group -H 2
C-CH(CH
3 )-, R' and R 3 stand for hydrogen, X stands for NMe and R2 has one of the meanings listed in Table 2. Group 70 25 Compounds of Group 70 correspond to the general formula (I), in which A-B stands for the group -HC=CH-, R' stands for hydrogen, R 3 stands for hydroxy, X stands for NMe and R 2 has one of the meanings listed in Table 2.
-44 Group 71 Compounds of Group 70 correspond to the general formula (I), in which A-B stands for the group -HC=C(CH 3 )-, R' stands for hydrogen, R 3 stands for hydroxy, X stands for NMe and R2 has one of the meanings listed in Table 2. 5 Group 72 Compounds of Group 72 correspond to the general formula (I), in which A-B stands for the group -H 2
C-CH
2 -, RI stands for hydrogen, R 3 stands for hydroxy, X stands for NMe and R2 has one of the meanings listed in Table 2. 10 Group 73 Compounds of Group 73 correspond to the general formula (I), in which A-B stands for the group -H 2
C-CH(CH
3 )-, R' stands for hydrogen, R 3 stands for hydroxy, X stands for NMe and R 2 has one of the meanings listed in Table 2. 15 Group 74 Compounds of Group 74 correspond to the general formula (I), in which A-B stands for the group -HC=CH-, R' stands for an amino sugar shown in formula l a Me Me Me2N,, MeN S R Me H la 20 R3 stands for hydrogen, X stands for NMe and R2 has one of the meanings listed in Table 2. Group 75 Compounds of Group 75 correspond to the general formula (I), in which A-B stands 25 for the group -HC=C(CH 3 )-, R' stands for an amino sugar shown in formula la -45 Me Me Me 2 N,, M N SR R Me H 1a R3 stands for hydrogen, X stands for NMe and R2 has one of the meanings listed in Table 2. 5 Group 76 Compounds of Group 76 correspond to the general formula (I), in which A-B stands for the group -H2C-CH 2 -, R I stands for an amino sugar shown in formula la Me Me Me2N,, MeN R Me H la R3 stands for hydrogen, X stands for NMe and R2 has one of the meanings listed in 10 Table 2. Group 77 Compounds of Group 74 correspond to the general formula (I), in which A-B stands for the group -H 2
C-CH(CH
3 )-, R' stands for an amino sugar shown in formula la Me Me MezN,, S MeN S R Me H 15 la R3 stands for hydrogen, X stands for NMe and R2 has one of the meanings listed in Table 2.
- 46 Group 78 Compounds of Group 78 correspond to the general formula (I), in which A-B stands for the group -HC=CH-, RI stands for an amino sugar shown in formula lb Me Me MeHN,, O H N ,_ _ S o R Me H lb 5 R3 stands for hydrogen, X stands for NMe and R2 has one of the meanings listed in Table 2. Grout 79 Compounds of Group 79 correspond to the general formula (I), in which A-B stands 10 for the group -HC=C(CH 3 )-, R' stands for an amino sugar shown in formula lb Me Me MeHN,, R HN -S RR Me H 1 b
R
3 stands for hydrogen, X stands for NMe and R 2 has one of the meanings listed in Table 2. 15 Group 80 Compounds of Group 80 correspond to the general formula (I), in which A-B stands for the group -H 2
C-CH
2 -, R' stands for an amino sugar shown in formula lb Me Me MeHN,, R I R HN S'RIR Me H 1 b
R
3 stands for hydrogen, X stands for NMe and R 2 has one of the meanings listed in 20 Table 2.
-47 Group 81 Compounds of Group 81 correspond to the general formula (I), in which A-B stands for the group -H 2
C-CH(CH
3 )-, R' stands for an amino sugar shown in formula lb Me Me MeHN,, HN sR R Me H 5 1b R3 stands for hydrogen, X stands for NMe and R 2 has one of the meanings listed in Table 2. Group 82 10 Compounds of Group 82 correspond to the general formula (I), in which A-B stands for the group -HC=CH-, R stands for an amino sugar shown in formula le Me H HN, S R O Me H 1c
R
3 stands for hydrogen, X stands for NMe and R2 has one of the meanings listed in Table 2. 15 Group 83 Compounds of Group 83 correspond to the general formula (I), in which A-B stands for the group -H 2
C-CH(CH
3 )-, R stands for an amino sugar shown in formula lc Me
H
2 N H - R Me H 1c - 48 R3 stands for hydrogen, X stands for NMe and R 2 has one of the meanings listed in Table 2. Group 84 5 Compounds of Group 84 correspond to the general formula (I), in which A-B stands for the group -HC=CH-, R' stands for an amino sugar shown in formula Id Mex Me 0H O0 0 Me 2 N R S0 7- -- O S R, Me Me 2 N 'Me 1d R3 stands for hydrogen, X stands for NMe and R2 has one of the meanings listed in Table 2. 10 Group 85 Compounds of Group 85 correspond to the general formula (I), in which A-B stands for the group -HC=C(CH 3 )-, R' stands for an amino sugar shown in formula 1 d Me Me 0 0 Me2N 0 R S R SR Me Me 2 N 'Me 1d 15 R3 stands for hydrogen, X stands for NMe and R2 has one of the meanings listed in Table 2. Group 86 Compounds of Group 86 correspond to the general formula (I), in which A-B stands 20 for the group -H 2
C-CH
2 -, R' stands for an amino sugar shown in formula Id -49 Me Me 0 H
O
0 0 Me 2 N R .RSO0 O .S R , Me Me 2 N Me 1d
R
3 stands for hydrogen, X stands for NMe and R 2 has one of the meanings listed in Table 2. 5 Group 87 Compounds of Group 87 correspond to the general formula (I), in which A-B stands for the group -H 2
C-CH(CH
3 )-, R' stands for an amino sugar shown in formula Id Me Me 0 0 Me 2 N R S R 7; O ,S R,"' Me Me 2 N Me 1d R3 stands for hydrogen, X stands for NMe and R2 has one of the meanings listed in 10 Table 2. Group 88 Compounds of Group 88 correspond to the general formula (), in which A-B stands for the group -HC=CH-, R' stands for an amino sugar shown in formula le H OH HO Me2N- R S O 47ZZO S R Me Me 2 N Me 15 1e
R
3 stands for hydrogen, X stands for NMe and R2 has one of the meanings listed in Table 2.
-50 Group 89 Compounds of Group 89 correspond to the general formula (I), in which A-B stands for the group -HC=C(CH 3 )-, R' stands for an amino sugar shown in formula le H OH HO M e 2 R S R ~S R, Me Me2N 'Me 5 le
R
3 stands for hydrogen, X stands for NMe and R 2 has one of the meanings listed in Table 2. Group 90 10 Compounds of Group 90 correspond to the general formula (I), in which A-B stands for the group -H 2
C-CH
2 -, R stands for an amino sugar shown in formula le H OH HO Me2NR S RO ,S R Me Me2N" Me le R3 stands for hydrogen, X stands for NMe and R 2 has one of the meanings listed in Table 2. 15 Group 91 Compounds of Group 91 correspond to the general formula (I), in which A-B stands for the group -H 2
C-CH(CH
3 )-, R stands for an amino sugar shown in formula le H OH HO Me 2 N R S RC Me Me2N 'Me le -51 R3 stands for hydrogen, X stands for NMe and R2 has one of the meanings listed in Table 2. Group 92 5 Compounds of Group 92 correspond to the general formula (I), in which A-B stands for the group -HC=CH-, R' stands for an amino sugar shown in formula If CH O 0 Me2N
-
RS O Oi --- , S R, Me Me 2 N Me 1f
R
3 stands for hydrogen, X stands for NMe and R 2 has one of the meanings listed in Table 2. 10 Group 93 Compounds of Group 93 correspond to the general formula (I), in which A-B stands for the group -HC=C(CH 3 )-, R' stands for an amino sugar shown in formula If O<CH0 CH O 3 OzCH 3 H O O Me2N R S RC *S R, Me Me2N 'Me 1f 15 R3 stands for hydrogen, X stands for NMe and R2 has one of the meanings listed in Table 2. Group 94 Compounds of Group 94 correspond to the general formula (I), in which A-B stands 20 for the group -HC=CH-, R' stands for an amino sugar shown in formula ig -52 0 Me Me 4 Me 4 Me 's RRO M e & =R Me H 1g
R
3 stands for hydrogen, X stands for NMe and R 2 has one of the meanings listed in Table 2. 5 Another subject of the present invention is a method for the manufacture of the new 9-keto spinosyn derivatives according to the general formula (I), 1x 17 CH3 O HH N 2 HC 21 0 -- R (I) and derived salts, 10 where R', R 2 , R 3 , X and A-B have the meanings indicated previously, in which 15 the 9-keto spinosyn derivatives according to the general formula (II) -53 R 0 17 CH 3 3H H 3 OZ R 3 H H A-B H (II) where 5 RI, R 3 and A-B have the meanings indicated previously, are reacted with amino compounds according to the general formula (III)
H
2
N-X-R
2 (11I) 10 where R2 and X have the meanings indicated previously, in the presence of a basic additive and possibly in the presence of a diluent. 15 Methods for the introduction of possibly substituted imino functions are sufficiently known from literature (see A. Lachman, Org. Synth., Coll. Vol. II, 1943, p. 70; W. L. Semon, Org. Synth., Coll. Vol. 1, 1941, p. 318; Houben-Weyl, Methoden der Organischen Chemie (Methods of Organic Chemistry), Bd. X/4, G. Thieme Verlag, 20 Stuttgart New York, p. 55). It was then surprisingly found that the new 9-keto spinosyn derivatives according the the invention according to the general formula (I) could also be obtained via carbonyl reaction from corresponding 9-keto spinosyn derivatives with amino compounds 25 according to the general formula (III).
- 54 In the following section, the method according to the invention will be explained on the basis of selected examples (also see Examples of Manufacture). 5 If 9-keto spinosyn A-aglycone (R' = -H, R3 = -H, A-B = -HC=CH-) is utilised as a compound according to the general formula (II) and O-(4-phenoxy-benzyl) hydroxylamine (X = 0, R2: -CH 2
-C
6
H
4 -0-C 6 H5) is utilised as a compound according to the general formula (III) for the manufacture of the new 9-keto spinosyn derivatives according to the general formula (I) according to the invention-related 10 method, the method can be shown by the following reaction diagram in Figure 1: Figure 1 OH -CH 3 17
H
2 N, O H H O 2'O H 3C 22100 O ,Base OH -CH 3 17 H3I210 (E)-Isomer (anti) 0H H 173 0+ 3 N (Z)-Isomer (syn) H H 'H If 17--desosaminyl-9-keto spinosyn A-aglycone (R = D-desosaminyl, R 3 = -H, A-B = -HC=CH-) is utilised as a compound according to the general formula (II) and -55 O-(4-amino-benzyl)-hydroxylamine (X = 0, R 2: -CH 2
-C
6
H
4
-NH
2 ) is utilised as a compound according to the general formula (III) in another embodiment of the method according to the invention for the manufacture of the new 9-keto spinosyn derivatives according to the general formula (I), the method can be shown by the 5 following reaction diagram in Figure 2: Figure 2 OH (CHC3)2N H 3C : CH3 O g O H2, NH HO Base H --- H OH (CH3A2N0 H 3C CH3 17 3 (E)-Isomer (synt) OHH O o H H (Z)-asmer (syn) 1021 HH HI ~~- (Ia) ca ocu(aE ixue fte E-somer (antifr)ad()ioe snfr). 100 -56 If 9-keto spinosyn A-aglycone (R1 = -H, R3 = -H, A-B = -HC=CH-) is utilised as a compound according to the general formula (II) and N-(4-trifluoromethoxy-phenyl semicarbazide (X = NH, R2 = -CO-NH-C 6
H
4
-OCF
3 ) is utilised as a compound according to the general formula (III) in another embodiment of the method 5 according to the invention for the manufacture of the new 9-keto spinosyn derivatives according to the general formula (I), the method can be shown by the following reaction diagram in Figure 3: Figure 3 10 OH - CH 3 H 17 1 H HHH2,N NN HC 3 O 2 Base H H'
--
OH 17 CH 3 CF3 3 H H (E)-Isomer (anti) OHCF O N (Z)-Isomer (syn) 3C H H H - 57 With the use of the amino compounds according to the general formula (UI) in the method according to the invention, the compounds according to the general formula (Ia) can occur as a mixture of the (E)-isomer (anti form) and (Z)-isomer (syn form). 5 The 9-keto spinosyn derivatives required as initial substances for performing the method according to the invention are generally defined by formula (H). In formula (H), R' and A-B preferably stand for the moieties, which were already mentioned in conjunction with the description of the compounds according to the 10 invention according to the general formula (I), as being preferred for this substituent or the group. The 9-keto spinosyn derivatives according to the general formula (H) used as initial substances, where R3 stands for hydrogen, are known from a previous patent, and can 15 be respectively obtained via selective oxidation using chemical and biochemical methods (see WO 02/079184). The 9-keto spinosyn derivatives according to the general formula (H) used as initial substances, in which R 3 stands for hydroxy, can be obtained via selective and/or 20 stereospecific hydroxylation, for example, i.e. by way of bioconversion using suitable microorganisms or their enzymes. In particular, compounds according to the general formula (Ha) 17 CH3 25C 21 0H 25C OHr 20 0 H H A'B H 25OH (1Ha) - 58 where A-B and R' have the meanings indicated above, 5 can be obtained by bringing compounds according to the general formula (fib) (fib 7 CH3 H37 CH 00 H H A-B H (1b 10 where A-B and R 1 have the meanings indicated above, into contact with a microorganism in an aqueous culture medium under aerobic 15 conditions. The compounds according to the general formula (fIb) are known (see Creemer L. C. et al., 1998, J. Antibiotics 51 (8): 795-800; Sparks T. C. et al., 1998, J. Econ. Entomol. 91 (6): 1277-1283; Sparks T. C. et al., 2000, Pestic. Biochem. Physiol. 67 20 (3): 187-197; Paquette L. A. et al., 1998, J. Am. Chem. Soc. 120 (11): 2553-2563; Evans D. A. et al., 1993, J. Am. Chem. Soc. 115 (11): 4497-4513; Crouse G. D. et al., 2001, Pest. Manag. Sci. 57 (2): 177-185; Creemer L. C. et al., 2000, J. Antibiotics 53 (2): 171-178; Sparks T. C. et al., 2000, Proc.-Beltwide Cotton Conf. Vol. 2: 1225 1229) or can be produced according to the method described in WO 01/16303. In a 25 similar manner, the initial compounds to be used in the method described above can -59 be obtained on the basis of the corresponding natural spinosyns (see PCT/EPO2/07572). For example, one of the following strains can be used for this method, which are on 5 deposit at the Deutsche Sammlung von Mikroorganismen und Zellkulturen GmbH (DSMZ) (German Collection of Microorgansims and Cell Cultures), Mascheroder Weg lb, D-38124 Braunschweig, Germany, in accordance with the requirements of the Budapest Treaty: 10 Name Deposit Number Streptomyces djakartensis DSM 14327 Streptomyces griseofuscus DSM 14330 Streptomyces caelestis DSM 14328 Streptomyces antibioticus DSM 14329 Streptomyces griseus DSM 14331 Streptomyces aureofaciens DSM 14332 The aqueous culture medium typically contains an assimilable carbon source and an assimilable nitrogen source. 15 The compounds according to formula (Ha) are produced, for example, when one of the following strains are fermented in an aqueous culture medium under aerobic conditions in the presence of compounds according to formula (I1b): Streptomyces djakartensis, S. griseofuscus, S. caelestis, S. antibioticus, S. griseus or S. aureofaciens. The microorganisms are typically fermented in a culture medium, 20 which contains a carbon source and possibly a protein-like material. Preferred carbon sources include glucose, brown sugar, saccharose, glycerine, starch, cornstarch, lactose, dextrin, molasses, etc. Preferred nitrogen sources include cottonseed flour, yeast, autolysed bakers yeast, solid milk components, soybean flour, maize flour, -60 pancreatic or papain digested decomposition products from casein, solid distillation components, stocks from animal peptone, pieces of meat and pieces of bone, etc. Preferably combinations of these carbon sources and nitrogen sources are used. Trace elements, e.g. zinc, magnesium, manganese, cobalt, iron, etc., do not have to be 5 added to the cultivation medium, as long as tap water and unpurified components are used as components in the medium. The production of the compounds according to the general formula (Ha) can be induced at any temperature that guarantees sufficient growth of the microorganisms. 10 The temperature is preferably between 21'C and 32'C, particularly preferably approximately 28'C. In general, optimal production of the compounds according to formula (Ila) is obtained from 2 to 4 days after the compounds according to formula (Ilb) are added to the culture. The production of the compounds according to the invention can take place both in shake flasks and in stirred fermentors. 15 Various methods can be used in order to isolate the compounds from the fermentation broth and to purify them, e.g. preparative gel chromatography, reversed phase preparative chromatography or preparative absorption chromatography. Detection can occur using UV-absorption or mass spectrometry, for example. 20 Compounds according to the general formula (H), in which R' stands for an amino sugar shown in formula ld or le, and R 3 and A-B have the meanings indicated above, are novel and are a subject of the present invention. 25 Compounds according to the general formula (II), in which R' stands for an amino sugar shown in formula la, R 3 stands for hydrogen or hydroxy, and A-B stands for one of the following groups: -HC=C(CH 3 )-, -H 2
C-CH
2 - or -H 2
C-CH(CH
3 )-, are novel and are a subject of the present invention. 30 The additional initial substances of the amino compounds used for carrying out the method according to the invention are defined by the general formula (III).
-61 In formula (IIl), X and R 2 have the meanings that were already mentioned, in conjunction with the description of the compounds according to the invention according to the general formula (I), as being preferred for this substituent. 5 The amino compounds according to formula (III) are partially commercially available, some of them are known, and can they be obtained according to known methods (e.g. see hetaryl-methoxamine: US-A 5,489,680; DE-A 21 19 012, alkoxyamine: EP-A 495 750; DE-A 22 06 890; D. Favara et al., Farmaco, Ed. Sci. 42 10 (10), 1987, p. 697). A general method for the manufacture of aminoxy compounds (R 2 -X-, where X = 0) according to formula (III), for example, consists in reacting a hydroxylamine derivative, which exhibits a protective group on the nitrogen (e.g. R' and R" 15 together: phthaloyl group, isopropylidene group, a-hydroxy-benzylidene group), with a compound R 2 -E (0-alkylation) in a diluent, and the protective group is subsequently separated. In the R 2-E compound, R 2 has the same meaning as indicated previously, and E stands for a nucleofuge leaving group, for example aliphatically or aromatically substituted sulphonyloxy, e.g. methanesulphonyloxy, salts of the 20 sulphonic acid, p-toluene-sulphonyloxy (tosyloxy), and also halogen, for example, particularly bromine, chlorine or iodine (see O-alkylation). In Figure 4 below, the production of amino compounds according to formula (III) is shown (R -X, where X =0): 25 Figure 4
R
2 R' HO-N + R-E O-N - 0-NH2 R" R" - 62 Alternatively, an intermolecular dehydration reaction can be performed by using a hydroxy compound, (R 2 -OH, in Figure 4, E = OH) for example. In particular, a variant of the Mitsunobu reaction comes under consideration (see Synthesis 1976, p. 682), in which the hydroxy compounds are reacted with N-protected hydroxylamine 5 derivatives, such as N-hydroxyphthalimide, N-hydroxy-5-norbomene-2,3 dicarboxylic acid imide or acethydroxamic acid ethyl ester, as well as triphenyl phosphine and N,N'-azodicarboxylic acid diethyl ester, for example. The compounds according to formula (I) can be purposefully released in the 10 following manner: the hydrazinolysis can preferably take place in a diluent, for example alcohol, at boiling temperature. Hydrolysis can preferably be carried out in an aqueous, aqueous-alcohol or alcohol solution by heating it for several hours. If R' and R" together designate an isopropylidene group, acidic hydrolysis can be used, and if R' and R" together designate an cx-hydroxy-benzylidene group or if R" 15 designates a carbethoxy group, both alkaline and acidic hydrolysis can be used (see DE-A 21 19 012; D. Favara et al., Farmaco, Ed. Sci. 42 (10), (1987) p. 697). For the production of the salts, inorganic acids, such as hydrochloric acid or sulphuric acid in ethanolic or isopropanolic solution are preferably used. 20 According to the invention, a possibly substituted aryl moiety or arylalkyl moiety can stand for the R2 moiety, if necessary. If R2 stands for an amino-substituted aryl moiety or arylalkyl moiety, the aromatic NH 2 group can be modified according to generally known methods. It can be advantageous for the acylation reactions, 25 alkylation reactions or sulphonylation reactions to already take place in the protected intermediate R'R"N-O-R 2 in the presence of basic reaction additives and in the presence of a suitable diluent. The compounds according to the general formula (IIa) can be released according to the methods described above (also see Figure 5): - 63 Figure 5 A
H
2 N R' A-Hal HN C R' R"'-Hal 0-N 0-N R" R" R'Na t R' :R'N R O-N 0-NH 2 R" (Illa) A = SO -R' (z.B. R = Halalkyl, Alkyl, Aryl, Arylalkyl) CO-R' , CO-0-R R = H, Methyl R = Halalkyl, Alkyl, Arylalkyl, Acyl n = 1, 2 A general method for the manufacture of aminoxy compounds (R 2 -X-, where X = NH, NR 4 ) according to formula (III) consists in, for example, reacting a suitable primary or secondary amino compound with an N-tert-butyloxycarbonyl (Boc) transfer reagent, e.g. the commercially available N-Boc-3-(4 5 cyanophenyl)oxaziridine (BCPO), according to known methods (J. Vidal et al., J. Chem. Soc., Chem. Commun. 1991, 435-437; J. Org. Chem. 1993, 58, 4791-4793). Alternatively, the commercially available N-(Boc-amino)phthalimide or N (benzyloxycarbonyl-amino)phthalimide can be used as suitable initial components (N. Brosse et al., J. Org. Chem. 2001, 66, 2869). The R 2 moiety can be introduced via 10 a Mitsunobu reaction or N-alkylation. After separating the protective groups (Boc, benzyloxycarbonyl), the hydrazines can be utilised for the reaction according to the invention (also see Figure 6).
