N- (TETRAZOL-5-IL)

专利摘要:
Patent Summary: "N- (Tetrazol-5-yl) - and N- (Triazol-5-yl) arylcarboxylic acid amides and their use as herbicides". The present invention relates to n- (tetrazol-5-yl) - and n- (triazol-5-yl) arylcarboxylic acid amides of the general formula (i) as herbicides. In this formula (i), x, y, z and r represent radicals such as hydrogen, organic radicals such as alkyl and other radicals such as halogen. a and b represent n and cy.
公开号:BR112014002191B1
申请号:R112014002191
申请日:2012-07-30
公开日:2018-07-17
发明作者:Van Almsick Andreas；Köhn Arnim；Hugh Rosinger Christopher；Gatzweiler Elmar；Dietrich Hansjörg；Ahrens Hartmut；Heinemann Ines；Häuser- Hahn Isolde；Braun Ralf；Dörner- Rieping Simon；Lehr Stefan
申请人:Bayer Ip Gmbh；
IPC主号:

专利说明:

(54) Title: N- (TETRAZOL-5-IL) - OR N- (TRIAZOL-5-IL) ARYCHARBOXYLIC ACID AMIDAS, ITS USE, HERBICIDE COMPOSITION, AND PROCESS FOR COMBATING UNWANTED PLANTS (51) Int.CI. : C07D 249/14; C07D 257/06; C07D 401/12; A01N 43/713; A01N 43/653 (30) Unionist Priority: 03/08/2011 EP 11 176378.5 (73) Holder (s): BAYER INTELLECTUAL PROPERTY GMBH (72) Inventor (s): RALF BRAUN; SIMON DÕRNER-RIEPING; ARNIM KÕHN; HARTMUT AHRENS; STEFAN LEHR; ANDREAS VAN ALMSICK; ISOLDE HÀUSER-HAHN; HANSJÕRG DIETRICH; ELMAR GATZWEILER; INES HEINEMANN; CHRISTOPHER HUGH ROSINGER
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Invention Patent Descriptive Report for N- (TETRAZOL-5-IL) - OR N- (TRIAZOL-5ILJARYL CARBOXYLIC ACID STARCHES, ITS USE, HERBICIDE COMPOSITION, AND PROCESS FOR COMBATING UNWANTED PLANTS.
Description [001] The present invention relates to the technical field of herbicides, in particular, that of herbicides for the selective control of weeds and weeds in useful plant cultures.
[002] From W02003 / 010143 and W02003 / 010153 are known N- (tetrazol-5-yl) - and N- (triazol-5-yl) benzamides and their pharmacological effect. From the oldest, unpublished EP101748937 priority, certain N- (tetrazol-5-yl) - and N- (triazol-5-yl) benzamides and nicotinamides are known as herbicides. It was then found that amides and nicotinamides of (tetrazol-5-yl) - and N- (triazol-5yl) arylcarboxylic acid, which at position 1 of the tetrazole or triazole ring carry special substituents, are particularly well suited as herbicides.