- 64 Figure 6 0 R N 4 4 R2-N + Bo+ R2-N - R-N H NC NH-Boc
NH
2 BCPO (llIb) O O H R 2 / - -H 2Y 2 N H-N RN R N N-R"' N-R" N-R'" R" R" R" 2H R-N
NH
2 (i c) The reaction of the 9-keto spinosyn derivatives according to the general formula (II), with the amino compounds according to the general formula (III), are preferably carried out in the presence of a basic reaction additive while using diluents. 5 All suitable acid binders can be used as basic reaction additives for performing the method according to the invention, such as amines, particularly tertiary amines, alkaline and alkaline earth compounds. As examples, the following are given: hydroxides, oxides and carbonates of lithium, 10 sodium, potassium, magnesium, calcium and barium, additional basic compounds such as amidine bases or guanidine bases like 7-methyl-1,5,7-triazabicyclo(4.4.0)dec 5-ene (MTBD); diazabicyclo(4.3.0)nonene (DBN), diazabicyclo(2.2.2)-octane (DABCO), 1,8-diaza-bicyclo(5.4.0)undecene (DBU), cyclohexyl-tetrabutylguanidine (CyTBG), cyclohexyltetramethylguanidine (CyTMG), N,N,N,N-tetramethyl-1,8 15 naphthalinediamine, pentamethylpiperidine, tertiary amines such as triethylamine, trimethylamine, tribenzylamine, triisopropylamine, tributylamine, tribenzylamine, tricyclohexylamine, triamylamine, trihexylamine, N,N-dimethyl-aniline, N,N dimethyl-toluidine, N,N-dimethyl-p-aminopyridine, N-methyl-pyrrolidine, N-methyl piperidine, N-methyl-imidazole, N-methyl-pyrrole, N-methyl-morpholine, N-methyl- -65 hexamethylenimine, pyridine, 4-pyrrolidinopyridine, 4-dimethylamino-pyridine, quinoline, ca-picoline, 1-picoline, isoquinoline, pyrimidine, acridine, N,N,N',N' tetramethylenediamine, N,N',N'-tetraethylenediamine, quinoxaline, N-propyl-diiso propylamine, N-ethyl-diisopropylamine, N,N'-dimethylcyclo-hexyl-amine, 2,6 5 lutidine, 2,4-lutidine or triethylenediamine. Aromatic amines, particularly pyridine, or tertiary amines, particularly trialkylamines such as triethylamine, N,N-diisopropyl-ethylamine, N-propyl-diisopropylamine, N,N'-dimethylcyclohexyl-amine or N-methylmorpholine, are used preferably. 10 In general it is beneficial to perform the method according to the invention in the presence of diluents. It is best if diluents are used in such a quantity that the reaction mixture can be easily stirred during the entire process. All inert organic solvents can be used as diluents for carrying out the method according to the invention. 15 The following are given as examples: halogenated hydrocarbons, particularly chlorohydrocarbons such as tetrachloroethylene, tetrachloroethane, dichloropropane, methylenechloride, dichlorobutane, chloroform, tetrachlorocarbon, trichloroethane, trichloroethylene, pentachloroethane, difluorobenzene, 1,2-dichloroethane, 20 chlorobenzene, bromobenzene, dichlorobenzene, chlorotoluene, trichlorobenzene; alcohols such as methanol, ethanol, isopropanol, butanol; ethers such as ethylpropylether, methyl-tert-butylether, n-butylether, anisole, phenetol, cyclohexylmethylether, dimethylether, diethylether, dipropylether, diisopropylether, di-n-butylether, diisobutylether, diisoamylether, ethyleneglycole-dimethylether, 25 tetrahydrofuran, dioxane, dichlorodiethylether and polyethers of ethyleneoxide and/or propyleneoxide: amines such as trimethyl-, triethyl-, tripropyl-, tributylamine, N methyl-morpholine, pyridine and tetramethylenediamine, nitrohydrocarbons such as nitromethane, nitroethane, nitropropane, nitrobenzene, chloronitrobenzene, o nitrotoluene; nitriles such as acetonitrile, propionitrile, butyronitrile, isobutyronitrile, 30 benzonitrile, m-chlorobenzonitrile, as well as compounds such as tetra- -66 hydrothiophenedioxide and dimethylsulphoxide, tetramethylenesulphoxide, dipropyl sulphoxide, benzylmethylsulphoxide, diisobutylsulphoxide, dibutylsulphoxide, dilsoamylsulphoxide; sulphones such as dimethyl-, diethyl-, dipropyl-, dibutyl-, diphenyl-, dihexyl-, methylethyl-, ethylpropyl-, ethylisobutyl- and 5 pentamethylenesulphone; aliphatic, cycloaliphatic or aromatic hydrocarbons such as pentane, hexane, heptane, octane, nonane and technical hydrocarbons, for example so-called white spirits with components that have boiling points in the range of 40'C to 250'C, for example, cymene, petroleum fractions within a boiling point range of 70'C to 190'C, cyclohexane, methylcyclohexane, petroleum ether, ligroin, octane, 10 benzene, toluene, chlorobenzene, bromobenzene, nitrobenzene, xylene; esters such as methyl-, ethyl-, butyl-, isobutylacetate, as well as dimethyl-, dibutyl-, ethylenecarbonate; amides such as hexamethylenephosphortriamide, formamide, N methyl-formamide, N,N-dimethyl-formamide, N,N-dipropylformamide, N,N dibutylformamide, N-methyl-pyrrolidine, N-methyl-caprolactam, 1,3-dimethyl 15 3,4,5,6-tetrahydro-2(1 H)-pyrimidine, octylpyrrolidone, octylcaprolactam, 1,3 dimethyl-2-imidazolindione, N-formyl-piperidine, N,N'-1,4-diformylpiperazine; ketones such as acetone, acetophenone, methylethylketone, methylbutylketone. Of course mixtures of the indicated solvents and diluents can be used in the method 20 according to the invention. Preferred diluents for performing the method according to the invention, however, are amines such as trimethyl-, triethyl-, tripropyl-, tributylamine, N-methyl morpholine and pyridin, amides such as N,N-dimethylformamide, N,N-dipropyl 25 formamide, N,N-dibutylformamide or N-methyl-pyrrolidine. Reactions of the amino compounds according to the general formula (III) can be carried out by reacting 17-p-desosaminyl-9-keto spinosyn and the 9-keto spinosyn aglycone derivatives according to the general formula (H) in the presence of an amino - 67 compound according to the general formula (III) and in the presence of one of the basic reaction additives indicated, and possibly in one of the diluents indicated The reaction time preferably amounts to between 10 minutes and 48 hours. The 5 reaction preferably occurs at temperatures between -10 0 C and +200'C, more preferably between +10 0 C and +180'C, most preferably at room temperature. It is basically possible to perform the work at normal pressure. The work is preferably done at normal pressure or at pressures up to 15 bar, and possible in a protective gas atmosphere (nitrogen or helium). 10 In order to carry out the process according to the invention, generally 0.5 to 7.0 mol, preferably 1.0 to 5.0 mol, particularly preferably 1.5 to 2.5 mol of amino compound according to the general formula (II) is employed for the oxime formation in the general formula (II). 15 After completing the reaction, the entire reaction compound is concentrated in a vacuum and purified in the customary manner using column chromatography (also see the Examples of Manufacture). 20 The active substances exhibit good plant tolerability, favourable endothermic toxicity, good environmental tolerability, and are suitable for protecting plants and plant organs, increasing harvest yields, improving the quality of the harvest product and controlling animal pests, in particular insects, arachnids and nematodes, which occur in the agricultural industry, forests, gardens and recreational equipment, as well 25 as in the areas of inventory and product protection and the hygiene sector. They are preferably used as plant protective agents. They are effective against regularly sensitive and resistant types, as well as against all or certain stages of development. The following pests are included in those mentioned above: 30 From the order of Isopoda, for example, Oniscus asellus, Armadillidium vulgare, Porcellio scaber.
- 68 From the order of Diplopoda, for example, Blaniulus guttulatus. From the order of Chilopoda, for example, Geophilus carpophagus, Scutigera spp. 5 From the order of Symphyla, for example, Scutigerella immaculata. From the order of Thysanura, for example, Lepisma saccharina. 10 From the order of Collembola, for example, Onychiurus armatus. From the order of Orthoptera, for example, Acheta domesticus, Gryllotalpa spp., Locusta migratoria migratorioides, Melanoplus spp., Schistocerca gregaria. 15 From the order of Blattaria, for example, Blatta orientalis, Periplaneta americana, Leucophaea maderae, Blattella germanica. From the order of Dermaptera, for example, Forficula auricularia. 20 From the order of Isoptera, for example, Reticulitermes spp. From the order of Phthiraptera, for example, Pediculus humanus corporis, Haematopinus spp., Linognathus spp., Trichodectes spp., Damalinia spp. 25 From the order of Thysanoptera, for example, Hercinothrips femoralis, Thrips tabaci, Thrips palmi, Frankliniella accidentalis. From the order of Heteroptera, for example, Eurygaster spp., Dysdercus intermedius, Piesma quadrata, Cimex lectularius, Rhodnius prolixus, Triatoma spp. 30 -69 From the order of Homoptera, for example, Aleurodes brassicae, Bemisia tabaci, Trialeurodes vaporariorum, Aphis gossypii, Brevicoryne brassicae, Cryptomyzus ribis, Aphis fabac, Aphis pomi, Eriosoma lanigerum, Hyalopterus arundinis, Phylloxera vastatrix, Pemphigus spp., Macrosiphum avenae, Myzus spp., Phorodon 5 humuli, Rhopalosiphum padi, Empoasca spp., Euscelis bilobatus, Nephotettix cincticeps, Lecanium comi, Saissetia oleae, Laodelphax striatellus, Nilaparvata lugens, Aonidiella aurantii, Aspidiotus hederae, Pseudococcus spp., Psylla spp. From the order of Lepidoptera, for example, Pectinophora gossypiella, Bupalus 10 piniarius, Cheimatobia brumata, Lithocolletis blancardella, Hyponomeuta padella, Plutella xylostella, Malacosoma neustria, Euproctis chrysorrhoea, Lymantria spp., Bucculatrix thurberiella, Phyllocnistis citrella, Agrotis spp., Euxoa spp., Feltia spp., Earias insulana, Heliothis spp., Mamestra brassicae, Panolis flammea, Spodoptera spp., Trichoplusia ni, Carpocapsa pomonella, Pieris spp., Chilo spp., Pyrausta 15 nubilalis, Ephestia kuehniella, Galleria mellonella, Tineola bisselliella, Tinea pellionella, Hofmannophila pseudospretella, Cacoecia podana, Capua reticulana, Choristoneura fumiferana, Clysia ambiguella, Homona magnanima, Tortrix viridana, Cnaphalocerus spp., Oulema oryzae. 20 From the order of Coleoptera, for example, Anobium punctatum, Rhizopertha dominica, Bruchidius obtectus, Acanthoscelides obtectus, Hylotrupes bajulus, Agelastica alni, Leptinotarsa decemlineata, Phaedon cochleariae, Diabrotica spp., Psylliodes chrysocephala, Epilachna varivestis, Atomaria spp., Oryzaephilus surinamensis, Anthonomus spp., Sitophilus spp., Otiorrhynchus sulcatus, 25 Cosmopolites sordidus, Ceuthorrhynchus assimilis, Hypera postica, Dermestes spp., Trogoderma spp., Anthrenus spp., Attagenus spp., Lyctus spp., Meligethes aeneus, Ptinus spp., Niptus hololeucus, Gibbium psylloides, Tribolium spp., Tenebrio molitor, Agriotes spp., Conoderus spp., Melolontha melolontha, Amphimallon solsti tialis, Costelytra zealandica, Lissorhoptrus oryzophilus. 30 - 70 From the order of Hymenoptera, for example, Diprion spp., Hoplocampa spp., Lasius spp., Monomorium pharaonis, Vespa spp. From the order of Diptera, for example, Aedes spp., Anopheles spp., Culex spp., 5 Drosophila melanogaster, Musca spp., Fannia spp., Calliphora erythrocephala, Lucilia spp., Chrysomyia spp., Cuterebra spp., Gastrophilus spp., Hyppobosca spp., Stomoxys spp., Oestrus spp., Hypoderma spp., Tabanus spp., Tannia spp., Bibio hortulanus, Oscinella frit, Phorbia spp., Pegomyia hyoscyami, Ceratitis capitata, Dacus oleae, Tipula paludosa, Hylemyia spp., Liriomyza spp. 10 From the order of Siphonaptera, for example, Xenopsylla cheopis, Ceratophyllus spp. From the class of Arachnida, for example, Scorpio maurus, Latrodectus mactans, Acarus siro, Argas spp., Ornithodoros spp., Dermanyssus gallinae, Eriophyes ribis, 15 Phyllocoptruta oleivora, Boophilus spp., Rhipicephalus spp., Amblyomma spp., Hyalomma spp., Ixodes spp., Psoroptes spp., Chorioptes spp., Sarcoptes spp., Tarsonemus spp., Bryobia praetiosa, Panonychus spp., Tetranychus spp., Hemitarsonemus spp., Brevipalpus spp. 20 The following belong to the group of plant-parasitic nematodes, for example: Pratylenchus spp., Radopholus similis, Ditylenchus dipsaci, Tylenchulus semipenetrans, Heterodera spp., Globodera spp., Meloidogyne spp., Aphelenchoides spp., Longidorus spp., Xiphinema spp., Trichodorus spp., Bursaphelenchus spp. 25 The substances according to the invention exhibit strong microbicidal efficacy and can be used for controlling undesired microorganisms, such as fungi and bacteria, in the areas of plant and material protection. Fungicides can be used in the area of plant protection for controlling plasmodiophoro 30 mycetes, oomycetes, chytridiomycetes, zygomycetes, ascomycetes, basidiomycetes and deuteromycetes.
-71 Bactericides can be used in the area of plant protection for controlling Pseudomonada ceae, Rhizobiaceae, Enterobacteriaceae, Corynebacteriaceae and Streptomycetaceae. 5 The following is a non all-inclusive list of some pathogens from fungal and bacterial infections, which fall under the abovementioned general headings: Xanthomonas species, such as, for example, Xanthomonas campestris pv. oryzae; 10 Pseudomonas species, such as, for example, Pseudomonas syringae pv. lachrymans; Erwinia species, such as, for example, Erwinia amylovora; Pythium species, such as, for example, Pythium ultimum; 15 Phytophthora species, such as, for example, Phytophthora infestans; Pseudoperonospora species, such as, for example, Pseudoperonospora humuli or Pseudoperonospora cubensis; 20 Plasmopara species, such as, for example, Plasmopara viticola; Bremia species, such as, for example, Bremia lactucae; 25 Peronospora species, such as, for example, Peronospora pisi or P. brassicae; Erysiphe species, such as, for example, Erysiphe graminis; Sphaerotheca species, such as, for example, Sphaerotheca fuliginea; 30 Podosphaera species, such as, for example, Podosphaera leucotricha; -72 Venturia species, such as, for example, Venturia inaequalis; Pyrenophora species, such as, for example, Pyrenophora teres or P. graminea 5 (Conidial form: Drechslera, syn: Helminthosporium); Cochliobolus species, such as, for example, Cochliobolus sativus (Conidial form: Drechslera, syn: Helminthosporium); 10 Uromyces species, such as, for example, Uromyces appendiculatus; Puccinia species, such as, for example, Puccinia recondita; Sclerotinia species, such as, for example, Sclerotinia sclerotiorum; 15 Tilletia species, such as, for example, Tilletia caries; Ustilago species, such as, for example, Ustilago nuda or Ustilago avenae; 20 Pellicularia species, such as, for example, Pellicularia sasakii; Pyricularia species, such as, for example, Pyricularia oryzae; Fusarium species, such as, for example, Fusarium culmorum; 25 Botrytis species, such as, for example, Botrytis cinerea; Septoria species, such as, for example, Septoria nodorum; 30 Leptosphaeria species, such as, for example, Leptosphaeria nodorum; -73 Cercospora species, such as, for example, Cercospora canescens; Alternaria species, such as, for example, Alternaria brassicae; and 5 Pseudocercosporella species, such as, for example, Pseudocercosporella herpotri choides. The active compounds according to the invention also have very good fortifying action in plants. Accordingly, they can be used for mobilizing the defences of the 10 plant against attack by undesirable microorganisms. In the present context, plant-fortifying (resistance-inducing) substances are to be understood as meaning those substances, which are capable of stimulating the defence system of plants such that, when the treated plants are subsequently 15 innoculated with undesirable microorganisms, they show substantial resistance against these microorganisms. In the present case, undesirable microorganisms are to be understood as meaning phytopathogenic fungi, bacteria and viruses. Accordingly, the substances according 20 to the invention can be used to protect plants for a certain period after the treatment against attack by the pathogens mentioned. The period for which protection is provided generally extends over 1 to 10 days, preferably 1 to 7 days, after the treatment of the plants with the active compounds. 25 The fact that the active compounds are well tolerated by plants at the concentrations required for controlling plant diseases permits the treatment of aboveground parts of plants, of propagation stock and seeds, and of the soil. The active compounds according to the invention can be used to treat all plants and 30 parts of plants. By plants are understood here all plants and plant populations such as desired and undesired wild plants or crop plants (including naturally occurring crop - 74 plants). Crop plants can be plants which can be obtained by conventional breeding and optimisation methods or by biotechnological and genetic engineering methods or combinations of these methods, including the transgenic plants and including the plant varieties which can or cannot be protected by varietal property rights. Parts of 5 plants are to be understood as meaning all above-ground and below-ground parts and organs of plants, such as the shoot, leaf, flower and root, examples which may be mentioned being leaves, needles, stems, trunks, flowers, fruit-bodies, fruits and seeds and also roots, tubers and rhizomes. Parts of plants also include harvested plants and vegetative and generative propagation material, for example seedlings, tubers, 10 rhizomes, cuttings and seeds. Particularly preferably, plants of the plant cultivated plants, which are in each case commercially available or in use, are treated according to the invention. Plant cultivated plants are to be understood as meaning plants having new properties 15 ("traits") and which have been obtained by conventional breeding, by mutagenesis or by recombinant DNA techniques. They can be cultivated plants, varieties, bio- or genotypes. Depending on the plant species or plant cultivated plants, their location and growth 20 conditions (soils, climate, vegetation period, nutrition), the treatment according to the invention may also result in super-additive ("synergistic") effects. Thus, for example, reduced application rates and/or a widening of the activity spectrum and/or an increase in the activity of the substances and compositions which can be used according to the invention, better plant growth, increased tolerance to high or low 25 temperatures, increased tolerance to drought or to water or soil salt content, increased flowering performance, easier harvesting, accelerated maturation, higher harvest yields, better quality and/or a higher nutritional value of the harvested products, better storage stability and/or processability of the harvested products are possible, which exceed the effects which were actually to be expected. 30 -75 The transgenic plants or plant cultivated plants (i.e. those obtained by genetic engineering), which are preferably treated according to the invention, include all plants which, in the genetic modification, received genetic material which imparted particularly advantageous useful properties ("traits") to these plants. Examples of 5 such properties are better plant growth, increased tolerance to high or low temperatures, increased tolerance to drought or to water or soil salt content, increased flowering performance, easier harvesting, accelerated maturation, higher harvest yields, better quality and/or a higher nutritional value of the harvested products, better storage stability and/or processability of the harvested products. Further and 10 particularly emphasized examples of such properties are a better defence of the plants against animal and microbial pests, such as against insects, mites, phytopathogenic fungi, bacteria and/or viruses, and also increased tolerance of the plants to certain herbicidally active compounds. Examples of transgenic plants which may be mentioned are the important crop plants, such as cereals (wheat, rice), maize, soya 15 beans, potatoes, cotton, tobacco, oilseed rape and also fruit plants (with the fruits apples, pears, citrus fruits and grapes), and particular emphasis is given to maize, soya beans, potatoes, cotton, tobacco and oilseed rape. Traits that are emphasised are in particular increased defence of the plants against insects by toxins formed in the plants, in particular those formed in the plants by the genetic material from Bacillus 20 thuringiensis (for example by the genes CryIA(a), CryIA(b), CryIA(c), CryIIA, CryIIA, CryIIIB2, Cry9c Cry2Ab, Cry3Bb and CrylF and also combinations thereof) (hereinafter referred to as "Bt plants"). Traits that are also particularly emphasised are the increased defence of the plants against fungi, bacteria and viruses by systemic acquired resistance (SAR), systemin, phytoalexins, elicitors and resistance genes and 25 correspondingly expressed proteins and toxins. Traits that are furthermore particularly emphasized are the increased tolerance of the plants to certain herbicidally active compounds, for example imidazolinones, sulphonylureas, glyphosates or phosphinotricin (for example the "PAT" gene). The genes, which impart the desired traits in question, can also be present in combination with one 30 another in the transgenic plants. Examples of "Bt plants" which may be mentioned are maize varieties, cotton varieties, soya bean varieties and potato varieties which - 76 are sold under the trade names YIELD GARD@ (for example maize, cotton, soya beans), KnockOut@ (for example maize), StarLink@ (for example maize), Bollgard@ (cotton), Nucotn@ (cotton) and NewLeaf@ (potato). Examples of herbicide-tolerant plants which may be mentioned are maize varieties, cotton varieties and soya bean 5 varieties, which are sold under the trade names Roundup Ready@ (tolerance to glyphosates, for example maize, cotton, soya bean), Liberty Link@ (tolerance to phosphinotricin, for example oilseed rape), IMI® (tolerance to imidazolinones) and STS@ (tolerance to sulphonylureas, for example maize). Herbicide-resistant plants (plants bred in a conventional manner for herbicide tolerance), which may be 10 mentioned, include the varieties sold under the name Clearfield@ (for example maize). Of course, these statements also apply to plant cultivated plants having these genetic traits or genetic traits still to be developed, which will be developed and/or marketed in the future. 15 The plants listed can be treated according to the invention in a particularly advantageous manner with the compounds according to the general formula (I) or the active substance mixtures according to the invention. The preferred ranges stated above for the active compounds and mixtures also apply to the treatment of these plants. Particular emphasis is given to the treatment of plants with the compounds or 20 mixture specifically mentioned in the present text. The treatment of the plants and the parts of plants with the active compounds according to the invention is carried out directly or by action on their surroundings, habitat or storage space, according to customary treatment methods, for example by 25 dipping, spraying, evaporating, atomising, strewing, spreading and, in the case of propagation material, in particular in the case of seeds, further with single or multi layer coating. In the protection of materials, the compounds according to the invention can be 30 employed for protecting industrial materials against infection with, and destruction by, undesired microorganisms.
-77 Industrial materials in the present context are understood as meaning non-living materials that have been prepared for use in industry. For example, industrial materials, which are intended to be protected by active compounds according to the 5 invention from microbial change or destruction, can be adhesives, glues, paper and cardboard, textiles, leather, wood, paints and plastic articles, cooling lubricants and other materials which can be infected with, or destroyed by, microorganisms. Parts of production plants, for example cooling-water circuits, which may be impaired by the proliferation of microorganisms may also be mentioned within the scope of the 10 materials to be protected. Industrial materials, which may be mentioned within the scope of the present invention, are preferably adhesives, glues, paper and cardboard, leather, wood, paints, cooling lubricants and heat-transfer liquids, particularly preferably wood. 15 Microorganisms capable of degrading or changing the industrial materials are, for example, bacteria, fungi, yeasts, algae and slime organisms. The active compounds according to the invention preferably act against fungi, in particular moulds, wood discolouring and wood-destroying fungi (Basidiomycetes), and against slime organisms and algae. 20 Microorganisms of the following genera may be mentioned as examples: Alternaria, such as Alternaria tenuis; 25 Aspergillus, such as Aspergillus niger; Chaetomium, such as Chaetomium globosum; Coniophora, such as Coniophora puetana; 30 Lentinus, such as Lentinus tigrinus; -78 Penicillium, such as Penicillium glaucum; Polyporus, such as Polyporus versicolor; 5 Aureobasidium, such as Aureobasidium pullulans; Sclerophoma, such as Sclerophoma pityophila; 10 Trichoderma, such as Trichoderma viride; Escherichia, such as Escherichia coli; Pseudomonas, such as Pseudomonas aeruginosa; 15 Staphylococcus, such as Staphylococcus aureus. Depending on their particular physical and/or chemical properties, the active compounds can be converted to the customary formulations, such as solutions, 20 emulsions, suspensions, powders, foams, pastes, granules, aerosols and micro encapsulations in polymeric substances and in coating compositions for seeds, and ULV cool and warm fogging formulations. These formulations are produced in a known manner, for example by mixing the 25 active compounds with extenders, that is, liquid solvents, liquefied gases under pressure, and/or solid carriers, optionally with the use of surfactants, that is emulsifiers and/or dispersants, and/or foaming agents. If the extender used is water, it is also possible to employ, for example, organic solvents as auxiliary solvents. Essentially, suitable liquid solvents are: aromatics such as xylene, toluene or 30 alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatic hydrocarbons - 79 such as cyclohexane or paraffins, for example petroleum fractions, alcohols such as butanol or glycol and their ethers and esters, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents such as dimethylformamide or dimethyl sulphoxide, as well as water. Liquefied gaseous 5 extenders or carriers are to be understood as meaning liquids which are gaseous at standard temperature and under atmospheric pressure, for example aerosol propellants such as halogenated hydrocarbons, or else butane, propane, nitrogen and carbon dioxide. Suitable solid carriers are: for example, ground natural minerals such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous 10 earth, and ground synthetic minerals such as highly disperse silicic acid, aluminium oxide and silicates. Suitable solid carriers for granules are: for example crushed and fractionated natural rocks such as calcite, marble, pumice, sepiolite and dolomite, or else synthetic granules of inorganic and organic meals, and granules of organic material such as sawdust, coconut shells, maize cobs and tobacco stalks. Suitable 15 emulsifiers and/or foaming agents are: for example non-ionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkylsulphonates, alkyl sulphates, arylsulphonates, or else protein hydrolysates. Suitable dispersants are: for example, lignosulphite waste liquors and methylcellulose. 20 Bonding agents such as carboxymethylcellulose and natural and synthetic polymers in the form of powders, granules or latex-forming polymers, such as Gum Arabic, polyvinyl alcohol and polyvinyl acetate, as well as natural phospholipids such as cephalins and lecithins and synthetic phospholipids can be used in the formulations. 25 Other possible additives are mineral and vegetable oils. It is possible to use colourants such as inorganic pigments, for example iron oxide, titanium oxide and cyan blue, and organic dyes such as alizarin dyes, azo dyes and metal phthalocyanine dyes, and trace nutrients such as salts of iron, manganese, 30 boron, copper, cobalt, molybdenum and zinc.
- 80 The formulations generally comprise between 0.1 and 95 percent by weight of active compound, preferably between 0.5 and 90%. The active compounds according to the invention can be used as such or in their 5 formulations, also in a mixture with known fungicides, bactericides, acaricides, nematicides or insecticides, to broaden, for example, the activity spectrum or to prevent development of resistance. In many cases, synergistic effects are obtained, i.e. the activity of the mixture is greater than the activity of the individual components. 10 Examples of suitable mixing components are the following: Fungicides: 15 2-phenylphenol; 8 -hydroxyquinoline sulphate; acibenzolar-S-methyl; aldimorph; amidoflumet; ampropylfos; ampropylfos-potassium; andoprim; anilazine; azaconazole; azoxystrobin; benalaxyl; benodanil; benomyl; benthiavalicarb isopropyl; benzamacril; benzamacryl-isobutyl; bilanafos; binapacryl; biphenyl; bitertanol; blasticidin-S; bromuconazole; bupirimate; buthiobate; butylamine; 20 calcium polysulphide; capsimycin; captafol; captan; carbendazim; carboxin; carpropamid; carvon; quinomethionate; chlobenthiazone; chlorfenazole; chloroneb; chlorothalonil; chlozolinate; clozylacon; cyazofamid; cyflufenamid; cymoxanil; cyproconazole; cyprodinil; cyprofuram; Dagger G; debacarb; dichlofluanid; dichlone; dichlorophen; diclocymet; diclomezine; dicloran; diethofencarb; difenoconazole; 25 diflumetorim; dimethirimol; dimethomorph; dimoxystrobin; diniconazole; diniconazole-M; dinocap; diphenylamine; dipyrithione; ditalimfos; dithianon; dodine; drazoxolon; edifenphos; epoxiconazole; ethaboxam; ethirimol; etridiazole; famoxadon; fenamidone; fenapanil; fenarimol; fenbuconazole; fenfuram; fenhexamid; fenitropan; fenoxanil; fenpiclonil; fenpropidin; fenpropimorph; ferbam; 30 fluazinam; flubenzimine; fludioxonil; flumetover; flumorph; fluoromide; fluoxastrobin; fluquinconazole; flurprimidol; flusilazole; flusulphamide; flutolanil; -81 flutriafol; folpet; fosetyl-aluminium; fosetyl-sodium; fuberidazole; furalaxyl; furametpyr; furcarbanil; furmecyclox; guazatine; hexachlorobenzene; hexaconazole; hymexazole; imazalil; imibenconazole; iminoctadine triacetate; iminoctadine tris albesilate; iodocarb; ipconazole; iprobenfos; iprodione; iprovalicarb; irumamycin; 5 isoprothiolane; isovaledione; kasugamycin; kresoxim-methyl; mancozeb; maneb; meferimzone; mepanipyrim; mepronil; metalaxyl; metalaxyl-M; metconazole; methasulphocarb; methfuroxam; metiram; metominostrobin; metsulphovax; mildiomycin; myclobutanil; myclozolin; natamycin; nicobifen; nitrothal-isopropyl; noviflumuron; nuarimol; ofurace; orysastrobin; oxadixyl; oxolinic acid; 10 oxpoconazole; oxycarboxin; oxyfenthiin; paclobutrazol; pefurazoate; penconazole; pencycuron; phosdiphen; phthalide; picoxystrobin; piperalin; polyoxin; polyoxorim; probenazole; prochloraz; procymidone; propamocarb; propanosine-sodium; propiconazole; propineb; proquinazid; prothioconazole; pyraclostrobin; pyrazophos; pyrifenox; pyrimethanil; pyroquilon; pyroxyfur; pyrrolnitrine; quinconazole; 15 quinoxyfen; quintozene; simeconazole; spiroxamine; sulphur; tebuconazole; tecloftalam; tecnazene; tetcyclasis; tetraconazole; thiabendazole; thicyofen; thifluzamide; thiophanate-methyl; thiram; tioxymid; toiclofos-methyl; tolylfluanid; triadimefon; triadimenol; triazbutil; triazoxide; tricyclamide; tricyclazole; tridemorph; trifloxystrobin; triflumizole; triforine; triticonazole; uniconazole; 20 validamycin A; vinclozolin; zineb; ziram; zoxamide; (2S)-N-[2-[4-[[3-(4 chlorophenyl)-2-propynyl]oxy]-3-methoxyphenyl]ethyl]-3-methyl- 2 [(methylsulphonyl)amino]-butanamide; 1-(1-naphthalenyl)-1H-pyrrol-2,5-dione; 2,3,5, 6 -tetrachloro-4-(methylsulphonyl)-pyridine; 2-amino-4-methyl-N-phenyl-5 thiazolecarboxamide; 2-chloro-N-(2,3-dihydro-1,1,3-trimethyl-1H-inden-4-yl)-3 25 pyridinecarboxamide; 3, 4 ,5-trichloro-2,6-pyridinedicarbonitrile; actinovate; cis-1-(4 chlorophenyl)-2-(1H-1,2,4-triazole-1-yl)-cycloheptanol; methyl 1-(2,3-dihydro-2,2 dimethyl-1H-inden-1-yl)-1H-imidazole-5-carboxylate; monopotassium carbonate; N
(
6 -methoxy-3-pyridinyl)-cyclopropanecarboxamide; N-butyl-8-(1,1-dimethylethyl)-1 oxaspiro[4.5]decan-3-amine; sodium tetrathiocarbonate; 30 -82 as well as copper salts and preparations, such as Bordeaux mixture; copper hydroxide; copper naphthenate; copper oxychloride; copper sulphate; cufraneb; copper oxide; mancopper; and oxine-copper. 5 Bactericides: Bronopol, dichlorophen, nitrapyrin, nickel dimethyldithiocarbamate, kasugamycin, octhilinone, furancarboxylic acid, oxytetracycline, probenazole, streptomycin, tecloftalam, copper sulphate and other copper preparations. 10 Insecticides / Acaricides / Nematicides: Abamectin, ABG-9008, acephate, acequinocyl, acetamiprid, acetoprole, acrinathrin, AKD-1022, AKD-3059, AKD-3088, alanycarb, aldicarb, aldoxycarb, allethrin, 15 allethrin IR isomers, alpha-cypermethrin (alphamethrin), amidoflumet, aminocarb, amitraz, avermectin, AZ-60541, azadirachtin, azamethiphos, azinphos-methyl, azin phos-ethyl, azocyclotin, Bacillus popilliae, Bacillus sphaericus, Bacillus subtilis, Bacillus thuringiensis, 20 Bacillus thuringiensis strain EG-2348, Bacillus thuringiensis strain GC-91, Bacillus thuringiensis strain NCTC-11821, Baculo viruses, Beauveria bassiana, Beauveria tenella, bendiocarb, benfuracarb, bensultap, benzoximate, beta-cyfluthrin, beta-cyper methrin, bifenazate, bifenthrin, binapacryl, bioallethrin, bioallethrin-S-cyclopentyl isomer, bioethanomethrin, biopermethrin, bioresmethrin, bistrifluron, BPMC, brofen 25 prox, bromophos-ethyl, bromopropylate, bromfenvinfos (-methyl), BTG-504, BTG 505, bufencarb, buprofezin, butathiofos, butocarboxim, butoxycarboxim, butyl pyridaben, cadusafos, camphechlor, carbaryl, carbofuran, carbophenothion, carbosulphan, 30 cartap, CGA-50439, quinomethionate, chlordane, chlordimeform, chloethocarb, chlorethoxyfos, chlorfenapyr, chlorfenvinphos, chlorfluazuron, chlormephos, chloro- -83 benzilate, chloropicrin, chlorproxyfen, chlorpyrifos-methyl, chlorpyrifos (-ethyl), chlovaporthrin, chromafenozide, cis-cypermethrin, cis-resmethrin, cis-permethrin, clocythrin, cloethocarb, clofentezine, clothianidin, clothiazoben, codlemone, couma phos, cyanofenphos, cyanophos, cycloprene, cycloprothrin, Cydia pomonella, cy 5 fluthrin, cyhalothrin, cyhexatin, cypermethrin, cyphenothrin (IR trans-isomer), cyromazine, DDT, deltamethrin, demeton-S-methyl, demeton-S-methylsulphon, diafenthiuron, di alifos, diazinon, dichlofenthion, dichlorvos, dicofol, dicrotophos, dicyclanil, diflu 10 benzuron, dimethoate, dimethylvinphos, dinobuton, dinocap, dinotefuran, diofenolan, disulphoton, docusat-sodium, dofenapyn, DOWCO-439, eflusilanate, emamectin, emamectin-benzoate, empenthrin (1R isomer), endosulphan, Entomopthora spp., EPN, esfenvalerate, ethiofencarb, ethiprole, ethion, ethoprophos, 15 etofenprox, etoxazole, etrimfos, famphur, fenamiphos, fenazaquin, fenbutatin oxide, fenfluthrin, fenitrothion, fenobu carb, fenothiocarb, fenoxacrim, fenoxycarb, fenpropathrin, fenpyrad, fenpyrithrin, fenpyroximate, fensulphothion, fenthion, fentrifanil, fenvalerate, fipronil, flonicamid, 20 fluacrypyrim, fluazuron, flubenzimine, flubrocythrinate, flucycloxuron, flucythrinate, flufenerim, flufenoxuron, flufenprox, flumethrin, flupyrazofos, flutenzin (flufenzine), fluvalinate, fonofos, formetanate, formothion, fosmethilan, fosthiazate, fubfenprox (fluproxyfen), furathiocarb, 25 gamma-HCH, gossyplure, grandlure, granuloseviruses, halfenprox, halofenozide, HCH, HCN-801, heptenophos, hexaflumuron, hexy thiazox, hydramethylnone, hydroprene, 30 IKA-2002, imidacloprid, imiprothrin, indoxacarb, iodofenphos, iprobenfos, isazofos, isofenphos, isoprocarb, isoxathion, ivermectin, - 84 japonilure, kadethrin, nuclear polyhedral viruses, kinoprene, 5 lambda-cyhalothrin, lindane, lufenuron, malathion, mecarbam, mesulphenfos, metaldehyde, metam-sodium, methacrifos, methamidophos, Metharhizium anisopliae, Metharhizium flavoviride, methidathion, 10 methiocarb, methomyl, methoprene, methoxychlor, methoxyfenozide, metolcarb, metoxadiazone, mevinphos, milbemectin, milbemycin, MKI-245, MON-45700, monocrotophos, moxidectin, MTI-800, naled, NC-104, NC-170, NC-184, NC-194, NC-196, niclosamide, nicotine, niten 15 pyram, nithiazine, NNI-0001, NNI-0101, NNI-0250, NNI-9768, novaluron, novi flumuron, OK-5101, OK-5201, OK-9601, OK-9602, OK-9701, OK-9802, omethoate, oxamyl, oxydemeton-methyl, 20 Paecilomyces fumosoroseus, parathion-methyl, parathion (-ethyl), permethrin (cis-, trans-), petroleum, PH-6045, phenothrin (1R trans-isomer), phenthoate, phorate, phosalone, phosmet, phosphamidon, phosphocarb, phoxim, piperonyl butoxide, pirimicarb, pirimiphos-methyl, pirimiphos-ethyl, prallethrin, profenofos, promecarb, 25 propaphos, propargite, propetamphos, propoxur, prothiofos, prothoate, protrifenbute, pymetrozine, pyraclofos, pyresmethrin, pyrethrum, pyridaben, pyridalyl, pyridaphen thion, pyridathion, pyrimidifen, pyriproxyfen, quinalphos, 30 resmethrin, RH-5849, ribavirin, RU-12457, RU-15525, -85 S-421, S-1833, salithion, sebufos, SI-0009, silafluofen, spinosad, spirodiclofen, spiromesifen, sulphluramid, sulphotep, sulprofos, SZI-121, 5 tau-fluvalinate, tebufenozide, tebufenpyrad, tebupirimfos, teflubenzuron, tefluthrin, temephos, temivinphos, terbam, terbufos, tetrachlorvinphos, tetradifon, tetramethrin, tetramethrin (IR isomer), tetrasul, theta-cypermethrin, thiacloprid, thiamethoxam, thiapronil, thiatriphos, thiocyclam hydrogen oxalate, thiodicarb, thiofanox, thio meton, thiosultap-sodium, thuringiensin, tolfenpyrad, tralocythrin, tralomethrin, 10 transfluthrin, triarathene, triazamate, triazophos, triazuron, trichlophenidine, trichlor fon, triflumuron, trimethacarb, vamidothion, vaniliprole, verbutin, Verticillium lecanii, 15 WL-108477, WL-40027, YI-5201, YI-5301, YI-5302, XMC, xylylcarb, 20 ZA-3274, zeta-cypermethrin, zolaprofos, ZXI-8901, the compound 3 -methyl-phenyl-propylcarbamate (Tsumacide Z), the compound 3 -(5-Chlor- 3 -pyridinyl)-8-(2,2,2-trifluoroethyl)-8-azabicyclo[3.2.1] octane-3-carbonitrile (CAS-Reg.-No. 185982-80-3) and the corresponding 3-endo 25 isomers (CAS-Reg.-No. 185984-60-5) (see WO-96/37494, WO-98/25923), as well as other preparations, which contain plant extracts effective as insecticides, nematodes, fungi or viruses. 30 A mixture with other known active compounds, such as herbicides, or with fertilizers and growth regulators, safeners or semiochemicals is also possible.
- 86 In addition, the compounds of the formula (I) according to the invention also have very good antimycotic activity. They have a very broad antimycotic activity spectrum in particular against dermatophytes and yeasts, moulds and diphasic fungi, (for 5 example against Candida species, such as Candida albicans, Candida glabrata), and Epidermophyton floccosum, Aspergillus species, such as Aspergillus niger and Aspergillus fumigatus, Trichophyton species, such as Trichophyton mentagrophytes, Microsporon species such as Microsporon canis and audouinii. The list of these fungi by no means covers the entire extent of the mycotic spectrum covered, but is only for 10 illustration. When the active substances according to the invention are used as fungicides, the application rate can be varied within a large range depending on the type of application. When treating plant parts, the application rates of the active substance are generally 15 between 0.1 and 10,000 g/ha, preferably between 10 and 1,000 g/ha. When treating seeds, the application rates of the active substance are generally between 0.001 and 50 g per kilogram of seeds, preferably between 0.01 and 10 g per kilogram of seeds. When treating soil, the application rates of the active substance are generally between 0.1 and 10,000 g/ha, preferably between 1 and 5,000 g/ha. 20 When used as insecticides, the active substances according to the invention can furthermore be present in their commercial formulations and in the forms of use prepared from these formulations, in mixtures with synergists. Synergists are compounds which increase the activity of the active compounds, without it being 25 necessary for the added synergist to be active itself. When used as insecticides, the active substances according to the invention can furthermore be present in their commercial formulations and in the forms of use prepared from these formulations, in mixtures with inhibitors, which reduce 30 decomposition of the active substance after application in the vicinity of the plant, on the surface of plant parts or in plant tissue.
- 87 The application is carried out in a manner that is adapted to the form of use. When used against hygiene pests and stored product pests, the active substance is 5 distinguished by excellent residual activity on wood and clay, and by good alkaline stability on limed substrates. The active substances according to the invention act not only against plant, hygiene and stored product pests, but also in the veterinary medicine sector against animal 10 parasites (ectoparasites), such as hard ticks, soft ticks, mange mites, leaf mites, flies (biting and licking), parasitic fly larvae, lice, hair lice, feather lice and fleas. These parasites include: From the order of Anoplurida, for example, Haematopinus spp., Linognathus spp., 15 Pediculus spp., Phtirus spp., Solenopotes spp. From the order of Mallophagida and the suborders of Amblycerina and Ischnocerina, for example, Trimenopon spp., Menopon spp., Trinoton spp., Bovicola spp., Werneckiella spp., Lepikentron spp., Damalina spp., Trichodectes spp., Felicola spp. 20 From the order of Diptera and the suborders of Nematocerina and Brachycerina, for example, Aedes spp., Anopheles spp., Culex spp., Simulium spp., Eusimulium spp., Phlebotomus spp., Lutzomyia spp., Culicoides spp., Chrysops spp., Hybomitra spp., Atylotus spp., Tabanus spp., Haematopota spp., Philipomyia spp., Braula spp., Musca 25 spp., Hydrotaea spp., Stomoxys spp., Haematobia spp., Morellia spp., Fannia spp., Glossina spp., Calliphora spp., Lucilia spp., Chrysomyia spp., Wohlfahrtia spp., Sarcophaga spp., Oestrus spp., Hypoderma spp., Gasterophilus spp., Hippobosca spp., Lipoptena spp., Melophagus spp. 30 From the order of Siphonapterida, for example, Pulex spp., Ctenocephalides spp., Xenopsylla spp., Ceratophyllus spp.
- 88 From the order of Heteropterida, for example, Cimex spp., Triatoma spp., Rhodnius spp., Panstrongylus spp. 5 From the order of Blattarida, for example, Blatta orientalis, Periplaneta americana, Blattela germanica, Supella spp. From the subclass of Acaria (Acarida) and the orders of Meta- and Mesostigmata, for example, Argas spp., Ornithodorus spp., Otobius spp., Ixodes spp., Amblyomma 10 spp., Boophilus spp., Dermacentor spp., Haemophysalis spp., Hyalomma spp., Rhipicephalus spp., Dermanyssus spp., Raillietia spp., Pneumonyssus spp., Sternostoma spp., Varroa spp. From the order of Actinedida (Prostigmata) und Acaridida (Astigmata), for example, 15 Acarapis spp., Cheyletiella spp., Ornithocheyletia spp., Myobia spp., Psorergates spp., Demodex spp., Trombicula spp., Listrophorus spp., Acarus spp., Tyrophagus spp., Caloglyphus spp., Hypodectes spp., Pterolichus spp., Psoroptes spp., Chorioptes spp., Otodectes spp., Sarcoptes spp., Notoedres spp., Knemidocoptes spp., Cytodites spp., Laminosioptes spp. 20 The active substances according to the invention according to formula (1) are also suitable for controlling arthropods which attack agricultural livestock such as, for example, cattle, sheep, goats, horses, pigs, donkeys, camels, buffalo, rabbits, chickens, turkeys, ducks, geese, honey bees, other domestic animals such as, for 25 example, dogs, cats, caged birds, aquarium fish and so-called experimental animals such as, for example, hamsters, guinea pigs, rats and mice. By controlling these arthropods, cases of death and reductions in productivity (for meat, milk, wool, hides, eggs, honey and the like) should be diminished, so that more economical and simpler animal husbandry is possible with the use of the active compounds according to the 30 invention.