[003] An object of the present invention is, therefore, N- (tetrazol-5-yl) - and N- (triazol-5-yl) arylcarboxylic acid amides of the formula (I) or their salts
in which
A represents N or CY,
B represents N or CH,
X represents nitro, halogen, cyano, formyl, rhodan, (CiCej-alkyl, halogeno- (C1-C6) -alkyl, (C2-C6) -alkenyl, halogeno- (C2Petition 870180050694, 06/13/2018, pg. 6/104
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Cej-alkenyl, (C2-Cs) -alkyl, halogen- (C3-C6) -alkynyl, (C3-C6) cycloalkyl, halogen- (C3-C6) -cycloalkyl, (C3-C6) -cycloalkyl- (Ci- C6) alkyl, halogen- (C3-C6) -cycloalkyl- (C1-C6) -alkyl, COR ¹ , COOR ¹ , OCOOR ⁱ , NR ⁱ COOR ⁱ , C (O) N (R ⁱ ) 2, NR ⁱ C (O) N (R ⁱ ) 2, OC (O) N (R ⁱ ) 2, C (O) NR ¹ OR ¹ , OR ¹ , OCOR ¹ , OSO2R ² , S (O) nR ² , SO2OR ¹ , SO2N (R ¹ ) 2, NR ¹ SO2R ² , NR ¹ COR ¹ , (C1-C6) -alkyl-S (O) nR ² , (C1-C6) -alkyl-OR ¹ , (C1C6) -alkyl-OCOR ¹ , (C1-C6) -alkyl-OSO2R ² , (C1-C6) -alkyl-CO2R ¹ , (C1C6) -alkyl-SO2OR ¹ , (C1-C6) -alkyl-CON (R ¹ ) 2, (C1- C6) -alkyl-SO2N (R ¹ ) 2, (C1-C6) -alkyl-NR ¹ COR ¹ , (C1-C6) -alkyl-NR ¹ SO2R ² , NR1R2, P (O) (OR ⁵ ) 2, CH2P (O) (OR ⁵ ) 2, (C1-C6) -alkyl-heteroaryl, (C1-C6) -alkyl-heterocyclyl, the last two radicals mentioned being replaced each by halogen radicals, (C1-Cs) -alkyl, halogen- (C1-C6) -alkyl, S (O) n- (C1-Cs) -alkyl, (C1-C6) -alkoxy, halogen- (C1-C6) -alkoxy and in which the heterocyclyl bears n oxo groups,
Y represents hydrogen, nitro, halogen, cyano, rhodan, (C1-Cs) -alkyl, halogen- (C1-C6) -alkyl, (C2-C6) -alkenyl, halogen (C2-C6) -alkenyl, (C2- C6) -alkynyl, halogeno- (C2-C6) -alkynyl, (C3-C6) cycloalkyl, halogeno- (C3-C6) -cycloalkyl, (C3-C6) -cycloalkyl- (C1-C6) alkyl, halogeno- ( C3-C6) -cycloalkyl- (C1-C6) -alkyl, COR ¹ , COOR ¹ , OCOOR ¹ , NR ¹ COOR ¹ , C (O) N (R ¹ ) 2, NR ¹ C (O) N (R ¹ ) 2, OC (O) N (R ¹ ) 2, CO (NOR ¹ ) R ¹ , NR ¹ SO2R ² , NR ¹ COR ¹ , OR ¹ , OSO2R ² , S (O) nR ² , SO2OR ¹ , SO2N ( R ¹ ) 2, (C1-C ₆ ) -alkyl-S (O) nR ² , (C1-C6) -alkyl-OR ¹ , (C1-C6) -alkylOCOR ¹ , (C1-C6) -alkyl-OSO2R ² , (C1-C6) -alkyl-CO2R ¹ , (C1-Ce) -alkylCN, (C1-C6) -alkyl-SO2OR ¹ , (C1-C6) -alkyl-CON (R ¹ ) 2, (C1- C6) -alkylSO2N (R ¹ ) 2, (C1-C6) -alkyl-NR ¹ COR ¹ , (C1-C6) -alkyl-NR ¹ SO2R ² , N (R ¹ ) 2, P (O) (OR ⁵ ) 2, CH2P (O) (OR ⁵ ) 2, (C1-C6) -alkyl-phenyl, (C1-C6) -alkyletheroaryl, (C1-C6) -alkyl-heterocyclyl, phenyl, heteroaryl or heterocyclyl, last 6 radicals mentioned are subst each by radicals of the halogen group, nitro, cyano, (C1C6) -alkyl, halogen- (C1-C6) -alkyl, (C3-C6) -cycloalkyl, S (O) n- (C1Petition 870180050694, of 13 / 06/2018, p. 7/104
3/89