- 89 The active substances according to the invention are used in the veterinary sector in a known manner via enteral administration in the form of, for example, tablets, capsules, potions, drenches, granules, pastes, boli, the feed-through method, suppositories, via parenteral administration such as, for example, by injections 5 (intramuscularly, subcutaneously, intravenously, intraperitoneally and the like), by implants, by nasal administration, by dermal administration in the form of, for example, immersing or dipping, spraying, pouring-on, spotting-on, washing, dusting, and with the aid of moulded articles containing active substances such as collars, ear tags, tail tags, limb bands, halters, marking devices and the like. 10 When used for cattle, poultry, domestic animals and the like, the active substances according to formula () can be applied as formulations (for example powders, emulsions, flowing agents), which contain the active substances in an amount of 1 to 80% by weight, either directly or after 100- to 10,000-fold dilution, or they may be 15 used as a chemical bath. Moreover, it has been found that the active substances according to the invention exhibit potent insecticidal action against insects that destroy industrial materials. 20 The following insects may be mentioned as an example and with preference, but not as a limitation: Beetles, such as, for example, Hylotrupes bajulus, Chlorophorus pilosis, Anobium punctatum, Xestobium rufovillosum, Ptilinus pecticornis, Dendrobium pertinex, 25 Ernobius mollis, Priobium carpini, Lyctus brunneus, Lyctus africanus, Lyctus planicollis, Lyctus linearis, Lyctus pubescens, Trogoxylon aequale, Minthes rugicollis, Xyleborus spec. Tryptodendron spec. Apate monachus, Bostrychus capucins, Heterobostrychus brunneus, Sinoxylon spec. Dinoderus minutus; 30 Dermapterans such as, for example, Sirex juvencus, Urocerus gigas, Urocerus gigas taignus, Urocerus augur; -90 Termites, such as, for example, Kalotermes flavicollis, Cryptotermes brevis, Heterotermes indicola, Reticulitermes flavipes, Reticulitermes santonensis, Reticulitermes lucifugus, Mastotermes darwiniensis, Zootermopsis nevadensis, 5 Coptotermes formosanus; Bristletails, such as, for example, Lepisma saccharina; Industrial materials in the present context are understood as meaning non-living 10 materials such as, preferably, plastics, adhesives, glues, paper and cardboard, leather, wood, timber products and paints. The materials, which are to be protected from insect attack, are especially preferably wood and timber products. 15 Wood and timber products, which can be protected by the substance according to the invention, or mixtures containing the substance, are to be understood as meaning, for example: 20 Construction timber, wooden beams, railway sleepers, bridge components, jetties, wooden vehicles, boxes, pallets, containers, telephone poles, wood lagging, wooden windows and doors, plywood, clipboard, joinery, or timber products which quite generally are used in house construction or building joinery. 25 The insecticidal compounds or concentrates used for protecting wood and timber products contain the active substance according to the invention in a concentration of 0.0001 to 95% by weight, in particular 0.001 to 60% by weight. The amount of compound or concentrate employed depends on the species and the 30 abundance of the insects and on the medium. The optimal quantity to be employed can be determined in each case by test series upon application. In general, however, it -91 will suffice to employ 0.0001 to 20% by weight, preferably 0.001 to 10% by weight, of the active substance, based on the material to be protected. A suitable solvent and/or diluent is an organochemical solvent or solvent mixture 5 and/or an oily or oil-type organochemical solvent or solvent mixture of low volatility and/or a polar organochemical solvent or solvent mixture and/or water and, if appropriate, an emulsifier and/or wettening agent. Organochemical solvents, which are preferably, employed are oily or oil-type 10 solvents with an evaporation number of above 35 and a flash point of above 30'C, preferably above 45'C. Such oily and oil-type solvents which are insoluble in water and of low volatility and which are used are suitable mineral oils or their aromatic fractions or mineral-oil-containing solvent mixtures, preferably white spirit, petroleum and/or alkylbenzene. 15 Mineral oils, which are preferably used, are those with a boiling range of 170 to 220'C, white spirit with a boiling range of 170 to 220'C, spindle oil with a boiling range of 250 to 350'C, petroleum and aromatics with a boiling range of 160 to 280'C, turpentine oil, and the like. 20 In a preferred embodiment, liquid aliphatic hydrocarbons with a boiling range of 180 to 210"C or high-boiling mixtures of aromatic and aliphatic hydrocarbons with a boiling range of 180 to 220"C and/or spindle oil and/or monochloronaphthalene, preferably a.-monochloronaphthalene are used. 25 The organic oily or oil-type solvents of low volatility and with an evaporation number of above 35 and a flash point of above 30'C, preferably above 45"C, can be replaced in part by organochemical solvents of high or medium volatility, provided that the solvent mixture also has an evaporation number of above 35 and a flash point - 92 of above 30"C, preferably above 45'C, and that the insecticide/fungicide mixture is soluble or emulsifiable in this solvent mixture. In a preferred embodiment, some of the organochemical solvent or solvent mixture is 5 replaced by an aliphatic polar organochemical solvent or solvent mixture. Aliphatic organochemical solvents that contain hydroxyl and/or ester and/or ether groups are preferably used, such as, for example, glycol ethers, esters or the like. Organochemical binders used for the purposes of the present invention are the 10 synthetic resins and/or binding drying oils which are known per se and which can be diluted in water and/or dissolved or dispersed or emulsified in the organochemical solvents employed, in particular binders composed of, or comprising, an acrylate resin, a vinyl resin, for example polyvinyl acetate, polyester resin, polycondensation or polyaddition resin, polyurethane resin, alkyd resin or modified alkyd resin, phenol 15 resin, hydrocarbon resin such as indene/coumarone resin, silicone resin, drying vegetable and/or drying oils and/or physically drying binders based on a natural and/or synthetic resin. The synthetic resin employed as binder can be employed in the form of an emulsion, 20 dispersion or solution. Bitumen or bituminous substances may also be used as binders, in amounts of up to 10% by weight. In addition, colorants, pigments, water repellents, odour-masking agents, and inhibitors or anticorrosive agents and the like, all of which are known in their own right, can be employed. 25 In accordance with the invention, the compound or the concentrate preferably comprises, as organochemical binders, at least one alkyl resin or modified alkyl resin and/or a drying vegetable oil. Alkyd resins, which are preferably used in accordance with the invention, are those with an oil content of over 45% by weight, preferably 50 to 68% by weight. 30 - 93 Some or all of the abovementioned binders can be replaced by a fixative (mixture) or plasticiser (mixture). These additives are intended to prevent volatilisation of the active substances, as well as crystallisation or precipitation. They preferably replace 0.01 to 30% of the binder (based on 100% of binder employed). 5 The plasticisers are from the chemical classes of phthalic acid esters, such as dibutyl phthalate, dioctyl phthalate or benzyl butyl phthalate, phosphoric acid esters such as tributyl phosphate, adipic acid esters such as di-(2-ethylhexyl)-adipate, stearates such as butyl stearate or amyl stearate, oleates such as butyl oleate, glycerol ethers or 10 higher-molecular-weight glycol ethers, glycerol esters and p-toluenesulphonic esters. Fixatives are based chemically on polyvinyl alkyl ethers such as, for example, polyvinyl methyl ether, or ketones such as benzophenone and ethylenebenzophenone. 15 Other suitable solvents or diluents are, in particular, also water, if appropriate as a mixture with one or more of the abovementioned organochemical solvents or diluents, emulsifiers and dispersants. Particularly effective timber protection is achieved by industrial-scale impregnation 20 processes, for example vacuum, double-vacuum or pressure processes. The ready-to-use compositions can also comprise other insecticides, if appropriate, and also one or more fungicides, if appropriate. 25 Preferable additives are the insecticides and fungicides mentioned in WO 94/29268. The compounds mentioned in this document are an explicit component of the present patent application. Especially preferred mixing partners which may be mentioned are insecticides, such 30 as chlorpyriphos, phoxim, silafluofin, alphamethrin, cyfluthrin, cypermethrin, deltamethrin, permethrin, imidacloprid, NI-25, flufenoxuron, hexaflumuron, -94 transfluthrin, thiacloprid, methoxyphenoxide, triflumuron, clothianidine, spinosad and tefluthirn, and also fungicides, such as epoxyconazole, hexaconazole, azaconazole, propiconazole, tebuconazole, cyproconazole, metconazole, imazalil, dichlorfluanid, tolylfluanid, 3-iodo-2-propinyl-butyl carbamate, N-octyl-isothiazolin 5 3-one and 4,5-dichloro-N-octylisothiazolin-3-one. The compounds according to the invention can also be employed for protecting objects from fouling which come into contact with saltwater or brackish water, such as ships' hulls, screens, nets, buildings, moorings and signalling systems. 10 Fouling by sessile Oligochaeta, such as Serpulidae, and by shells and species from the Ledamorpha group (goose barnacles), such as various Lepas and Scalpellum species, or by species from the Balanomorpha group (acorn barnacles), such as Balanus or Pollicipes species, increases the frictional drag of ships and, as a 15 consequence, leads to a marked increase in operation costs owing to higher energy consumption and additionally owing to frequent residence in the dry dock. Apart from fouling by algae, for example Ectocarpus sp. and Ceramium sp., fouling by sessile Entomostraka groups, which come under the generic term Cirripedia 20 (cirriped crustaceans), is of particular importance. Surprisingly, it has now been found that the active compounds according to the invention have an outstanding antifouling action, either alone or in combination with other active substances. 25 By using the compounds according to the invention by themselves or in combination with other active substances, one can avoid the use of, or significantly reduce the concentration of compounds containing, heavy metals, such as, for example, in bis(trialkyltin) sulphides, tri-n-butyltin laurate, tri-n-butyltin chloride, copper(I) 30 oxide, triethyltin chloride, tri-n-butyl(2-phenyl-4-chlorophenoxy)tin, tributyltin oxide, molybdenum disulphide, antimony oxide, polymeric butyl titanate, phenyl- -95 (bispyridine)-bismuth chloride, tri-n-butyltin fluoride, manganese ethylenebisthiocarbamate, zinc dimethyldithiocarbamate, zinc ethylenebisthiocarbamate, zinc salts and copper salts of 2-pyridinethiol 1-oxide, bisdimethyldithiocarbamoylzinc ethylenebisthiocarbamate, zinc oxide, copper(I) 5 ethylene-bisdithiocarbamate, copper thiocyanate, copper naphthenate and tributyltin halides. If appropriate, the ready-to-use antifouling paints can additionally comprise other active substances, preferably algicides, fungicides, herbicides, molluscicides, or other 10 antifouling active substances. Preferably, substances to be used in combination with the antifouling compounds according to the invention are: 15 Algicides, such as 2 -tert.-butylamino-4-cyclopropylamino-6-methylthio- 1,3,5 triazine, dichlorophen, diuron, endothal, fentine acetate, isoproturon, methabenzthiazuron, oxyfluorfen, quinoclamine and terbutryn; Fungicides, such as benzo[blthiophenecarboxylic acid cyclohexylamide S,S-dioxide, 20 dichlofluanid, fluor-folpet, 3-iodo-2-propinyl butylcarbamate, tolylfluanid and azoles such as azaconazole, cyproconazole, epoxyconazole, hexaconazole, metconazole, propiconazole and tebuconazole; Molluscicides, such as fentin acetate, metaldehyde, methiocarb, niclosamide, 25 thiodicarb and trimethacarb; Ferrous chelates, or conventional antifouling active substances, such as 4,5-dichloro-2-octyl-4 30 isothiazolin-3-one, diiodomethylparatryl sulphone, 2-(N,N-di methylthiocarbamoylthio)-5-nitrothiazyl, potassium, copper, sodium and zinc salts of -96 2-pyridinethiol I-oxide, pyridine-triphenylborane, tetrabutyldistannoxane, 2,3,5,6 tetrachloro-4-(methylsulphonyl)-pyridine, 2,4,5, 6 -tetrachloroisophthalonitrile, tetramethylthiuram disulphide and 2
,
4
,
6 -trichlorophenylmaleinimide. 5 The antifouling compounds used comprise the active compound combinations according to the invention in a concentration of 0.001 to 50% by weight, in particular 0.01 to 20% by weight. Moreover, the antifouling compounds according to the invention comprise the 10 customary components such as, for example, those described in Ungerer, Chem. Ind. 1985, 37, 730-732 and Williams, Antifouling Marine Coatings, Noyes, Park Ridge, 1973. Besides the algicidal, fungicidal, molluscicidal active substances and insecticidal 15 active substances according to the invention, antifouling paints contain, in particular, binders. Examples of recognized binders are polyvinyl chloride in a solvent system, chlorinated rubber in a solvent system, acrylic resins in a solvent system, in particular 20 in an aqueous system, vinyl chloride/vinyl acetate copolymer systems in the form of aqueous dispersions or in the form of organic solvent systems, butadiene/styrene/acrylonitrile rubbers, drying oils such as linseed oil, resin esters or modified hardened resins in combination with tar or bitumens, asphalt and epoxy compounds, small amounts of chlorine rubber, chlorinated polypropylene and vinyl 25 resins. If appropriate, paints also contain inorganic pigments, organic pigments or colourants, which are preferably insoluble in salt water. Paints may furthermore contain materials such as colophonium to allow controlled release of the active 30 substances. Furthermore, the paints may comprise plasticisers, which are modifiers that affect the rheological properties and other conventional constituents. The - 97 compounds according to the invention or the abovementioned mixtures may also be incorporated into self-polishing antifouling systems. The active compound combinations are also suitable for controlling animal pests, in 5 particular insects, arachnids and mites, which are found in enclosed spaces such as, for example, dwellings, factory halls, offices, vehicle cabins and the like. They can be employed alone or in combination with other active substances and additives in domestic insecticide products for controlling these pests. They are active against sensitive and resistant species and against all developmental stages. These pests 10 include: From the order of Scorpionidea, for example, Buthus occitanus. From the order of Acarina, for example, Argas persicus, Argas reflexus, Bryobia 15 spp., Dermanyssus gallinae, Glyciphagus domesticus, Ornithodorus moubat, Rhipicephalus sanguineus, Trombicula alfreddugesi, Neutrombicula autumnalis, Dermatophagoides pteronissimus, Dermatophagoides forinae. From the order of Araneae, for example, Aviculariidae, Araneidae. 20 From the order of Opiliones, for example, Pseudoscorpiones chelifer, Pseudoscorpiones cheiridium, Opiliones phalangium. From the order of Isopoda, for example, Oniscus asellus, Porcellio scaber. 25 From the order of Diplopoda, for example, Blaniulus guttulatus, Polydesmus spp. From the order of Chilopoda, for example, Geophilus spp. 30 From the order of Zygentoma, for example, Ctenolepisma spp., Lepisma saccharina, Lepismodes inquilinus.
-98 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 fuliginosa, 5 Supella longipalpa. From the order of Saltatoria, for example, Acheta domesticus. From the order of Dermaptera, for example, Forficula auricularia. 10 From the order of Isoptera, for example, Kalotermes spp., Reticulitermes spp. From the order of Psocoptera, for example, Lepinatus spp., Liposcelis spp. 15 From the order of Coleptera, for example, Anthrenus spp., Attagenus spp., Dermestes spp., Latheticus oryzae, Necrobia spp., Ptinus spp., Rhizopertha dominica, Sitophilus granarius, Sitophilus oryzae, Sitophilus zeamais, Stegobium paniceum. From the order of Diptera, for example, Aedes aegypti, Aedes albopictus, Aedes 20 taeniorhynchus, Anopheles spp., Calliphora erythrocephala, Chrysozona pluvialis, Culex quinquefasciatus, Culex pipiens, Culex tarsalis, Drosophila spp., Fannia canicularis, Musca domestica, Phlebotomus spp., Sarcophaga carnaria, Simulium spp., Stomoxys calcitrans, Tipula paludosa. 25 From the order of Lepidoptera, for example, Achroia grisella, Galleria mellonella, Plodia interpunctella, Tinea cloacella, Tinea pellionella, Tineola bisselliella. From the order of Siphonaptera e.g. Ctenocephalides canis, Ctenocephalides felis, Pulex irritans, Tunga penetrans, Xenopsylla cheopis. 30 -99 From the order of Hymenoptera, for example, Camponotus herculeanus, Lasius fuliginosus, Lasius niger, Lasius umbratus, Monomorium pharaonis, Paravespula spp., Tetramorium caespitum. 5 From the order of Anoplura, for example, Pediculus humanus capitis, Pediculus humanus corporis, Phthirus pubis. From the order of Heteroptera, for example, Cimex hemipterus, Cimex lectularius, Rhodinus prolixus, Triatoma infestans. 10 Use in the area of domestic insecticides occurs alone or in combination with other suitable active substances, such as phosphoric acid esters, carbamates, pyrethroids, neonicotinoids, growth regulators or active substances from other known classes of insecticides. 15 They are used as aerosols, pressure-free spray products, for example pump and atomizer sprays, automatic fogging systems, foggers, foams, gels, evaporator products with evaporator tablets made of cellulose or polymer, liquid evaporators, gel and membrane evaporators, propeller-driven evaporators, energy-free or passive 20 evaporation systems, moth paper, moth bags and moth gels, as granules or dusts, in baits for spreading or in bait stations.
-100 Anwendun2sbeispiele Beispiel A 5 Meloidogyne-Test Lbsungsmittel: 7 Gewichtsteile Dimethylformamid Emulgator: 2 Gewichtsteil Alkylarylpolyglykolether 10 Zur Herstellung einer zweckmaBigen Wirkstoffzubereitung vermischt man 1 Ge wichtsteil Wirkstoff mit den angegebenen Mengen Lsungsmittel und Emulgator und verdunnt das Konzentrat mit Wasser auf die gewUnschte Konzentration. GefaBe werden mit Sand, Wirkstoffl6sung, Meloidogyne incognita-Ei-Larven-Sus 15 pension und Salatsamen geftillt. Die Salatsamen keimen und die Pflinzchen ent wickeln sich. An den Wurzeln entwickeln sich die Gallen. Nach der gewdnschten Zeit wird die nematizide Wirkung an Hand der Gallenbildung in % bestimmt. Dabei bedeutet 100 %, dass keine Gallen gefunden wurden; 0 % 20 bedeutet, dass die Zahl der Gallen an den behandelten Pflanzen der der unbe handelten Kontrolle entspricht. Bei diesel Test zeigen z.B. die Verbindungen der Herstellungsbeispiele 1-66, 1-72, I 76, 1-99, 1-135, 1-144, 1-150 und 1-155 gute Wirksamkeit.
- 101 Beispiel B Myzus-Test (Spritzbehandlung) 5 Lusungsmittel: 78 Gewichtsteile Aceton 1,5 Gewichtsteile Dimethylformamid Emulgator: 0,5 Gewichtsteile Alkylarylpolyglykolether Zur Herstellung einer zweckmaBigen Wirkstoffzubereitung vermischt man 1 Ge 10 wichtsteil Wirkstoff mit den angegebenen Mengen L6sungsmittel und Emulgator und verdiinnt das Konzentrat mit emulgatorhaltigem Wasser auf die gewUnschte Kon zentration. Chinakohlblattscheiben (Brassica pekinensis), die von allen Stadien der Grunen 15 Pfirsichblattlaus (Myzus persicae) befallen sind, werden mit einer Wirkstoff zubereitung der gewiinschten Konzentration gespritzt. Nach der gewUnschten Zeit wird die Wirkung in % bestimmt. Dabei bedeutet 100 %, dass alle Blattlause abgetbtet wurden; 0 % bedeutet, dass keine Blattliuse abgetotet 20 wurden. Bei diesem Test zeigen z.B. die Verbindungen der Herstellungsbeispiele 1-91, 1-126 und 1-140 gute Wirksamkeit.
- 102 Beispiel C Phaedon-Test (Spritzbehandlung) 5 L6sungsmittel: 78 Gewichtsteile Aceton 1,5 Gewichtsteile Dimethylformamid Emulgator: 0,5 Gewichtsteile Alkylarylpolyglykolether Zur Herstellung einer zweckma1igen Wirkstoffzubereitung vermischt man 1 Ge 10 wichtsteil Wirkstoff mit den angegebenen Mengen L6sungsmittel und Emulgator und verdbinnt das Konzentrat mit emulgatorhaltigem Wasser auf die gewinschte Kon zentration. Chinakohlblattscheiben (Brassica pekinensis) werden mit einer Wirkstoffzubereitung 15 der gewtinschten Konzentration gespritzt und nach dem Abtrocknen mit Larven des Meerrettichblattkafers (Phaedon cochleariae) besetzt. Nach der gewinschten Zeit wird die Wirkung in % bestimmt. Dabei bedeutet 100 %, dass alle Kaferlarven abgetotet wurden; 0 % bedeutet, dass keine Kaferlarven ab 20 get6tet wurde. Bei diesem Test zeigt z.B. die Verbindung des Herstellungsbeispiels 1-105 gute Wirksamkeit.
- 103 Beispiel D Spodoptera frugiperda-Test 5 L6sungsmittel: 7 Gewichtsteile Dimethylformamid Emulgator: 2 Gewichtsteile Alkylarylpolyglykolether Zur Herstellung einer zweckmaBigen Wirkstoffzubereitung vermischt man 1 Ge wichtsteil Wirkstoff mit den angegebenen Mengen L6sungsmittel und Emulgator und 10 verdiUnnt das Konzentrat mit emulgatorhaltigem Wasser auf die gewtinschte Kon zentration. Kohlblatter (Brassica oleracea) werden durch Tauchen in die Wirkstoffzubereitung der gewtinschten Konzentration behandelt und mit Raupen des Heerwurms 15 (Spodopterafrugiperda) besetzt, solange die Blatter noch feucht sind. Nach der gewunschten Zeit wird die Abt6tung in % bestimmt. Dabei bedeutet 100 %, dass alle Raupen abget6tet wurden; 0 % bedeutet, dass keine Raupen abget6tet wurden. 20 Bei diesem Test zeigt z.B. die Verbindung des Herstellungsbeispiels 1-70 gute Wirk samkeit.
- 104 Beispiel E Spodoptera frugiperda-Test/Kunstfutter 5 Lbsungsmittel: 31 Gewichtsteile Aceton Emulgator: 1 Gewichtsteil Alkylarylpolyglykolether Zur Herstellung einer zweckmaBigen Wirkstoffzubereitung vermischt man 1 Ge wichtsteil Wirkstoff mit den angegebenen Mengen Lbsungsmittel Emulgator und 10 verdunnt das Konzentrat mit emulgatorhaltigem Wasser auf die gewiinschte Kon zentration. Auf eine genormte Menge Kunstfutter wird eine angegebene Menge Wirk stoffzubereitung der gewUnschten Konzentration pipettiert. In 6-facher Wiederholung 15 werden je eine Larve (L3) des Heerwurms (Spodoptera frugiperda) auf das Futter gesetzt. Nach der gewtinschten Zeit wird die Abtbtung in % bestimmt. Dabei bedeutet 100 %, dass alle Tiere abgetbtet wurden; 0 % bedeutet, dass keine Tiere abget6tet wurden. 20 Bei diesem Test zeigt z.B. die Verbindung des Herstellungsbeispiels 1-22 gute Wirk samkeit.
- 105 Beispiel F Tetranychus-Test (OP-resistent/Spritzbehandlung) 5 L6sungsmittel: 78 Gewichtsteile Aceton 1,5 Gewichtsteile Dimethylformamid Emulgator: 0,5 Gewichtsteile Alkylarylpolyglykolether Zur Herstellung einer zweckmaUigen Wirkstoffzubereitung vermischt man I Ge 10 wichtsteil Wirkstoff mit den angegebenen Mengen L6sungsmittel und Emulgator und verdfinnt das Konzentrat mit emulgatorhaltigem Wasser auf die gewiinschte Kon zentration. Bohnenblattscheiben (Phaseolus vulgaris), die von allen Stadien der gemeinen 15 Spinnmilbe (Tetranychus urticae) befallen sind, werden mit einer Wirkstoffzube reitung der gewiinschten Konzentration gespritzt. Nach der gewfinschten Zeit wird die Wirkung in % bestimmt. Dabei bedeutet 100 %, dass alle Spinnmilben abget6tet wurden; 0 % bedeutet, dass keine Spinnmilben ab 20 get6tet wurden. Bei diesem Test zeigen z.B. die Verbindungen der Herstellungsbeispiele 1-90 und 1-95 gute Wirksamkeit.
- 106 Beispiel G Tetranychus-Test (OP-resistent/Tauchbehandlung) 5 L6sungsmittel: 7 Gewichtsteile Dimethylformamid Emulgator: 2 Gewichtsteil Alkylarylpolyglykolether Zur Herstellung einer zweckmaBigen Wirkstoffzubereitung vermischt man 1 Ge wichtsteil Wirkstoff mit den angegebenen Mengen Lbsungsmittel und Emulgator und 10 verdUnnt das Konzentrat mit emulgatorhaltigem Wasser auf die gewflnschte Kon zentration. Bohnenpflanzen (Phaseolus vulgaris), die stark von allen Stadien der Gemeinen Spinnmilbe (Tetranychus urticae) befallen sind, werden in eine Wirkstoffzubereitung 15 der gewiinschten Konzentration getaucht. Nach der gewtinschten Zeit wird die Wirkung in % bestimmt. Dabel bedeutet 100 %, dass alle Spinnmilben abgetbtet wurden; 0 % bedeutet, dass keine Spinnmilben abge t6tet wurden. 20 Bei diesem Test zeigt z. B. die Verbindung des Herstellungsbeispiels 1-22 gute Wirk samkeit.
- 107 Herstellungsbeispiele Beispiel (1-1) 5 (E/Z)-9-(3,4-Dichlorbenzyloxyimino)-spinosyn A-Aglykon: Das 9-Ketospinosyn A-Aglykon [Verbindung der allgemeinen Formel (II), worn R' fur Wasserstoff und A-B fUr die Gruppe -HC=CH- steht], kann entsprechend WO 02/079184 hergestellt werden. 10 50,0 mg (0,125 mmol) des 9-Ketospinosyn A-Aglykon wird in 2 ml abs. Pyridin verrnhrt und mit 143,lg (0,625 mmol) O-(3,4-Dichlorbenzyl)-hydroxylamin versetzt. Nach 24 Stunden Ruhren bei 25 'C wird der gesamte Reaktionsansatz im Vakuum eingeengt. AnschlieBend erfolgt eine Saulenchromatographie an Kiesel (Kieselgel 15 60-Merck, Komgrf3e: 0,04 bis 0,063 mm) mit dem FlieBmittel Cyclohexan: Essigsaureethylester (4:1) und Auftrennung des (E/Z)-Isomerengemisches. Man erhalt 46,8 mg (65,2 % der Theorie) des (Z)-9-(3,4-Dichlorbenzyloxyimino)-spinosyn A-Aglykon und 27,1 mg (37,7 % der Theorie) des (E)-9-(3,4-Dichlorbenzyl oxyimino)-spinosyn A-Aglykon. 20 (Z)-9-(3,4-Dichlorbenzyloxyimino)-spinosyn A-Aglykon:
C
31
H
3 7 Cl 2
NO
5 (574,5) LC-MS: m/z (%) = 574 (M*, 100); R, = 8,50 min. 25 (E)-9-(3,4-Dichlorbenzyloxyimino)-spinosyn A-Aglykon: 3 C-NMR: DMF-d 7 , 6 = 9,5, 16,2 (CH 3 ); 22,5, 28,9, 30,5, 34,3; 35,6 (5x CH 2 ); 33,1 (C-8); 35,1 (C-10); 41,8; 41,9, 46,3, 48,7, 48,8, 49,5, (CH); 72,1 (CH-OH); 74,0 (0
CH
2 ); 76,7 (CH-O-);129,8, 129,6 (-HC=CH-); 128,6, 130,3, 131,2, 141,1 (4x Ar-C); 30 131,1, 132,0 (2x Ar-C-Cl); 145,0, 147,9 (-HC=C-) 162,9 (C=N-); 172,7, 203,9 (C=0) ppm. Cs 3
H
37 Cl 2
NO
5 (574,5) LC-MS: m/z (%) = 574 (M+); R, = 8,74 min.
- 108 Beispiel (1-2) (E/Z)-1 7 - -Desosaminyl-9-[2-chloro-pyrid-5-yl-methoximino)-spinosyn A: 5 Das 17-0-Desosaminyl-9-ketospinosyn A 9-Pseudoaglykon [Verbindung der allgemeinen Formel (II), worn R' fur den Desosaminylrest und A-B fir die Gruppe -HC=CH- steht], kann entsprechend WO 02/079184 hergestellt werden. 10 287,5 mg (0,515 mmol) des 17-p-Desosaminyl-9-ketospinosyn A 9-Pseusoaglykons werden in 25 ml abs. Pyridin verriihrt und mit 327,0 g (2,06 mmol) O-(2-Chloro pyrid-5-yl-methy)-hydroxylamin versetzt. Nach 24 Stunden Ruhren bei 25 'C wird der gesamte Reaktionsansatz im Vakuum eingeengt. Anschlief3end erfolgt eine Saulenchromatographie an Kieselgel (Kieselgel 60-Merck, Komgr6Be: 0,04 bis 0,063 15 mm) mit dem FlieBmittel Dichlormethan: Methanol (10:1) und Auftrennung des (E/Z)-Isomerengemisches. Man erhalt 128 mg (35,5 % der Theorie) des (Z)-17- Desosaminyl-9-[2-chloro-pyrid-5-yl-methoximino)-spinosyn A und 68,9 mg (19,1 % der Theorie) des (E)-1 7 - -Desosaminyl-9-[2-chloro-pyrid-5-yl-methoximino) spinosyn A. 20 (Z)-1 7 - -Desosaminyl-9-[2-chloro-pyrid-5-yl-methoximino)-spinosyn A: 13C-NMR: DMF-dy, 5 = 32,5 (C-10); 35,5 (C-8) ppm.
C
38
H
5 2
CN
3 0 7 (698,3) LC-MS: m/z (%) = 698 (M*); Rt = 5.98 min. 25 (E)-17- -Desosaminyl-9-[2-chloro-pyrid-5-yl-methoximino)-spinosyn A: 13C-NMR: DMF-d 7 , 8 = 35,3 (C-10); 33,3 (C-8) ppm.
C
38
H
5 2 C1N 3 0 7 (698,3) LC-MS: m/z (%) = 698 (M*); R, = 5.68 min. 30 - 109 Beispiel (1-3) (E/Z)-9- [N-( 4 -Trifluoromethoxy-phenyl-aminocarbonyl)-hydrazono)-spinosyn
A
Aglykon: 5 Das 9-Ketospinosyn A-Aglykon [Verbindung der allgemeinen Formel (II), worn R' fUr Wasserstoff und A-B fur die Gruppe -HC=CH- steht], kann entsprechend WO 02/079184 hergestellt werden. 10 150,0 mg (0,375 mmol) des 9-Ketospinosyn A-Aglykon werden in 20 ml abs. Pyridin verrifhrt und mit 353,3 mg (1,49 mmol) 4 -(Trifluormethoxy-phenyl)-semicarbazid versetzt. Nach 24 Stunden Ruhren bei 25 'C wird der gesamte Reaktionsansatz im Vakuum eingeengt. AnschlieBend erfolgt eine erste Vorreinigung mittels Saulen chromatographie an Kieselgel (Kieselgel 60-Merck, Korngr6Be: 0,04 bis 0,063 mm) 15 mit dem FlieBmittel Cyclohexan: Aceton (2:1) und danach eine zweite Saulen chromatographie mit dem FlieBmittel Cyclohexan: Aceton (3:1). Danach wird das (E/Z)-Isomerengemisches mittels praparativer HPLC aufgetrennt. Man erhalt 56,2 mg (24,3 % der Theorie) des (Z)- 9
-[N-(
4 -Trifluoromethoxy-phenyl-aminocarbonyl) hydrazono)-spinosyn A-Aglykon und 92,0 mg (39,7 % der Theorie) des (E)-9-[N-(4 20 Trifluoromethoxy-phenyl-aminocarbonyl)-hydrazono)-spinosyn A-Aglykon. (Z)-9-[N-( 4 -Trifluoromethoxy-phenyl-aminocarbonyl)-hydrazono)-spinosyn
A
Aglykon: 25 3 C-NMR (DMF-d 7 , 6) = 32,9 (C-10); 38,0 (C-8) ppm.
C
32
H
3 8 F3N 3 0 6 (617,6) LC-MS: m/z (%) = 618 (MH*); R, = 7,69 min.
(E)-
9
-[N-(
4 -Trifluoromethoxy-phenyl-aminocarbonyl)-hydrazono)-spinosyn
A
Aglykon: 30
C
32
H
3 8 F3N 3 0 6 (617,6) LC-MS: m/z (%) = 618 (MH*); R, = 7,59 min.
-110 Analog den vorhergehenden Beispielen I-1 bis 1-3 k6nnen die in der nachstehenden Tabelle 3 aufgeffihrten Spinosyn-Derivate der allgemeinen Formel (1) hergestellt werden.
00000 I CCiO SU~r S 00 00 0~ ±N:- 0+ Q) 0 IT~ z IP 0 00 x 9 0 ~ 00 N N N -~ -~ z -~ U U U 00 '-N - ,~N - ,~N E 00 o~ -~ 0 5 ~ 0 5 - 00 -~ ~ I ~J ~ K '~ 00 Lr~ ~ in .~ & -
~
'- c~ ~ in 'no ~ o ~ o -~ ~ ~ 0 t n 0 in C~ .- 0 0 ~ ~ ~ 0+ ~ 0 ~ +~+~0 ~ 1+ CJ 1 Z~ ~ '- '-' ' (N (N (N ~ U U U U U U U II Ii II Ii II II II U U U U U U U LL L. II\ C-) (/) Q fr~ 0 0 0 0 0 0 0 N o ~ N N LI~ N N N-' U, c~ 0 C~ z~OO - - S S S - - - 0 m0 00 0 00 00 ot (Z) i, 00 if) 00 . 0 1 - 00 00 'o Cu u u 0 i,- 0 ur u 08 T IIIIii IIz IIz cfI z~ JQz t 00 0 Z 0 0 u u u,~ 00i W 000 n M C 2, ol 2r 00 in 0 0' QI 0 + 5 5s (Z) 0 0 Cr 00 00 0 +N C1 - - o 0 00 QQQ 0 0 oq en kn 0 0 / 00 u u I l 00 r- 00 00 0 ~ ~0 Cl 00 U --- u 0 06' r-: 06- : - U - ~ U ~ N 0 t~. ~ C~r N'~00 ~&0-'0 * , ;-: a 00 0 oc 00 0 C 00 ~ 0 "~0 ~~ ~ ~~ 0 ~ 0 0 0C 0 I', 0 00 - U 00 C-4I 00 -' W-' S U (-- 0- 06 n n5 o6 0 0 C)) 0r ;0 0 (z) ' ~ 0 ~ 0~ 1+~~ + 7 + ~ r ~ ±' WC) -. I) .C4 0 C Cl I) kn GC "~ m4 GC m5 r l~ N l C) " tn ~ W' W) m r in m kr 'n U cn x 0 = 0 0 0 U U 0 r) ~ 0 in-1- 0 . ~ ~ ~ Q C)) CD- - ~ + -~ Q) + ~ Q + + 01 0 A NA 0 0 n'U U U U u 00 ) 00 00 z 00 0 C) + Ne + W) 00 in 11 CN 00 kn 00 C4 m m~ in U cn Vn U c n r n U -' c n s. U U U U uU o 0 0 0 o w ow E- [-tNNNN C0 mt nk nM -kr- --- -- A in C)0 Q-' b~ Q) c b + + + kn Ml kn Cl( / ::N W) ON , SU uUUUU z0 0 ~ 00 0 0 0 z Tz 1 il 00 i 00 5l w ~ o 0 U' U U 0 U~t' - 0 0 0~45' 0 ~ 0'~ S - C>C SU U U U U U U zL z 0 T 0 0 0 0 0 0 0 z z z 00 0 00 o m0 I I0 C , , _ - U t- n ~ (9 CN ( - ( cn 0., - - V C - - r CS, m- m 0) Z- C N 0 % ) SU u u U 9(9( IIIIIIt II II 0 U) U)U oo Iv I~z S00 0 0 0 0 0 0 0' cJ. o Qo z T zT z T z ;o En NN op, 4 . - 00 00 0 0~I~~ Q b ~ Q n b + Q. j in .. 0 0 .) CM' G) ,n G) m0 m ~ (n C >= + Z 0 0 6- 0 0 0 + 0 6 ± ~~M Tn -Z m fl 0 ~ C~ n CfZ C U C c Z c O U 0 00 ,0 .00 0 00 IlIZIZo C) C) 00 o6 ~~. 00 + Q) Q.-)~ - c Z) -, - C 000 in -4 L C) )C 0 00 >==o )==o ca '~ t.0 0 00 0 z- 0 . .
-r o6o 00 u 0 O 00 00 In 00: .- 00t r) C 'ON 0 O ' c' ~ ~ ~ ~ ~ 0 O E. 6 m or i'- 6U~~~ 0 0 EA 00 = . 0-- 00 04 ~ 0 00 00 N 60 1rC) CiCU C0 0 ' + - + + . Do ciqic ,I ,. F0 u W) -s4 CS4 4 u u ~t1 0 0 0 (n ONal ;4 04 cif) C ) I K Cu - * ' 0. _ _ * Ci Cl 00 CC U 00 c'iS Co * Cl -N .5 c - ) N - 00 ~ 0- 00 l 0 =Z TZ Ta _T aS ~ ~ - ~+ N W NC W 00 7 c" 00 t" t, O) 00 *~0 C0 0 1 0 c00O + ~~~ +r' += -0 r- 00 000 ml - 0 ,o 00 IC UKII (9~~k /9(9(9(9 z~ Z 0 0 0I.(J I -C Z-, -( / a: N~~ N_____ ' 00 E~ m* 0 0 00 Cud eCn 0N-e - I) 00 a) 0c - C Cu u u ON ~ ON C) rj) L~ ~ O N ~ O ,.C) 0 0-~ .O0 C) 0 00 C u u
-
.~ ~ . ~00 k 0 0000 ~ > 00 i 00 C) CN 0 00 cf 00~ 0 00 0o0 TZ Il m TZ TZ E 0 00 0 h C_ C) ~0 0 O U ~>= 0 0 * Z N)- 0 ~~ cmo ~ (9 u u Q. Z rI cn U U U U 06 0 C .~ ~ ) CN 00 060) ~O CI -- N 0 - IN -- N u .4 V) a) 0l q 0) 0 r- -- r-CA 1- 11 0 N u -z 300 0 0 00 Qz '-.,0 en IT - r-U -~r 0 0 c~ 2 E C rq 00 I 000 0C 0 N 0 C In C 0 0- In i C r 0 c~'. 0- cn CD c C 00 C n 0 004 r- r- N 1 In 10 c 1 C) ) I I I - (XZ-0) Z-0) Z- Zz o = z T S0 0 0 000
NO
* D 00 C) c0 00 0 0 00 S0 ~ 0 r 10. r 0 0 0 0. 0 Ln 00 m tn - ON 0 +' Q)~0 +~r - QN +' Q + Q) + Q 0 ~ i N t0r)0 '. Nr cr~Cf ~~C ~ 20 0~ 0 z z 0 Ia 0 0 x 0 0 0 0 N ___ _____ o ~ N ~ en .0 00 o" . 0 6 ON 06 ON 06 - (N 0 0 C:) '- 0 N CD 0 D 0D 0 ON4 N O O. N ON -- ON + + Q) + + _~r ONC ON NCC 0 C) 0 11 )0C 0U 0.1U - -, ) 0( K 0 m ' 0l 0 Cf y o o 0 0 0 0 0 z0 0 0 0 0 0 00 00 0- 0 -- 0 ~ 0 n 0 0nC)L 0 CO 0 0C)c 0' a, Cl C' 0- 0a C-C) 0~, o" 0 - 0 0 0 '-, 0 00 .00 00 ON O' 0 'C C) 0 0 0 CA 0N N -- ON 0 0 ON T 0NO >1 0 W I cnC Ii0/ ON OC O ON 6 c 0 0 o" 04 0 O- 'MII 0 +.C D+ ON 0 Z 0c x 0 0 0 0 0 - 0 0 S - 00N ol * OC 0 00 O 0 O O C) Cl C) 00~ 0 0 cu~ L: + ~ ~ * oz en Cu ~ N - C -~U C9 C) Z
NN
- 141 Ausgangsstoffe der Formel (II) Beispiel (II-1) 5 9-Ketospinosyn A-Aglykon: Das 9-Ketospinosyn A-Aglykon (Ha) [Verbindung der allgemeinen Formel (H), worn Rl fUr Wasserstoff und A-B fUr die Gruppe -HC=CH- steht], kann wie in WO 02/079184 beschrieben mittels Pyridiniumdichromat-Oxidation aus der dem 10 Spinosyn A-Aglykon (vgl. WO 01/16303) hergestellt werden. 46.55 g (115.6 mmol) des Spinosyn A-Aglykons (H-1) wurden unter Inertgas in 1100 ml abs. Dichlormethan gelost und mit 43.51 g (115.6 mmol) Pyridiniumdichromat (PDC) versetzt. Nach 4 Stunden Ruhren bei 25 C und Zugabe von 900 ml 15 Diethylether wurden die ausgefallenen Chromsalze abfiltriert und das Filtrat im Vakuum eingeengt. Shulenchromatographie an Kieselgel (Kieselgel 60-Merck, KomgrdBe: 0,04 bis 0,063 mm) zunschst mit dem FlieBmittel Cyclohexan: Essigsaureethylester (1:1), dann 100 % Essigssureethylester. Man erhalt 3.68 g 9,17 Diketospinosyn-Aglykon und 23.40 g einer ca. 9:1-Mischung des Spinosyn A 20 Aglykons und 17-Ketospinosyn-Aglykon (11-1) neben 11.74 g zurtickgewonnenem Spinosyn A-Aglykon. Durch Umkristallisation der Mischung in Cyclohexan/Essig saureethylester wird das 9-KetospinosynA-Aglykon (H-1) auf > 98 % angereichert. Man erhalt 20.78 g 9-KetospinosynA-Aglykon (H-1) als farblose Kristalle. 25 DC: Rf (SiO 2 , Essigsaureethylester) = 0.44 'H-NMR (CDCI 3 , 6) = 6.77 (s, 13-H); 5.97 (d, 6-H); 5.88 (m, 5-H); 4.72 (m, 21-H); 3.69 (m, 17-H) u. a. - LC/ESI-MS: m/z (%) = 401 (25 %) [M]*, 289 (100). 30 ' 3 C-NMR (600 MHz, CDC 3 , 8) = 9,3, 15,7 (2x CH 3 ); 21,5, 28,3, 30,0, 33,9, 34,8, 43,1, 43,8 (7x CH 2 ); 40,6, 41,1, 44,3, 47,7, 48,1, 49,2 (6x CH); 72,5 (CH-OH); 77,0 - 142 (CH); 128,1, 129,3 (-HC=CH-); 144,9, 146,1 (-HC=C-); 172,6 (-O-C=O); 202,6, 216,1 (2x C=O) ppm. 9,17-Diketospinosyn-A Aglykon: DC: Rf (Si02, Essigsaureethylester) = 0.64. 5 H-NMR: CDC1 3 , 6 = 6.92 (s, 13-H); 5.97 (d, 6-H); 5.87 (m, 5-H); 4.85 (m, 21-H); 4.25 (q, 16-H) u. a. - LC/ESI-MS: m/z (%) = 399 (MH*, 100). Beispiel (11-2) 10 5,6-Dihydro-9-ketospinosyn A-Aglykon: Das 5,6-Dihydro-9-ketospinosyn A-Aglykon (Ha) [Verbindung der allgemeinen Formel (II), worn R' fUr Wasserstoff und A-B fur die Gruppe -H 2 C-CH2- steht], 15 kann analog zu WO 02/079184 beschrieben mittels Pyridiniumdichromat-Oxidation aus der dem 5,6-Dihydro-spinosyn A-Aglykon (vgl. WO 01/16303) hergestellt werden. 202 mg (0,5 mmol) 5,6-Dihydro-spinosyn A-Aglykon werden unter Inertgas in 5 ml 20 absolute Dichlormethan gelkst und mit 188 mg (0,5 mmol) PDC versetzt. Nach 4 Stunden Ruhren bei 25'C und Zugabe von 5 ml Diethylether werden die ausge fallenen Chronsalze abfiltriert und das Filtrat im Vakuum eingeengt. AnschlieBend erfolgt eine Saulenchromatographie an Kieselgel (Kieselgel 60-Merck, Komgr6Be: 0,04 bis 0,063 mm) zunachst mit dem FlieBmittel Cyclohexan: Essigsaureethylester 25 (1:1), dann mit 100 % Essigsaureethylester. Man erhalt 24 mg 5,6-Dihydro-9,17 diketospinosyn-Aglykon und 103 mg 5,6-Dihydro-17-ketospinosyn-Aglykon (11-1) neben 41 mg zurtickgewonnenem 5,6-Dihydro-spinosyn A-Aglykon. DC: Rf (SiO 2 , Essigsaureethylester) = 0,44 30 - 143 H-NMR (CDC1 3 , 8) = 6.83 (s, 13-H); 4,68 (m, 21-H); 3,69 (m, 17-H) u. a. - LC/ESI MS: m/z (%) = 403 (MH*, 23), 291 (100). 5,6-Dihydro-9,17-diketospinosyn-A-Aglykon: 5 DC: Rf (S10 2 , Essigsaureethylester) = 0.64. 'H-NMR (CDC 3 , 6) = 6.99 (s, 13-H); 4.82 (m, 21-H); 4.23 (q, 16-H) u. a. - LC/ESI MS: m/z (%) = 423 (M+Na*, 100). 10 Beispiel (11-3) 17- -D-Forosaminyl-9-ketospinosyn A 9-Pseudoaglykon: 15 Das 17- -D-Forosaminyl-9-ketospinosyn A 9-Pseudoaglykon (11-2) [Verbindung der Formel (II), worn R' fur D-Forosaminyl, R 3 fUr Wasserstoff, A-B fUr die Gruppe -HC=CH- steht] kann in zwei Reaktionsschritten aus dem 9-Ketospinosyn A Aglykon (11-1) synthetisiert werden: 20 a) Synthese des Trichloracetimidats (vgl. auch Methode bei G. R. Duffin et al. (2000), J. Chem. Soc., Perkin Trans. 1: 2237-2242 und WO 02/079184). b) Glykosidierung von 9-Ketospinosyn A-Aglykon mit Trichloracetimidat Trichlor acetimidats (vgl. auch Methode bei G. R. Duffin et al. (2000), J. Chem. Soc., 25 Perkin Trans. 1: 2237-2242 und WO 02/079184). Beispiel (11-4) 17- -D-Desosaminyl-9-ketospinosyn A 9-Pseudoaglykon: 30 - 144 Das 17- -D-Desosaminyl-9-ketospinosyn A 9-Pseudoaglykon (II-2) [Verbindung der Formel (II), worn R' fur D-Desosaminyl, R 3 fUr Wasserstoff, A-B fur die Gruppe -HC=CH- steht] kann in zwei Reaktionsschritten aus dem 9-Ketospinosyn A Aglykon (11-1) synthetisiert werden: 5 a) Glycosidierung: Man versetzt 2,0 g Molsieb 4A bei Raumtemperatur unter Inertgas nacheinander mit 2,7 g (7,34 mMol) Bis(cyclopentadienyl)hafnium-di chlorid 1,5 g (7,31 mMol) Silberperchlorat, 1,17 g (2,92 mMol) 9-Ketospinosyn Aglykon (1-1) und 41 ml absol. Methylenchlorid. Nach Abkuhlen auf -20'C 10 werden 0,34 g (1,46 mMol) 1-Fluor-2-O-methoxycarbonyl-D-desosamin (vgl. K. Suzuki et al., Tetrahedron Lett. 29 (29), 3571-3574, 1988), gel6st in 10,0 ml absol. Methylenchlorid, hinzugegeben. Nach zweistUndigem RUhren bei 0-5 'C wird der Reaktionsansatz mit gesattigter Natriumhydrogencarbonat-L6sung versetzt, Uber Celite filtriert und im Vakuum eingeengt. Das zurickbleibende 15 Rohprodukt wird Uber eine Kieselgelsaule (Kieselgel 60-Merck, KomgrdBe: 0,04 bis 0,063 mm) mit dem FlieBmittel Cyclohexan: Aceton (2:1) chromatographiert. Man erhalt 927 mg (51,4 % der Theorie) des 2-0-Methoxycarbonyl-17-p-D desosaminyl-9-ketospinosyn A 9-Pseudoaglykons welches anschlieBend 0 deblockiert werden kann. 20
C
34
H
49
NO
9 (615,7); LC-MS m/z (%) = 616 (MH*, 100). b) O-Deblockierungsreaktion: 203 mg (0,33 mMol) 2-0-Methoxycarbonyl-17-$-D desosaminyl-9-ketospinosyn A 9-Pseudoaglykon werden mit einem Gemisch aus 25 15 ml Methanol, 1,5 ml Triethylamin und 1,5 ml Wasser versetzt und 48 Stunden bei Raumtemperatur gerifhrt. Nach dem Einengen im Vakuum erhalt man 180 mg (97,7 % der Theorie) 17- -D-Desosaminyl-9-ketospinosyn A 9-Pseudoaglykon, das fUr weitere Reaktionen verwendet werden kann. 30 C 32
H
47
NO
7 (557,7); LC-MS m/z (%) = 558 (MH*, 100); Rt = 4,96 min.