Ce) -alkyl, (C1-Cej-alkoxy, halo- (C1-C6) -alkoxy, (C1-C6) -alkoxy- (C1C4) -alkyl and cyanomethyl and where heterocyclyl carries n oxo groups,
Z represents halogen, cyano, rhodane, halogen- (C1-Ce) alkyl, (C2-Ce) -alkenyl, halogeno- (C2-Ce) -alkenyl, (C2-Ce) -alquinyl, halogeno- (C2-Ce) -alkynyl, (C3-Ce) -cycloalkyl, halo- (C3-Ce) cycloalkyl, (C3-C6) -cycloalkyl- (C1-Ce) -alkyl, halogeno- (C3-Ce) cycloalkyl- (C1-C6) -alkyl, COR ¹ , COOR ¹ , OCOOR ¹ , NR ¹ COOR ¹ , C (O) N (R ⁱ ) 2, NR ⁱ C (O) N (R ⁱ ) 2, OC (O) N (R ⁱ ) 2, CO (NOR ⁱ ) OR ⁱ ,
C (O) NR ¹ OR ¹ , OSO2R ² , S (O) nR ² , SO2OR ¹ , SO2N (R ¹ ) 2, NR ¹ SO2R ² , NR ¹ COR ¹ , (C1-C ₆ ) -alkyl-S ( O) nR ² , (C1-Ce) -alkyl-OR ¹ , (C1-Ce) -alkylOCOR ¹ , (C1-Ce) -alkyl-OSO2R ² , (C1-Ce) -alkyl-CO2R ¹ , (C1- Ce) -alkylSO2OR ¹ , (C1-Ce) -alkyl-CON (R ¹ ) 2, (C1-Ce) -alkyl-SO2N (R ¹ ) 2, (C1-C6) alkyl-NR ¹ COR ¹ , (C1 -Ce) -alkyl-NR ¹ SO2R ² , N (R ¹ ) 2, P (O) (OR ⁵ ) 2, heteroaryl, heterocyclyl or phenyl, with the last three radicals mentioned being replaced each by radicals of the halogen group , nitro, cyano, (C1-Ce) -alkyl, halogen- (C1-Ce) -alkyl, (C3-C6) cycloalkyl, S (O) n- (C1-Ce) -alkyl, (C1-Ce) - alkoxy or halo- (C1-Ce) alkoxy and the heterocyclyl having n oxo or Z groups can also represent hydrogen, (C1-Cs) -alkyl or (C1-Ce) -alkoxy, if Y represents the radical S (O ) nR ² ,
R represents CH2R ⁶ ,
CH2-heterocyclyl substituted by m oxo groups, (C3-C7) -cycloalkyl substituted by t (C1-Cs) -alkyl, (C2-Cs) -alkyl, (C3-C7) -cycloalkyl, halogen- (C2-Ce ) alkyl, (C2-Ce) -alkenyl, halogeno- (C2-Ce) -alkenyl, (C2-Ce) -alkynyl or halogeno- (C2-Ce) -alkynyl each substituted by u radicals in the group consisting of nitro, cyan , hydroxy, oxo, SiR ⁵ 3, PO (OR ⁵ ) 2, S (O) n- (C1Ce) -alkyl, (C1-Ce) -alkoxy, halogen- (C1-Ce) -alkoxy, N (R ³ ) 2, COR ³ , OCOR ³ , NR ³ COR ³ , NR ³ SO2R ⁴ , (C3-Ce) -cycloalkyl, heteroaryl, heterocyclyl, phenyl, Q-heteroaryl, Q-heterocyclyl, Q-phenyl and Q-benzyl,
Petition 870180050694, of 06/13/2018, p. 8/104
4/89 with the radicals (C3-Ce) -cycloalkyl, heteroaryl, heterocyclyl, phenyl, Q-heteroaryl, Q-heterocyclyl, Q-phenyl and Q-benzyl being substituted each by substituents of the group consisting of methyl, ethyl, methoxy, cyano, nitro, trifluoromethyl and halogen and in which heterocyclyl and cycloalkyl carry n oxo groups,
Q represents O, S or NR ³ ,