- 145 Beispiel (11-5) 17- -D-O-Acetyl-desosaminyl-9-ketospinosyn A 9-Pseudoaglykon: 5 200,0 mg (0,36 mmol) 17- -D-Desosaminyl-9-ketospinosyn A 9-Pseudo-aglykon (II 2) wird 25 ml Dichlormethan verriihrt und nacheinander mit 87,8 mg (102,09 mmol) Essigsaureanhydrid, 94,3 mg ((0,93 mmol) Triethylamin und 43,8 mg (0,36 mmol) 4 N,N-Dimethylamino-pyridin (DMAP) versetzt. Nach 18 Stunden Ruhren bei 10 Raumtemperatur wird der gesamte Reaktionsansatz im Vakuum eingeengt und uber eine Kieselgelsiule (Kieselgel 60-Merck, Korngr6Be: 0,04 bis 0,063 mm) mit dem FlieBmittel Dichlormethan: Methanol (15:1) chromatographiert. Man erhalt 148,1 mg (68,8 % der Theorie) des 17- -D-O-Acetyl-desosaminyl-9-ketospinosyn A 9 Pseudoaglykons welches anschlieBend fur Folgereaktionen verwendet werden kann. 15
C
34
H
49
NO
8 (599,7); LC-MS m/z (%) = 600 (MH', 100); R, = 5,13 min. 3 C-NMR (DMF-d 7 ): 6 = 21,3 (CH 3 ); 71,9 (-CH-O-); 170,1 (-O-C=O) ppm. Beispiel (111-1) 20 Darstellung von 4-(N'-Isopropyloxycarbonyl-N'-methylsulfonylamino-phenethoxy) ammn: a) 2-(4-tert-Butyloxycarbonylamino-phenyl)-ethanol: 25 24,7 g (180 mmol) 2-(4-Aminophenyl)-ethanol werden in 200 ml Tetrahydro furan verruihrt und bei 0 0 C mit innerhalb von einer Stunde tropfenweise mit einer Lbsung aus 49,1 g (225 mmol) Di-tert-butyldicarbonat in 50 ml Tetrahydrofuran versetzt. Bereits nach zwei Stunden ist ein Umsatz von 75 % (HPLC-Kontrolle) erfolgt. Zur Vervollstandigung der Reaktion werden nach vier Stunden nochmals 30 0,1 Aquivalent Di-tert-butyldicarbonat hinzugegeben und ca. 18 Stunden bei - 146 Raumtemperatur geriihrt. AnschlieBend werden weitere 0,1 Aquivalent Di-tert butyldicarbonat zugegeben und bis zum vollstandigen Umsatz bei Raumtempe ratur ger~ihrt (Gesamtreaktionszeit: 26,5 Stunden). Der Reaktionsansatz wird im Vakuum eingeengt, der zurockbleibende farblose Feststoff (43,2 g) wird in 5 300 ml n-Hexan verrieben und ca. 18 Stunden bei Raumtemperatur gerihrt. Danach wird der Feststoff abgetrennt, mit 300 ml n-Hexan nachgewaschen und im Hochvakuum getrocknet. Man erhalt 41,7 g (97,6 % der Theorie) 2-(4-tert Butyloxycarbonylamino-phenyl)-ethanol, das fUr Folgereaktionen verwendet werden kann. 10 b) N-(4-Amino-phenethoxy)-phthalimid Hydrochlorid: 1,7 g (7,25 mmol) 2-(4-tert-Butyloxycarbonylamino-phenyl)-ethanol, 1,3 g (7,97 mmol) N-Hydroxy-phthalimid und 2,1 g (7,97 mmol) Triphenylphosphin werden in 45 ml Tetrahydrofuran verriihrt und bei 0 0 C tropfenweise mit 1,5 g 15 (8,7 mmol) Diethylazodicarboxylat (DEAD) versetzt. AnschlieBend ruhrt man die Reaktionsmischung weitere zehn Stunden bei 25'C. Danach wird das Lbsungsmittel im Vakuum abgezogen, der verbleibende RUckstand in Chloro form aufgenommen und die organische Phase viermal mit Natriumhydrogen carbonat Ldsung und Wasser gewaschen. Die organische Phase wird abgetrennt 20 und uber Natriumsulfat getrocknet. Nach Abziehen des Lbsungsmittels verbleibt rohes N-(4-tert-Butyloxycarbonylamino-phenethoxy)-phthalimid, das nicht weiter gereinigt wird. Zur Abspaltung der Schutzgruppe (Boc) wird das Rohprodukt in 7 ml Dioxan gelbst, portionsweise mit insgesamt sieben Aquivalenten 4N Salzsiure in Dioxan versetzt (HPLC-Kontrolle) und ca. 18 Stunden bei Raumtemperatur 25 gerfihrt. Danach wird der ausgefallene Feststoff abgetrennt, mit Dioxan gewaschen und im Hochvakuum getrocknet. Man erhalt 2,3 g (100 % der Theorie) N-(4-Amino-phenethoxy)-phthalimid Hydrochlorid das fUr Folgereak tionen eingesetzt werden kann. 30 c) N-[4-(N'-Methylsulfonylamino-phenethoxy)]-phthalimid: - 147 24,0 g (60,2 mmol) N-(4-Amino-phenethoxy)-phthalimid Hydrochlorid werden in 400 ml Dichlormethan vorgelegt und mit 14,6 ml Pyridin versetzt. Nach Zutropfen von 6,9 g (60,2 mmol) Methansulfonylchlorid bei 0 0 C wird der Reaktionsansatz ca. 18 Stunden bei Raumtemperatur gertihrt. AnschlieBend wird 5 die Reaktionslksung einmal gegen 5% wassrige Salzsaure und zweimal gegen destilliertes Wasser geschUttelt. Die organische Phase wird abgetrennt, getrocknet und im Vakuum eingeengt. Der verbleibende RUckstand wird in heiBem Ethanol verrtihrt und nach Abkuhlen wird die Lbsung filtriert. Nach Einengen des Filtrats wird der zurtickgebliebene Feststoff aus Chloroform:Cyclohexan umkristallisiert. 10 Man erhalt 8,6 g (39,6 % der Theorie) kristallines N-[4-(N'-Methylsulfonyl amino-phenethoxy)]-phthalimid. Aus dem FilterrUckstand ktnnen nochmals 2,7 g N-[4-(N'-Methylsulfonylamino-phen-ethoxy)]-phthalimid erhalten werden.
C
17
H
16
N
2 0 5 S (360,3); LC-MS m/z (%) = 361 (MH*, 100); R,= 6,59 min. 15 d) N-[4-(N'-Isopropyloxycarbonyl-N'-methylsulfonylamino-phenethoxy)] phthalimid: 2,0 g (5,55 mmol) N-[4-(N'-Methylsulfonylamino-phenethoxy)]-phthalimid werden in 75 ml absol. Pyridin verruhrt und bei 0 0 C unter Schutzgasatmosphare 20 (Argon) mit 2,7 g (22,2 mmol) Chlorameisensaureisopropylester versetzt. Nach einer Stunde Ruhren bei Raumtemperatur wird der gesamte Reaktionsansatz im Vakuum eingeengt. Der verbleibende RUckstand wird in Essigsaureethylester aufgenommen und einmal gegen 5 %ige wassrige Salzsaure geschuttelt. Danach wird die organische Phase zweimal gegen Wasser geschUttelt, abgetrennt, 25 getrocknet und im Vakuum eingeengt. Der verbleibende RUckstand wird fiber eine Kieselgelshule (Kieselgel 60-Merck, Korngrb8e: 0,04 bis 0,063 mm) mit dem FlieBmittel Cyclohexan: Aceton (2:1) chromatographiert. Man erhalt 2,4 g (99,2 % der Theorie) N-[4-(N'-Isopropyloxy-carbonyl-N'-methylsulfonylamino phenethoxy)]-phthalimid. 30
C
2 1
H
22
N
2 0 7 S (446,4); LC-MS m/z (%) = 447 (MH*); R, = 8,00 min.
- 148 e) 4-(N'-Isopropyloxycarbonyl-N'-methylsulfonylamino-phenethoxy)-amin: 2,3 g (5,55 mmol) N- [4-(N'-Isopropyloxy-carbonyl-N'-methylsulfonylamino pheneth-oxy)]-phthalimid werden in 20 ml Dichlormethan verriihrt und bei 5 Raumtemperatur mit 1,0 ml Methanol und 0,52 g (10,44 mmol) Hydrazin-hydrat versetzt. Der Reaktionsgemisch wird 18 Stunden bei Raumtemperatur geruhrt. Anschlieend wird der gesamte Reaktionsansatz filtriert und das Filtrat einmal gegen 5N Ammoniak-Lbsung geschiittelt. Die organische Phase wird abgetrennt, getrocknet und im Vakuum eingeengt. Man erhalt 1,1 g (64,8 % der Theorie) 4 10 (N'-Isopropyloxycarbonyl-N'-methylsulfonylamino-phenethoxy)-amin.
C
13
H
20
N
2 0 5 S (316,3); LC-MS m/z (%)= 317 (MH*, 25); Rt= 4,05 min. Beispiel (111-2) 15 Darstellung von 4-(N'-Ethyl-N'-methylsulfonylamino-phenethoxy)-amin: a) N-[4-(N'-Ethyl-N'-methylsulfonylamino-phenethoxy)]-phthalimid: 5,0 g (13,8 mmol) 4-(N'-Methylsulfonylamino-phenethoxy)-phthalimid werden 20 in 100 ml N,N-Dimethylformamid vorgelegt und mit 0,52 g (20,8 mmol) Natriumhydrid versetzt. Nach ca. 15 Minuten Ruhren bei Raumtemperatur wird mit 3,2 g (20,8 mmol) Ethyliodid versetzt und 18 Stunden bei Raumtemperatur weitergeriihrt. AnschlieBend wird die Reaktionslosung vorsichtig mit 1 ml Wasser versetzt und 30 Minuten bei Raumtemperatur geruhrt. Danach wird der 25 gesamte Reaktionsansatz im Vakuum eingeengt und der verbleibende RUckstand fiber eine Kieselgelsaule (Kieselgel 60-Merck, KorngroBe: 0,04 bis 0,063 mm) mit dem Fliefmittel Cyclohexan: Aceton (3:1) chromatographiert. Man erhalt 4,25 g (78,8 % der Theorie) N-[4-(N'-Allyl-N'-methylsulfonylamino-pheneth oxy)]-phthalimid. 30 CigH 20
N
2 0 5 S (388,4); LC-MS m/z (%) = 389 (MH*, 100); Rt = 5,54 min.
- 149 b) 4-(N'-Ethyl-N'-methylsulfonylamino-phenethoxy)-amin: 4,0 g (10,3 mmol) N-[4-(N'-Ethyl-N'-methylsulfonylamino-phenethoxy)] phthalimid werden in 40 ml Dichlormethan verrihrt und bei Raumtemperatur mit 5 2,0 ml Methanol und 1,0 g (20,6 mmol) Hydrazin-hydrat versetzt. Das Reaktions gemisch wird 18 Stunden bei Raumtemperatur geruhrt. Anschliessend wird der gesamte Reaktionsansatz filtriert und das Filtrat einmal gegen 5N Ammoniak Lsung geschtittelt. Die organische Phase wird abgetrennt, getrocknet und im Vakuum eingeengt. Man erhalt 2,4 g (92,4 % der Theorie) 4-(N'-Ethyl-N' 10 methylsulfonylamino-phenethoxy)-amin.
C
11
H
18
N
2 0 3 S (258,3); LC-MS m/z (%) = 259 (MH', 25); Rt= 2,25 min. Analog den vorhergehenden Beispielen III-1 und 111-2 kbnnen die in der 15 nachstehenden Tabelle 4 aufgefUhrten Aminoxyverbindungen der allgemeinen Formel (III) hergestellt werden.
- 150 Tabelle 4 R2-X-NH 2 (Ill) Bsp.-Nr. X R2 Physikalische Daten SoCH, 289 (MH*, 100); 2,55 min 111-3 0 N, SoCH: C 11
H
16
N
2 0 5 S (288,3) o yO CH3 303 (MH*, 100); 3,42 min I1I-4 0 N, SoCCH C 12 HisN 2 0 5 S (302,3) y 0 o- CH 3 317 (MH*, 100); 4,16 min III-5 0 N SoJCHa C1 3
H
2
ON
2 0sS (316,3) o o*CH2 315 (MH , 100); 3,87 mi Ill-6 0 N SOCH" C1 3 HisN 2 0sS (314,3) O y CH, 317 (MH*, 100); 3,83 min III-7 0 N SOCHCH 3
C
13
H
20
N
2 0 5 S (316,4) 0 oo -CH, 331 (MH*, 100); 4,54 mi III-8 O N SO 2
CHCH
3
C
14
H
22
N
2 0 5 S (330,4) oCH 331 (MH , 100); 4,43 min CH3 III-9 0 NSOCH-CH C 14
H
22
N
2 0 5 S (330,4) y O CH 2 329 (MH*, 100); 4,26 min II-10 0 NsSo2CHCH3 C 4
H
2
ON
2 0sS (328,4) - 151 Tabelle 4 (Fortsetzung) Bsp.-Nr. X R2 Physikalische Daten o y CH, 331 (MH*, 100); 4,53 min I-1 1 0 N, SoCH2CHCH, CJ 4
H
22
N
2 05S (330,4) o oC CH3 345 (MH*, 100); 5,20 min III-12 0 N, SoCCH2CHCH3 15
H
24
N
2 0 5 S (344,4) o o0 CH 3 345 (MH , 100); 5,13 min Ir-13 0 NSo2CH2CH2CH3 C 1 5
H
24
N
2 0 5 S (344,4) So CH2 343 (MH*, 100); 4,93 min MI-14 0 N, SOCCH 1 CHCH, 1 5
H
22
N
2 0 5 S (342,4) o o*' CH3 345 (MH*, 100); 4,97 min Ir-15 O N, SOCH(CH,)2 C15H 2 4
N
2 05S (344,4) Oy-CH3 331 (MH , 100); 4,31 min III-16 0 N, SO 2
CH(CH
3
)
2
C
1 4
H
22
N
2 0 5 S (330,4) o o 3CH3 345 (MH*, 100); 4,86 min YCH rn-17 0 N SCH(CH) C 15
H
24
N
2 0 5 S (344,4) H3 245 (MH*, 100); 1,69 min III-18 0 "'~SoCH, CioH 1 N20 3 S (244,3) - 152 Tabelle 4 (Fortsetzung) Bsp.-Nr. X R2 Physikalische Daten H+ Ed-19 0 N N oCH 1.51 (MH*, 100) / 211 min CioH 14
N
2 0 3 (210.2) N III-20 0 N oCH 225 (MH', 100) / 2.19 min 0
CIIH
16
N
2 0 3 (224.3) 111-21 0 o* CH 239 (MH*, 100) / 2.84 min 0
C
12 HJiN 2 0 3 (238.3) H 111-22 0 O CH, 239 (MH*, 75) / 2.74 min 0 CH3
C
1 2 HisN 2 0 3 (238.3) 11-23 0 N K0ow CH2 237 (MH*, 100) / 2.55 min 0
C
12
H
1 6N20 3 (236.3) E1-24 0 H, 253 (MH*, 85) / 3.10 min N N C N OCH C 13
H
20
N
2 0 3 (252.3) 11-25 0 H CF3 375 (MH*, 100) / 4.46 min N o C 16 Hi 7
F
3
N
2 0 3 S (374.4) m-26 0 KCH CF3 389 (MH*, 100) / 4.77 min O OC 17
H
1 9
F
3
N
2 0 3 S (388.4) 111-27 0 H, CF , 401 (MH*, 100) / 4.95 min N FN C 18 Hi 9
F
3
N
2 0 3 S (400.4) 111-28 0 H 245 (MH*, 100) / 1.93 min
OH
3 / C 1 oH 16
N
2 0 3 S (244.3)
CH
3 IR-29 0 H3 259 (MH+, 100) / 2.42 min N C H CiiH 18
N
2 0 3 S (258.3)
CH
3 - 153 Tabelle 4 (Fortsetzung) Bsp.-Nr. X R2 Physikalische Daten I-30 0 Ha 253 (MH*, 8) / 3.48 min N O CH 3
C
13
H
20
N
2 0 3 (252.3) H
CH
3 III-31 N-Z 271 (MH*, 8) / 7.22 min CiHiN 2 0 2 (270.3) Z = -CO-0-CH 2 -Phenyl LC-MS (sauer) m/z (%) / Rt (min) 5 - 154 Patentanspruche: 1. Verbindungen der allgemeinen Formel (I) 17 CH3 00H HN-R HsC 5 R 3 HH A-B H und deren Salze, in welcher 10 X fUr 0, NH oder NR 4 steht, R' fur Wasserstoff oder fur einen Amino-Zucker steht, 15 R2 fur Wasserstoff oder fUr gegebenenfalls substituiertes Alkyl, Cyclo alkyl, Arylalkyl, Hetarylalkyl, Aryl oder Hetaryl steht, oder, wenn X fUr NH oder NR 4 steht, fUr CO-R' oder CS-R' steht, worm 20 R' fur Amino, fur gegebenenfalls substituiertes Alkyl, Alkyl amino, Dialkylamino, Aryl, Arylamino, Hetarylamino, Aryl alkyl, Hetaryl oder Hetarylalkyl steht, 25 R3 fUr Wasserstoff oder Hydroxy steht, - 155 R4 ffur gegebenenfalls substituiertes Alkyl steht oder mit R 2 einen 3-, 4-, 5-, 6-, 7- oder 8-gliedrigen Ring bildet, der durch ein oder mehrere Heteroatom(e) wie 0, S, SO, SO 2 , NH oder NR 5 unterbrochen sein 5 kann und gegebenenfalls substituiert ist, R 5 fUr gegebenenfalls substituiertes Alkyl, Cycloalkyl, Arylalkyl, Hetarylalkyl, Aryl oder Hetaryl steht, und 10 A-B fUr eine der folgenden Gruppen steht: -HC=CH-, -HC=C(CH 3 )-,
-H
2
C-CH
2 - oder -H 2
C-CH(CH
3 )-. 2. Verbindungen gemaB Anspruch 1, dadurch gekennzeichnet, dass 15 X fur 0, NH oder NMe steht, R' fUr Wasserstoff oder fUr einen Amino-Zucker der Formel la bis Ig steht Me Me Me2N,, Me-N SR R Me' R Me H 20 la Me Me MeHN,,, HN S Me H 1b - 156 Me H 2N, H 2N,, R0 M Me H 1c Me Me o Y H O O Me 2 N Rs O O S R , Me Me 2 N Me 1d H OH HO Me 2N RSRO *S R Me Me 2 N 'Me 1e
CH
3 O
CH
3 O= Y H O 0 Me2NR C O ,S R, Me Me 2 N 'Me 1f Me Me''N M_ Me s Me M Me H 5 1g R2 fUr gegebenenfalls substituiertes Aryl-C 1
-C
3 -alkyl, insbesondere fUr Benzyl, 1-Phenyl-ethyl, 2-Phenyl-ethyl, 3-Phenyl-propyl, 2-Phenyl propyl, 2-Phenyl-isopropyl, 1-Methyl-2-phenyl-ethyl, Hetaryl-Ci-C 3 10 alkyl, Hetarylmethyl, 1-Hetaryl-ethyl, 2-Hetaryl-ethyl, 3-Hetaryl- - 157 propyl, 2-Hetaryl-propyl, 2-Hetaryl-isopropyl, I-Methyl-2-hetaryl ethyl steht, wobei die Substituenten ausgewahlt sein kbnnen aus der Reihe Wasserstoff, geradkettiges oder verzweigtes Alkyl mit bis zu 4 Kohlenstoffatomen, insbesondere Methyl, Ethyl, Propyl, Isopropyl, 5 Butyl, Isobutyl, sec-Butyl, tert-Butyl, Halogenalkyl mit bis zu 2 Kohlensoffatomen, insbesondere Trifluormethyl, Difluorchlormethyl, Pentafluorethyl, Alkenyl mit bis zu 3 Kohlenstoffatomen, cyclisches Alkyl mit bis zu 6 Kohlenstoffatomen, insbesondere Cyclopropyl, Cyclobutyl, Cyclopentyl, Cyclohexyl, Hydroxy, Halogen, insbesondere 10 Brom, Chlor, Fluor oder lod, Alkoxy, insbesondere Methoxy, Ethoxy, Propoxy, Isopropoxy, Butoxy, Isobutoxy, sec-Butoxy, tert-Butoxy, Cycloalkoxy, insbesondere Cyclopropyloxy, Alkenyloxy, insbesondere Allyloxy, Dioxoalkylen, insbesondere Dioxomethylen, Halogenalkoxy, insbesondere Trifluormethoxy, Alkylthio, insbeson 15 dere Methylthio, Halogenalkylthio, insbesondere Trifluormethylthio, Alkylsulfonyl, insbesondere Methylsulfonyl, Halogenalkylsulfonyl, insbesondere Trifluormethylsulfonyl, Hetarylsulfonyl, insbesondere N Morpholinosulfonyl oder N-Pyrazolylsulfonyl, Nitro, Amino, eine geeignete cyclische Aminogruppe, insbesondere N-Pyrrolidino, N 20 Piperidino, N-Morpholino, N-(2,6-Dimethyl-morpholino), N-Methyl piperazino, N-Thiomorpholino oder N-Dioxothiomorpholino, Alkyl amino, insbesondere Methylamino, Ethylamino, Propylamino, Iso propylamino, Butylamino, sec-Butylamino, Isobutylamino, tert-Butyl amino, Alkylenamino, insbesondere Propylenamino, Dialkylamino, 25 insbesondere Dimethylamino, Diethylamino, Carboxyl, Carbamoyl, Cyano, Alkoxycarbonyl, insbesondere Methoxycarbonyl, Ethoxy carbonyl, Propyloxycarbonyl, Isopropyloxycarbonyl, Butyloxycarb onyl, sec-Butyloxycarbonyl, Isobutyloxycarbonyl, tert-Butyloxy carbonyl, Alkylenoxycarbonyl, insbesondere Propylenoxycarbonyl, N 30 Alkoxycarbonyl-amino, insbesondere N-Methoxycarbonylamino, N Ethoxycarbonylamino, N-Propyloxycarbonylamino, N-Isopropyloxy- - 158 carbonyl-amino, N-Butyloxycarbonyl-amino, N-sec-Butyloxycarb onylamino, N-Isobutyloxycarbonylamino, N-tert-Butyloxycarbonyl amino, Cyanoalkylencar-bonylamino, insbesondere Cyanomethylen carbonylamino, Cyanoethylen-carbonylamino, N-Alkylenoxycarbonyl 5 amino, insbesondere N-Propylenoxycarbonylamino, N-Alkyl sulfonylamino, insbesondere N-Methylsulfonyl-amino, N-Ethyl sulfonylamino, N-Propylsulfonylamino, N-Isopropylsulfonyl-amino, N-Butylsulfonylamino, N-sec-Butylsulfonylamino, N-Isobutyl sulfonyl-amino, N-tert-Butylsulfonylamino, N-Alkylensulfonylamino, 10 insbesondere N-Propylensulfonylamino, gegebenenfalls substituiertes Arylsulfonylamino, insbesondere 4-Trifluormethyl-phenylsulfonyl amino, N-Alkoxycarbonyl-N-alkyl-amino, insbesondere N-Methoxy carbonyl-N-methyl-amino, N-Methoxy-carbonyl-N-ethyl-amino, N Ethoxycarbonyl-N-methyl-amino, N-Ethoxycarbonyl-N-ethyl-amino, 15 N-Propyloxycarbonyl-N-methyl-anino, N-Propyloxycar-bonyl-N ethyl-amino, N-Isopropyloxycarbonyl-N-methyl-amino, N-Isopropyl oxycarbonyl-N-ethyl-amino, N-Butyloxycarbonyl-N-methyl-amino, N Butyloxy-carbonyl-N-ethyl-amino, N-sec-Butyloxycar-bonyl-N methyl-amino, N-sec-Butyloxycarbonyl-N-ethyl-amino, N-Isobutyl 20 oxy-carbonyl-N-methyl-amino, N-Isobutyloxycarbonyl-N-ethyl amino, N-tert-Butyloxycarbonyl-N-methyl-amino, N-tert-Butyloxy carbonyl-N-methyl-amino, N-Alkylenoxycarbonyl-N-alkyl-amino, insbesondere N-Propylenoxycarbonyl-N-methylamino, N-Propylen oxycarbonyl-N-methyl-amino, N-Alkylcarbonyl-N-alkylamino, insbe 25 sondere N-Methylcarbonyl-N-methyl-amino, N-Methyl-carbonyl-N ethyl-amino, N-Ethyl-carbonyl-N-methyl-amino, N-Ethylcarbonyl-N ethyl-amino, N-Cycloalkylcarbonylamino, insbesondere N-Cyclo propyl-carbonylamino, N-1-Methylcycloprop-1-yl-carbonyl-N-amino, N-Cyclobutyl-amino, N-Alkoxy-carbonyl-N-alkylsulfonyl-amino, 30 insbesondere N-Methoxy-carbonyl-N-methylsulfonyl-amino,
N
Methoxycarbonyl-N-ethyl-sulfonylamino, N-Ethoxy-carbonyl-N- -159 methylsulfonyl-amino, N-Ethoxy-carbonyl-N-ethyl-sulfonylamino, N Propyloxycarbonyl-N-methyl-sulfonyl-amino, N-Propyloxy-carbonyl N-ethylsulfonyl-amino, N-Isopropyloxycarbonyl-N-methylsulfonyl amino, N-Isopropyloxycarbonyl-N-ethylsulfonylamino, N-Butyl 5 oxycarbonyl-N-methylsulfonyl-amino, N-Butyloxycarbonyl-N-ethyl sulfonylamino, N-sec-Butyloxycarbonyl-N-methylsulfonyl-amino, N sec-Butyloxycarbonyl-N-ethyl-sulfonyl-amino, N-Isobutyloxycarb onyl-N-methyl-sulfonyl-amino, N-Isobutyloxycarbonyl-N-ethyl sulfonylamino, N-tert-Butyloxy-carbonyl-N-methyl-sulfonylamino, N 10 tert-Butyloxycarbonyl-N-methylsulfonyl-amino, N-Alkylen-oxycarb onyl-N-alkylsulfonyl-amino, insbesondere N-Propylenoxycarbonyl-N methylsulfonyl-amino, N-Propylenoxycarbonyl-N-methylsulfonyl amino, N-Alkylcarbonyl-N-alkylsulfonyl-amino, insbesondere N Methylcarbonyl-N-methylsulfonyl-amino, N-Methylcarbonyl-N-ethyl 15 sulfonyl-amino, N-Ethyl-carbonyl-N-methylsulfonyl-amino, N Ethylcarbonyl-N-ethyl-sulfonylamino, N-Cycloalkylcarbonyl-N-alkyl sulfonyl-amino, insbesondere N-Cyclopropyl-carbonyl-N-methyl sulfonyl-amino, N-1-Methylcycloprop-1-yl-carbonyl-N-methylsulfo nylamino, N-Cyclobutyl-N-methylsulfonylamino, Alkylamino 20 carbonylamino, insbesondere N-Methylaminocarbonylamino, N Ethylamino-carbonylamino, N,N-Dialkylaminocarbonylamino, insbe sondere N,N-dimethylaminocarbonylamino, N-Alkylaminosulfonyl amino, insbesondere N-Methylaminosulfonylamino, N,N-Dialkyl aminosulfonylamino, insbesondere N,N-Dimethylaminosulfonyl 25 amino, und wenn X fur NH oder NMe steht, R2 weiterhin fUr CO-R' oder CS-R' steht, 30 worm - 160 R' fUr Amino, fUr gegebenenfalls substituiertes CI-C 4 Alkyl, Ci-C 4 -Alkylamino, Di-C-C 4 -alkylamino, Aryl, Arylamino, Hetarylamino, Aryl-Ci-C 3 -alkyl, Hetaryl 5 oder Hetaryl-C 1
-C
3 -alkyl steht, R4 fUr gegebenenfalls substituiertes Ci-C 4 -Alkyl steht oder mit R2 einen 6-gliedrigen Ring bildet, der durch 0, S oder NR 5 unterbrochen sein kann und gegebenenfalls substituiert ist, und 10
R
5 fur gegebenenfalls substituiertes Ci-C 4 -Alkyl steht. 3. Verbindungen gemaB Anspruch 1 oder 2, dadurch gekennzeichnet, dass 15 X fur 0 oder NH steht, R' fUr Wasserstoff oder fur einen Amino-Zucker der Formel la, Id oder le steht Me Me Me N,,, MeN _ R Me H la Me Me O H 01 O O Me2 N Rs RC Me MeN2 N Me 20 1d - 161 H OH HO Me 2 N- Ij R sO0 O * eS R Me Me 2 N Me le R2 fur Aryl-Cr-C 3 -alkyl, insbesondere fur Benzyl, 1-Phenyl-ethyl, Hetaryl-C-C 3 -alkyl, Hetarylmethyl, insbesondere Pyridylmethyl, 5 Pyrimidylmethyl, Pyridazinylmethyl, Pyrazylmethyl, Furylmethyl, Thiazolylmethyl, Pyrazolylmethyl, Oxazolylmethyl, Isoxazolylmethyl, Thiazolylmethyl, Imidazolylmethyl, Triazolylmethyl, Tetrazolyl methyl, Dihydro-dioxazinylmethyl, 1-Hetaryl-ethyl, insbesondere 1 Pyridylethyl, 1-Pyrimidylethyl, 1-Pyridazinylethyl, 1-Pyrazylethyl, 1 10 Furylethyl, 1-Thiazolylethyl, 1-Pyrazolylethyl, 1-Oxazolylethyl, 1 Isoxazolylethyl, I-Thiazolylethyl, 1-Imidazolylethyl, 1-Triazolylethyl, 1-Tetrazolylethyl, 1-Dihydro-dioxazinylethyl steht, die jeweils gegebe nenfalls durch Reste aus der Reihe Wasserstoff, geradkettiges oder verzweigtes Alkyl mit bis zu 4 Kohlenstoffatomen, insbesondere 15 Methyl, Ethyl, Propyl, tert-Butyl, Halogenalkyl, insbesondere Trifluormethyl, Hydroxy, Halogen, insbesondere Brom, Chlor, Fluor oder lod, Alkoxy, insbesondere Methoxy, Ethoxy, tert-Butoxy, Halogenalkoxy, insbesondere Trifluormethoxy, Alkylthio, insbeson dere Methylthio, Halogenalkylthio, insbesondere Trifluormethylthio, 20 Alkylsulfonyl, insbesondere Methylsulfonyl, Halogenalkylsulfonyl, insbesondere Trifluormethylsulfonyl, Nitro, Amino, Alkylamino, insbesondere Methylamino, Ethylamino, N-Alkoxycarbonylamino, insbesondere N-Methoxycarbonylamino, N-Ethoxycarbonylamino, N Propyloxycarbonylamino, N-Isopropyloxycarbonyl-amino, N-Butyl 25 oxycarbonylamino, N-sec-Butyloxycarbonylamino, N-Isobutyloxy carbonylamino, N-tert-Butyloxycarbonylamino, N-Alkylenoxycarb onyl-amino, insbesondere N-Propylenoxycarbonylamino, N-Alkyl- - 162 sulfonylamino, insbesondere N-Methylsulfonylamino, N-Ethylsul fonylamino, N-Propyl-sulfonylamino, N-Isopropylsulfonylamino, N Butylsulfonylamino, N-sec-Butylsulfonylamino, N-Isobutylsulfonyl amino, N-tert-Butylsulfonylamino, N- N-Alkoxycarbonyl-N-alkyl 5 amino, insbesondere N-Methoxycarbonyl-N-methyl-amino, N-Meth oxy-carbonyl-N-ethyl-amino, N-Ethoxycarbonyl-N-methyl-amino, N Ethoxycarbonyl-N-ethyl-amino, N-Propyloxycarbonyl-N-methyl amino, N-Propyloxycar-bonyl-N-ethyl-amino, N-Isopropyloxycarb onyl-N-methyl-amino, N-Isopropyl-oxycarbonyl-N-ethyl-amino, N 10 Butyloxy-carbonyl-N-methyl-amino, N-Butyloxy-carbonyl-N-ethyl amino, N-sec-Butyloxycar-bonyl-N-methyl-amino, N-sec-Butyloxy carbonyl-N-ethyl-amino, N-Isobutyloxy-carbonyl-N-methyl-amino, N Isobutyloxycarbonyl-N-ethyl-amino, N-tert-Butyloxycarbonyl-N methyl-amino, N-tert-Butyloxycarbonyl-N-methyl-amino, N-Alkylen 15 oxycarbonyl-N-alkyl-amino, insbesondere N-Propylenoxycarbonyl-N methylamino, N-Propylenoxycarbonyl-N-methyl-amino, N-Alkyl carbonyl-N-alkylamino, insbesondere N-Methylcarbonyl-N-methyl amino, N-Methylcarbonyl-N-ethyl-amino, N-Ethyl-carbonyl-N methyl-amino, N-Ethylcarbonyl-N-ethyl-amino, N-Cycloalkylcarb 20 onylamino, insbesondere N-Cyclopropylcarbonylamino, N-1 Methylcycloprop-1-yl-carbonyl-N-amino, N-Cyclobutylamino, N Alkoxy-carbonyl-N-alkylsulfonyl-amino, insbesondere N-Methoxy carbonyl-N-methylsulfonyl-amino, N-Methoxycarbonyl-N-ethyl sulfonylamino, N-Ethoxy-carbonyl-N-methylsulfonyl-amino, N 25 Ethoxy-carbonyl-N-ethylsulfonyl-amino, N-Propyloxycarbonyl-N methyl-sulfonyl-amino, N-Propyloxycarbonyl-N-ethylsulfonyl-amino, N-Isopropyloxycarbonyl-N-methylsulfonyl-amino, N-Isopropyloxy carbonyl-N-ethylsulfonyl-amino, N-Butyloxycarbonyl-N-methyl sulfonylamino, N-Butyloxycarbonyl-N-ethyl-sulfonylamino, N-sec 30 Butyloxy-carbonyl-N-methylsulfonyl-amino, N-sec-Butyloxycarbonyl N-ethylsulfonyl-amino, N-Isobutyloxycarbonyl-N-methyl-sulfonyl- - 163 amino, N-Isobutyloxy-carbonyl-N-ethylsulfonyl-amino, N-tert Butyloxy-carbonyl-N-methylsulfonyl-amino, N-tert-Butyloxycarbonyl N-methylsulfonyl-amino, N-Alkylen-oxycarbonyl-N-alkylsulfonyl amino, insbesondere N-Propylenoxy-carbonyl-N-methylsulfonyl 5 amino, N-Propylenoxycarbonyl-N-methylsulfonyl-amino, N Alkylcarbonyl-N-alkylsulfonyl-amino, insbesondere N Methylcarbonyl-N-methylsulfonyl-amino, N-Methylcarbonyl-N-ethyl sulfonyl-amino, N-Ethyl-carbonyl-N-methylsulfonyl-amino, N-Ethyl carbonyl-N-ethyl-sulfonyl-amino, N-Cycloalkylcarbonyl-N-alkyl 10 sulfonyl-amino, insbesondere N-Cyclopropyl-carbonyl-N-methylsulfo nyl-amino, N-i -Methylcycloprop- 1 -yl-carbonyl-N-methylsulfonyl amino, N-Cyclobutyl-N-methylsulfonylamino, Alkylamino carbonylamino, insbesondere N-Methylaminocarbonylamino, N-Ethyl aminoicarbonylamino, N,N-Dialkylaminocarbonylamino, insbeson 15 dere N,N-dimethylaminocarbonylamino, N-Alkylaminosulfonylamino, insbesondere N-Methylaminosulfonylamino, N,N-Di alkylaminosulfonylamino, insbesondere N,N-Dimethylaminosulfonyl amino, substituiert sein k6nnen, und 20 wenn X fur NH oder NMe steht, R 2 weiterhin fur CO-R' oder CS-R' steht, worm 25 R' fUr Amino, Arylamino, insbesondere Trifluormeth oxyphenylamino, Trifluormethylphenylamino, Chlor phenylamino, Hetarylamino, insbesondere Brom pyridylamino, Trifluormethylpyridylamino steht. 30 - 164 4. Verbindungen gemaB einem der Ansprtiche 1 bis 3, dadurch gekennzeichnet, dass X fUr 0 steht, 5 R' fUr Wasserstoff oder fur einen Amino-Zucker der Formel 1 a oder le steht Me Me Me N, Me R Me H la H OH HO Me2N R S0O RS Me Me 2 N Me 1e 10 R2 fUr Benzyl, 1-Phenyl-ethyl, Hetarylmethyl, insbesondere Pyridylmethyl, Pyridazinylmethyl, Thiazolylmethyl, Pyrazolylmethyl, Isoxazolylmethyl, Imidazolylmethyl, Dihydro-dioxazinylmethyl, 1 Pyridylethyl, 1-Thiazolylethyl, 1-Dihydro-dioxazinylethyl steht, die 15 jeweils gegebenenfalls durch Reste aus der Reihe Wasserstoff, Methyl, tert-Butyl, Trifluormethyl, Brom, Chlor, Fluor, Methoxy, Trifluormethoxy, Nitro, Amino, Methylamino, Ethylamino, N Methoxycarbonylamino, N-Ethoxycarbonylamino, N-Propyloxy carbonyl-amino, N-Isopropyloxycarbonyl-amino, N-tert-Butyloxycarb 20 onylamino, N-Propylenoxycarbonylamino, N-Methylsulfonylamino, N-Ethylsulfonyl-amino, N-Methoxycarbonyl-N-methyl-amino, N Ethoxycarbonyl-N-methyl-amino, N-Isopropyloxycarbonyl-N-methyl amino, N-tert-Butyloxycarbonyl-N-methyl-amino, N-Propylenoxy- - 165 carbonyl-N-methylamino, N-Cyclopropyl-carbonylamino, N-1 Methylcycloprop- 1 -yl-carbonyl-N-amino, N-Methoxy-carbonyl-N methylsulfonyl-amino, N-Methoxycarbonyl-N-ethyl-sulfonylamino, N-Isobutyloxycarbonyl-N-methyl-sulfonyl-amino, N-tert 5 Butyloxycarbonyl-N-methylsulfonyl-amino, N-tert-Butyloxycarbonyl N-methylsulfonyl-amino, N-Propylenoxycarbonyl-N-methylsulfonyl amino, N-Cyclopropylcarbonyl-N-methyl-sulfonyl-amino, N-1 Methylcycloprop- 1 -yl-carbonyl-N-methyl-sulfonyl-amino, N,N Dialkylaminocarbonylamino, N-Methylaminosulfonylamino, N,N 10 Dialkylaminosulfonylamino, substituiert sein kinnen. 5. Verbindungen gemaB einem der AnsprUche 1 bis 4, dadurch gekennzeichnet, dass 15 A-B fur eine der folgenden Gruppen steht: -HC=CH- oder -H 2
C-CH
2 - steht. 6. Verfahren zum Herstellen einer Verbindung der allgemeinen Formel (I), Ri O 17 C3 0 H H __ 21 OO .-- xR R 3 H HA-B H 20 und deren Salze, in welcher - 166 R', R 2 , R 3 , X und A-B die in einem der Anspruche I bis 5 angegebenen Bedeutungen besitzen, dadurch gekennzeichnet, dass man 5 Verbindungen der allgemeinen Formel (II) 7 CH3 HH O 152 in welcher R , und X die oben angegebenen Bedeutungen besitzen, 20 in Gegenwart eines basischen Hilfsmittels und gegebenenfalls in Gegenwart eines Verdtinnungsmittels umsetzt. 7. Mittel zur Bekampfung von tierischen Schadlingen enthaltend eine oder 25 mehrere Verbindungen gemaB einem der AnsprUche 1 bis 5.
- 167 8. Verwendung von Verbindungen gemaB einem der AnsprUche 1 bis 5 zum Bekampfen von tierischen Schadlingen. 5 9. Verfahren zum Herstellen von Schadlingsbekampfungsmittel, dadurch gekennzeichnet, dass man eine oder mehrere Verbindungen gemaB einem der AnsprUche 1 bis 5 mit Streckmitteln und/oder oberflachenaktiven Substanzen vermischt. 10 10. Verbindungen der allgemeinen Formel (II) 1 CH3 H C 21 (11 3 O0 R 3 H H A-B H in welcher 15 5R fUr einen Amino-Zucker der Formel Id oder le steht Me Me OH 01 O= O O H O O Me2N Rs OC Me Me 2 N Me 1d - 168 H OH HO 2 RsO MS R Me Me 2 N Me 1e und
R
3 und A-B die in Anspruch1 angegebenen Bedeutungen besitzen. 5 11. Verbindungen der allgemeinen Formel (II) 17 CH3 O H HO H3C R 3 H H A-B H 10 in welcher R' fUr einen Amino-Zucker der Formel 1 a steht Me Me Me 2 N,, I~ RO0 Me' RO Me H 1a 15 R3 ffur Wasserstoff oder Hydroxy steht, und - 169 A-B fUr eine der folgenden Gruppen steht: -HC=C(CH 3 )-, -H 2
C-CH
2 - oder
-H
2
C-CH(CH
3
)-.
-170 9-Ketospinosyn-Derivate Zu s amime n fa s sung Die vorliegende Erfindung betrifft Derivate von 9-Ketospinosynen, die in C-9 Position mit einem Rest =N-(O, NH oder NRx)-Ry substituiert sind, Verfahren zu ihrer Herstellung und ihre Verwendung zur Bekampfung von tierischen Schadlingen.

权利要求:
Claims (6)
[1] 1. Verbindungen der allgemeinen Formel (I) R" 5O 17 CH3 H a C 2 0 H NH und deren Salze, in welche 10 X fur 0, NH older NR 4 steht, R 1 fur Wasserstoff oder far einen Amino-Zucker steht, 15 R 2 fur Wasserstoff older fur gegebenenfalls substituiertes Alkyl, Cyclo alkyl, Arylalkyl, Hetarylalkyl, Aryl oder Hetaryl steht, older, wenn X fur NH oder NR 4 steht, fur CO-R' oder CS-R' steht, worm 20 R' fir Amino, fur gegebenenfalls substituiertes Alkyl, Alkyl amino, Dialkylamino, Aryl, Arylamino, Hetarylamino, Aryl alkyl, Hetaryl oder Hetarylalkyl steht, 25 R 3 fdr Wasserstoff oder Hydroxy steht, WO 2004/065402 PCT/EP2004/000058 - 158 R 4 fur gegebenenfalls substituiertes Alkyl steht oder mit R 2 einen 3-, 4-,
[2] 5-, 6-, 7- oder 8-gliedrigen Ring bildet, der durch ein oder mehrere Heteroatom(e) wie 0, S, SO, SO 2 , NH oder NRs unterbrochen sein 5 kann und gegebenenfalls substituiert ist, R fur gegebenenfalls substituiertes Alkyl, Cycloalkyl, Arylalkyl, Hetarylalkyl, Aryl oder Hetaryl steht, und 10 A-B fur eine der folgenden Gruppen steht: -HC=CH-, -HC=C(CH 3 )-, -H2C-CH 2 - oder -H 2 C-CH(CH 3 )-. 2. Verbindungen gemaB Anspruch 1, dadurch gekennzeichnet, dass 15 X fr 0, NH oder NMe steht, R' fUr Wasserstoff oder fur einen Arnino-Zucker der Formel la bis lg steht Me Me Me 2 m, Me ' RR H 20 Me Me MHsN,,, HN O R Me H lb WO 2004/065402 PCT/EP2004/000058 -159 Me H 2 N, *' TR 0 Me H 10 Me Me 0 0 Mee" M Id OH HO -~ SR Me Me 2 N' Me le ~CH 3 O , CH 3 H Me eN Me 6 S Re Me Me2N' R Me MMe H 5 1 g R fdr gegebenenfalls substituiertes Aryl-Cl-C 3 -alkyl, insbesondere fik Benzyl, 1 -Phenyl-ethyl, 2-Phenyl-ethyl, 3-Phenyl-propyl, 2-Phenyl propyl, 2-Phenyl-isopropyl, 1 -Methyl-2-phenyl-ethyl, Hetaryl-C 1 -C 3 10 alkyl, Hetarylmethyl, 1 -Hetaryl-ethyl, 2-Hetaryl-ethyl, 3-Hetaryl- WO 2004/065402 PCT/EP2004/000058 -160 propyl, 2-Hetaryl-propyl, 2-Hetaryl-isopropyl, 1 -Methyl-2-hetaryl ethyl steht, wobei die Substituenten ausgewahlt sein kunnen aus der Reihe Wasserstoff, geradkettiges oder verzweigtes Alkyl mit bis zu 4 Kohlenstoffatomen, insbesondere Methyl, Ethyl, Propyl, Isopropyl, 5 Butyl, Isobutyl, sec-Butyl, tert-Butyl, Halogenalkyl mit bis zu 2 Kohlensoffatomen, insbesondere Trifluormethyl, Difluorchlormethyl, Pentafluorethyl, Alkenyl mit bis zu 3 Kohlenstoffatomen, cyclisches Alkyl mit bis zu 6 Kohlenstoffatomen, insbesondere Cyclopropyl, Cyclobutyl, Cyclopentyl, Cyclohexyl, Hydroxy, Halogen, insbesondere 10 Brom, Chlor, Fluor oder Iod, Alkoxy, insbesondere Methoxy, Ethoxy, Propoxy, Isopropoxy, Butoxy, Isobutoxy, sec-Butoxy, tert-Butoxy, Cycloalkoxy, insbesondere Cyclopropyloxy, Alkenyloxy, insbesondere Allyloxy, Dioxoalkylen, insbesondere Dioxomethylen, Halogenalkoxy, insbesondere Trifluormethoxy, Alkylthio, insbeson 15 dere Methylthio, Halogenalkylthio, insbesondere Trifluormethylthio, Alkylsulfonyl, insbesondere Methylsulfonyl, Halogenalkylsulfonyl, insbesondere Trifluormethylsulfonyl, Hetarylsulfonyl, insbesondere N Morpholinosulfonyl oder N-Pyrazolylsulfonyl, Nitro, Amino, eine geeignete cyclische Aminogruppe, insbesondere N-Pyrrolidino, N 20 Piperidino, N-Morpholino, N-(2,6-Dimethyl-morpholino), N-Methyl piperazino, N-Thiomorpholino oder N-Dioxothiomorpholino, Alkyl amino, insbesondere Methylamino, Ethylamino, Propylamino, Iso propylamino, Butylamino, sec-Butylamino, Isobutylamino, tert-Butyl amino, Alkylenamino, insbesondere Propylenamino, Dialkylamino, 25 insbesondere Dimethylamino, Diethylamino, Carboxyl, Carbamoyl, Cyano, Alkoxycarbonyl, insbesondere Methoxycarbonyl, Ethoxy carbonyl, Propyloxycarbonyl, Isopropyloxycarbonyl, Butyloxycarb onyl, sec-Butyloxycarbonyl, Isobutyloxycarbonyl, tert-Butyloxy carbonyl, Alkylenoxycarbonyl, insbesondere Propylenoxycarbonyl, N 30 Alkoxycarbonyl-amino, insbesondere N-Methoxycarbonylamino, N Ethoxycarbonylamino, N-Propyloxycarbonylamino, N-Isopropyloxy- WO 2004/065402 PCT/EP2004/000058 - 161 carbonyl-amino, N-Butyloxycarbonyl-amino, N-sec-Butyloxycarb onylamino, N-Isobutyloxycarbonylamino, N-tert-Butyloxycarbonyl amino, Cyanoalkylencar-bonylamino, insbesondere Cyanomethylen carbonylamino, Cyanoethylen-carbonylamino, N-Alkylenoxycarbonyl 5 amino, insbesondere N-Propylenoxycarbonylamino, N-Alkyl sulfonylamino, insbesondere N-Methylsulfonyl-amino, N-Ethyl sulfonylamino, N-Propylsulfonylamino, N-Isopropylsulfonyl-amino, N-Butylsulfonylamino, N-sec-Butylsulfonylamino, N-Isobutyl sulfonyl-amino, N-tert-Butylsulfonylamino, N-Alkylensulfonylamino, 10 insbesondere N-Propylensulfonylamino, gegebenenfalls substituiertes Arylsulfonylamino, insbesondere 4-Trifluormethyl-phenylsulfonyl amino, N-Alkoxycarbonyl-N-alkyl-amino, insbesondere N-Methoxy carbonyl-N-methyl-amino, N-Methoxy-carbonyl-N-ethyl-amino, N Ethoxycarbonyl-N-methyl-anino, N-Ethoxycarbonyl-N-ethyl-amino, 15 N-Propyloxycarbonyl-N-methyl-amino, N-Propyloxycar-bonyl-N ethyl-amino, N-Isopropyloxycarbonyl-N-methyl-amino, N-Isopropyl oxycarbonyl-N-ethyl-amino, N-Butyloxycarbonyl-N-methyl-amino, N Butyloxy-carbonyl-N-ethyl-amino, N-sec-Butyloxycar-bonyl-N methyl-amino, N-sec-Butyloxycarbonyl-N-ethyl-amino, N-Isobutyl 20 oxy-carbonyl-N-methyl-amino, N-Isobutyloxycarbonyl-N-ethyl amino, N-tert-Butyloxycarbonyl-N-methyl-amino, N-tert-Butyloxy carbonyl-N-methyl-anino, N-Alkylenoxycarbonyl-N-alkyl-amino, insbesondere N-Propylenoxycarbonyl-N-methylamino, N-Propylen oxycarbonyl-N-nethyl-amino, N-Alkylcarbonyl-N-alkylamino, insbe 25 sondere N-Methylcarbonyl-N-methyl-amino, N-Methyl-carbonyl-N ethyl-amino, N-Ethyl-carbonyl-N-methyl-amino, N-Ethylcarbonyl-N ethyl-amino, N-Cycloalkylcarbonylamino, insbesondere N-Cyclo propyl-carbonylamino, N-1-Methylcycloprop-1-yl-carbonyl-N-amino, N-Cyclobutyl-amino, N-Alkoxy-carbonyl-N-alkylsulfonyl-amino, 30 insbesondere N-Methoxy-carbonyl-N-methylsulfonyl-amino, N Methoxycarbonyl-N-ethyl-sulfonylamino, N-Ethoxy-carbonyl-N- WO 2004/065402 PCT/EP2004/000058 -162 methylsulfonyl-anino, N-Ethoxy-carbonyl-N-ethyl-sulfonylamino, N Propylox-ycarbonyl-N-methyl-sulfonyl-amiino, N-Propyloxy-carbonyl N-ethylsulfonyl-amino, N-Isopropyloxycarbonyl-N-methylsulfonyl amino, N-Isopropyloxycarbonyl-N-ethylsulfonylamino, N-Butyl 5 oxycarbonyl-N-methylsulfonyl-amino, N-Butyloxycarbonyl-N-ethyl sulfonylamino, N-sec-Butyloxycarbonyl-N-methylsulfonyl-amino, N sec-Butyloxycarbonyl-N-ethyl-sulfonyl-amnino, N-Isobutyloxycarb onyl-N-methyl-sulfonyl-amino, N-Isobutyloxycarbonyl-N-ethyl sulfonylamino, N-tert-Butyloxy-carbonyl-N-rnethyl-sulfonylamino, N 10 tert-Butyloxycarbonyl-N-methylsulfonyl-amino, N-Alklen-oxycarb onyl-N-alkvylsulfonyl-ainino, insbesondere N-Propylenoxycarbony-N methylsulfonyl-amino, N-PropylenoxycarbonylWN-methylsulfonyl amino, N-Alkykcarbonyl-N-alkylsulfonyl-amino, insbesondere N Methylcarbonyl-N-methylsulfonyl-amino, N-Methylcarbonyl-N-ethyl 15 sulfonyl-amino, N-Ethyl-carbonyl-N-methylsulfonyl-amino, N Ethylcarbonyl-N-ethyl-sulfonylamnino, N-Cycloalkylcarbonyl-N-alkyl sulfonyl-amnino, insbesondere N-Cyclopropyl-carbonyl-N-methyl sulfonyl-amnino, N-i -Methylcycloprop- 1-yl-carbonyl-N-methylsulfo nylamino, N-Cyclobutyl-N-methylsulfonylamnino, Alkylamnino 20 carbonylamino, insbesondere N-Methylaminocarbonylamino, N Ethylamino-carbonylamino, NN-Dialkylaminocarbonylamino, insbe sondere NT-dimethylaminocarbon: lamino, N-A ikylaminosulfonyl amino, insbesondere N-It~ethylaininosulfonylamino, NN-Dialkyl aminosulfbiylamino, insbesondere NN-Dimethylaminosulfbnyl 25 amino, und wenn X fdr NH oder NMe steht, R 2 weiterhin fdr CO-R' oder CS-R' steht, 30 worin WO 2004/065402 PCT/EP2004/000058 - 163 R' fLr Amino, fur gegebenenfalls substituiertes C 1 -C 4 Alkyl, CI-C 4 -Alkylamino, Di-C1-C 4 -alkylamino, Aryl, Arylamino, Hetarylamino, Aryl-C 1 -C 3 -alkyl, Hetaryl 5 oder Hetaryl-C1-C 3 -alkyl steht, R 4 filr gegebenenfalls substituiertes CI-C 4 -Alkyl steht oder mit R2 einen
[3] 6-gliedrigen Ring bildet, der durch 0, S oder NR unterbrochen sein kann und gegebenenfalls substituiert ist, und 10 Rs fur gegebenenfalls substituiertes C1-C 4 -Alkyl steht. 3. Verbindungen gemaB Anspruch 1 oder 2, dadurch gekennzeichnet, dass 15 X flir 0 oder NH steht, R fir Wasserstoff oder far einen Amino-Zucker der Formel Ia, 1d oder le steht Me Me Me N,, R e R R Me H Mes Me 0 1 O RS H 0 0 R Me2N /O O s 0 Me Me2N )RMe 20 Id WO 2004/065402 PCT/EP2004/000058 -164 H OH HO Me 2 N Rs RO -~ SR Me Me 2 N RMe le R 2 fir Aryl-Cl-C 3 -alkyl, insbesondere fur Benzyl, 1-Phenyl-ethyl, Hetaryl-C 1 -C 3 -alkyl, Hetarylmethyl, insbesondere Pyridylmethyl, 5 Pyrimidylmethyl, Pyridazinylmethyl, Pyrazylmethyl, Furylmethyl, Thiazolylmethyl, Pyrazolylmethyl, Oxazolylmethyl, Isoxazolylmethyl, Thiazolylmethyl, Imidazolylmethyl, Triazolylmethyl, Tetrazolyl methyl, Dihydro-dioxazinylmethyl, 1-Hetaryl-ethyl, insbesondere 1 Pyridylethyl, 1-Pyrimidylethyl, 1-Pyridazinylethyl, 1-Pyrazylethyl, 1 10 Furylethyl, 1-Thiazolylethyl, 1-Pyrazolylethyl, 1-Oxazolylethyl, 1 Isoxazolylethyl, 1-Thiazolylethyl, 1-Inidazolylethyl, 1-Triazolylethyl, 1 -Tetrazolylethyl, 1 -Dihydro-dioxazinylethyl steht, die jeweils gegebe nenfalls durch Reste aus der Reihe Wasserstoff, geradkettiges oder verzweigtes Alkyl mit bis zu 4 Kohlenstoffatomen, insbesondere 15 Methyl, Ethyl, Propyl, tert-Butyl, Halogenalkyl, insbesondere Trifluormethyl, Hydroxy, Halogen, insbesondere Brom, Chlor, Fluor oder Iod, Alkoxy, insbesondere Methoxy, Ethoxy, tert-Butoxy, Halogenalkoxy, insbesondere Trifluormethoxy, Alkylthio, insbeson dere Methylthio, Halogenalkylthio, insbesondere Trifluormethylthio, 20 Alkylsulfonyl, insbesondere Methylsulfonyl, Halogenalkylsulfonyl, insbesondere Trifluormethylsulfonyl, Nitro, Amino, Alkylamino, insbesondere Methylamino, Ethylamino, N-Alkoxycarbonylamino, insbesondere N-Methoxycarbonylamino, N-Ethoxycarbonylamino, N Propyloxycarbonylamino, N-Isopropyloxycarbonyl-amino, N-Butyl 25 oxycarbonylamino, N-sec-Butyloxycarbonylamino, N-Isobutyloxy carbonylamino, N-tert-Butyloxycarbonylamino, N-Alkylenoxycarb onyl-amino, insbesondere N-Propylenoxycarbonylamino, N-Alkyl- WO 2004/065402 PCT/EP2004/000058 - 165 sulfonylainino, insbesondere N-Methylsulfonylamino, N-Ethylsul fonylamino, N-Propyl-sulfonylainino, N-Isopropylsulfonylamino, N Butylsulfonylamino, N-sec-Butylsulfonylamnino, N-Isobutylsulfonyl amino, N-tert-Butylsulfonylaniino, N- N-Alkoxycarbonyl-N-alkyl 5 amino, insbesondere N-Methoxycarbonyl-N-methyl-amino, N-Meth oxy-carbonyl-N-ethyl-aniino, N-Ethoxyearbonyl-N-methyl-amino, N Ethoxycarbonyl-N-ethyl-amino, N-Propyloxycarbonyl-N-methyl amino, N-Propyloxycar-bonyl-N-ethyl-amino, N-Isopropyloxycarb onyl-N-methyl-axnino, N-Isopropyl-oxycarbonyl-'N-ethiyl-amino, N 10 Butyloxy-carbonyl-N-methiyl-amino, N-Butyloxy-carbonyl-N-ethyl amino, N-sec-Butyloxycar-bonyl-N-methyl-amino, N-see-Butyloxy carbonyl--N-ethyl-amnino, N-Isobutyloxy-carbonyl-N-methyl-anmino, N Isobutyloxycarbonyl-N-ethyl-amnino, N-tert-Butyloxycarbonyl-N methyl-amino, N-tert-Butyloxycarbonyl-N-methyl-amino, N-Alkylen 15 oxycarbonyl-N-alkyl-amino, insbesondere N-Propylenoxycarbonyl-N methylamino, N-Propylenoxycarbonyl-N-methyl-amnino, N-Alkyl carbonyl-N-alkylamino, insbesondere N-Methylcarbonyl-N-methyl amino, N-Methylearbonyl-N-etliyl-amino, N-Ethyl-carbonyl-N methyl-amino, N-Ethylcarbonyl-N-ethyl-amnino, N-Cycloalkylcarb 20 onylatmino, isbesondere N-Cyclopropylcarbonylaniino, N-i Methylcycloprop- 1-yl-carbonyl-N-amino, N-Cyclobutylamino, N Alkoxy-carbonyl-N-alkylsulfonyl-amino, insbesondere N-Methoxy carbonyl-N-methylsulfonyl-amino, N-Yiethoxycarbonyl-N-ethyl sulfonylarnino, N-Etho,-y-carbonyl-N-miethylsulfonyl-amino, N 25 Ethoxy-carbonyl-N-ethiylsulfoniyl-amnino, N-Propyloxycarbonyl-N methyl-sulfonyl-amino, NI-Propyloxycarbonyl--N-ethylsulfonyl-amino, N-Isopropyloxycarbonyl-N-methylsulfonyl-amino, N-Isopropyloxy carbonyl-N-ethylsulfonyl-amino, N-Butyloxycarbonyl-N-methyl sulfonylamino, N-Butyloxycarbonyl-N-ethyl-sulfonylamino, N-sec 30 Butyloxy-carbonyl-N-methylsulfonyl-atnino, N-sec-Butyloxycarbonyl N-ethylsulfonyl-ainino, N-Jsobutyloxycarbonyl-N-methyl-sulfonyl- WO 2004/065402 PCT/EP2004/000058 -166 amino, N-Isobutyloxy-carbonyl-N-ethylsulfonyl-amino, N-tert Butyloxy-carbonyl-N-methylsulfonyl-amino, N-tert-Butyloxycarbonyl N-methylsulfonyl-amino, N-Alkylen-oxycarbonyl-N-alkylsulfonyl amino, insbesondere N-Propylenoxy-carbonyl-N-methylsulfonyl 5 amino, N-Propylenoxycarbonyl-N-methylsulfonyl-amino, N Alkylcarbonyl-N-alkylsulfonyl-amino, insbesondere N Methylcarbonyl-N-methylsulfonyl-amino, N-Methylcarbonyl-N-ethyl sulfonyl-amino, N-Ethyl-carbonyl-N-methylsulfonyl-amino, N-Ethyl carbonyl-N-ethyl-sulfonyl-amino, N-Cycloalkylearbonyl-N-alkyl 10 sulfonyl-amino, insbesondere N-Cyclopropyl-carbonyl-N-methylsulfo nyl-amino, N-1-Methylcycloprop-1-yl-carbonyl-N-methylsulfonyl amino, N-Cyclobutyl-N-methylsulfonylamino, Alkylamino carbonylamino, insbesondere N-Methylaminocarbonylamino, N-Ethyl aminoicarbonylamino, NN-Dialkylaminocarbonylamino, insbeson 15 dere NN-dimethylaminocarbonylamino, N-Alkylaminosulfonylamino, insbesondere N-Methylaminosulfonylamino, NN-Di alkylaminosulfonylamino, insbesondere NN-Dimethylaminosulfonyl amino, substituiert sein knnen, und 20 wenn X fur NH oder NMe steht, R 2 weiterhin ftr CO-R' oder CS-R' steht, Worln 25 R' fUr Amino, Arylamino, insbesondere Trifluormeth oxyphenylamino, Trifluormethylphenylamino, Chlor phenylamino, Hetarylamino, insbesondere Brom pyridylamino, Trifluormethylpyridylamino steht. 30 WO 2004/065402 PCT/EP2004/000058 -167 4. Verbindungen gemRB einem der Ansprflche I bis 3, dadurch gekennzeichnet, dass, X fUr 0 steht, 5 R 1 fuir Wasserstoff oder fuir einen Amino-Zucker der Formel la oder le steht Me Me Me 2 N R o R Me 0 RR Me H Ia H OH HO C0 Me Me 2 N Me le 10 R 2 fur Benzyl, I-Phenyl-ethyl, Hetarylmethyl, insbesondere Pyridylmethyl, Pyridazinylmethyl, Thiazolylmethyl, Pyrazolylmethyl, Isoxazolylmethyl, Inidazolylmethyl, Dihydro-dioxazinylmethyl, 1 Pyridylethyl, 1-Thiazolylethyl, 1-Dihydro-dioxazinylethyl steht, die 15 jeweils gegebenenfalls durch Reste aus der Reihe Wasserstoff, Methyl, tert-Butyl, Trifluormethyl, Brom, Chlor, Fluor, Methoxy, Trifluormethoxy, Nitro, Amino, Methylamino, Ethylamino, N Methoxycarbonylamino, N-Ethoxycarbonylamino, N-Propyloxy carbonyl-anino, N-Isopropyloxycarbonyl-amino, N-tert-Butyloxycarb 20 onylamino, N-Propylenoxycarbonylamino, N-Methylsulfonylamino, N-Ethylsulfonyl-amino, N-Methoxycarbonyl-N-methyl-amino, N Ethoxycarbonyl-N-methyl-amino, N-Isopropyloxycarbonyl-N-methyl amino, N-tert-Butyloxycarbonyl-N-methyl-amino, N-Propylenoxy- WO 2004/065402 PCT/EP2004/000058 - 168 carbonyl-N-methylamino, N-Cyclopropyl-carbonylamino, N-i Methylcycloprop- l-yl-carbonyl-N-amino, N-Methoxy-earbonyl-N methylsulfonyl-amino, N-Methoxycarbonyl-N-ethyl-sulfonylamino, N-Isobutyloxycarbonyl-N-methyl-sulfonyl-amino, N-tert 5 Butyloxycarbonyl-N-methylsulfonyl-amnino, N-tert-Butyloxycarbonyl N-methylsulfonyl-amino, N-Propylenoxycarbonyl-N-methylsulfonyl amino, N-Cyclopropylcarbonyl-N-methyl-sulfonyl-arnino, N-i Methylcycloprop-l -yl-carbonyl-N-rnethyl-sulfonyl-amnino, NN DiaLkylaminocarbonylamino, N-Methylaminosulfonylamnino, NN 10 Dialkylaminosulfonylamino, substituiert sein konnen. 5. Verbindungen gemdBI einem der AnsprUche 1 bis 4, dadurch gekennzeicbnet. dass 15 A-B fikr eine der folgenden Gruppen steht: -HC=CH- oder -H 2 C-CH 2 - steht. 6. Verfahren. zum Herstellen einer Verbindung der aligemeinen Formel (I), 17 C H H 0HH 0 200 und. deren Salze, in welcher WO 2004/065402 PCT/EP2004/000058 -169 R, R 2 , R, X und A-B die in einem der Ansprache 1 bis 5 angegebenen Bedeutungen besitzen, dadurch gekennzeichnet, dass man 5 Verbindungen der allgemeinen Formel (II) 17 CH 3 0 ~H H H2C 21 O R 3 HH A-B H 10 in welcher R', R3 und A-B die oben angegebenen Bedeutungen besitzen, mit Aminoverbindungen der allgemeinen Formel (III) 15 H 2 N-X-R 2 (111) in welcher R2 und X die oben angegebenen Bedeutungen besitzen, 20 in Gegenwart eines basischen Hilfsmittels und gegebenenfalls in Gegenwart eines Verdinnungsmittels umsetzt.
[4] 7. Mittel zur Bekampfung von tierischen Schadlingen enthaltend eine oder 25 mehrere Verbindungen gemaB einem der Ansprache 1 bis 5. WO 2004/065402 PCT/EP2004/000058 -170
[5] 8. Verwendung von Verbindungen gemaB einem der Anspruche 1 bis 5 zum Bekampfen von tierischen Schadlingen. 5 9. Verfahren zum Herstellen von Schadlingsbekampfungsmittel, dadurch gekennzeichnet, dass man eine oder mehrere Verbindungen gemaB einem der Ansprliche 1 bis 5 mit Streckmitteln und/oder oberflachenaktiven Substanzen vermischt. 10 10. Verbindungen der allgemeinen Formel (II) 17 CH3 0 H H O Ha 21 (1 R 3 H H A'-B H in welcher 15 R' fur einen Amino-Zucker der Formel 1 d oder 1 e steht Mes Me O~ O O Me2N - SR Me Me2N Me 1d WO 2004/065402 PCT/EP2004/000058 - 171 H OH HO Me2 N Rs 0 Me Me 2 N RMe le und R 3 und A-B die in Anspruchl angegebenen Bedeutungen besitzen. 5
[6] 11. Verbindungen der allgemeinen Formel (II) CH3 17 CH 0 H HO HC 21 0(ii) Ra HH A-B H 10 in welcher R' fUr einen Amino-Zucker der Formel la steht Me Me H 1a 15 R3 flr Wasserstoff oder Hydroxy steht, und WO 2004/065402 PCT/EP2004/000058 -172 A-B fur eine der folgenden Gruppen steht: -HC=C(CH 3 )-, -H 2 C-CH 2 - oder -H 2 C-CH(CH 3 )--

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法律状态:
2010-08-05| MK4| Application lapsed section 142(2)(d) - no continuation fee paid for the application|

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DE10301519.1||2003-01-17||

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PCT/EP2004/000058|WO2004065402A1|2003-01-17|2004-01-08|9-ketospinosyn derivatives|

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