R ¹ represents hydrogen, (C1-Ce) -alkyl, (C1-C6) halogenoalkyl, (C2-Ce) -alkenyl, (C2-Ce) -halogenoalkenyl, (C2-C6) alkynyl, (C2-Ce) -halogenoalquinyl (C3-Ce) -cycloalkyl, (C3-C6) cycloalkenyl, (C3-Ce) -halogenocycloalkyl, (C1-Ce) -alkyl-O- (C1-Ce) alkyl, (C3-C6) -cycloalkyl- (C1 -Cs) -alkyl, phenyl, phenyl- (C1-Cs) -alkyl, heteroaryl, (C1-Ce) -alkyl-heteroaryl, heterocyclyl, (C1-Ce) -alkyleterocyclyl, (C1-Ce) -alkyl-O- heteroaryl, (C1-Cs) -alkyl-O-heterocyclyl, (C1-Ce) -alkyl-NR ³ -heteroaryl, (C1-C6) -alkyl-NR ³ -heterocyclyl, the last 21 radicals mentioned being replaced by radicals in the group consisting of cyan, halogen, nitro, rhodan, OR ³ , S (O) nR ⁴ , N (R ³ ) 2, NR ³ OR ³ , COR ³ , OCOR ³ , SCOR ⁴ , NR ³ COR ³ , NR ³ SO2R ⁴ , CO2R ³ , COSR ⁴ , CON (R ³ ) 2 and (C1-C4) -alkoxy- (C2-C6) -alkoxycarbonyl and where heterocyclyl carries n oxo groups,
R ² represents (C1-Ce) -alkyl, (C1-Ce) -halogenoalkyl, (C2Ce) -alkenyl, (C2-Ce) -halogenoalkenyl, (C2-Cs) -alkynyl, (C2-C6) halogenoalkynyl (C3- Ce) -cycloalkyl, (C3-Ce) -cycloalkenyl, (C3-C6) halogenocycloalkyl, (C1-C6) -alkyl-O- (C1-Ce) -alkyl, (C3-C6) cycloalkyl- (C1-Cs) -alkyl, phenyl, phenyl- (C1-Cs) -alkyl, heteroaryl, (C1Ce) -alkyl-heteroaryl, heterocyclyl, (C1-Ce) -alkyl-heterocyclyl, (C1-C6) alkyl-O-heteroaryl, (C1 -Ce) -alkyl-O-heterocyclyl, (C1-Ce) -alkyl-NR ³ heteroaryl, (C1-C6) -alkyl-NR ³ -heterocyclyl, the last 21 radicals mentioned being replaced by radicals from the group consisting of in cyan, halogen, nitro, rhodan, OR ³ , S (O) nR ⁴ , N (R ³ ) 2, NR ³ OR ³ , COR ³ , OCOR ³ , SCOR ⁴ , NR ³ COR ³ , NR ³ SO2R ⁴ , CO2R ³ ,
Petition 870180050694, of 06/13/2018, p. 9/104
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COSR ⁴ , CON (R ³ ) 2 and (C1-C4) -alkoxy- (C2-C6) -alkoxycarbonyl and where heterocyclyl carries n oxo groups,
R ³ represents hydrogen, (C1-Ce) -alkyl, (C2-Ce) -alkenyl, (C2-Cs) -alkynyl, (C3-Ce) -cycloalkyl or (C3-C6) -cycloalkyl- (C1-Cs) alkyl,
R ⁴ represents (C1-Ce) -alkyl, (C2-Ce) -alkenyl or (C2-C6) alkynyl, (C3-Ce) -cycloalkyl or (C3-C6) -cycloalkyl- (C1-Cs) -alkyl,
R ⁵ represents (C1-C4) -alkyl,
R ⁶ represents OCOOR ⁴ , NR ⁴ COOR ⁴ , S (O) _n - (C1-C _e ) -alkyl, S (O) n- (C1-Ce) -haloalkyl, nitro, cyano, SiR ⁵ 3, PO ( OR ⁵ ) 2, heterocyclyl or cycloalkyl, the last two radicals mentioned having m oxo or hydroxy groups, m represents 1 or 2, n represents 0, 1 or 2, s represents 0, 1, 2 or 3, t represents 1 , 2, 3 or 4, u represents 1, 2, 3, 4 or 5.
[004] In formula (I) and in all the following formulas, alkyl radicals with more than two carbon atoms, can be in a straight or branched chain. Alkyl radicals mean, for example, methyl, ethyl, n- or i-propyl, n-, i-, t- or 2-butyl, pentyls, hexyls, such as nhexyl, i-hexyl and 1,3-dimethylbutyl. Similarly, alkenyl means, for example, allyl, 1-methylprop-2-en-1-yl, 2-methyl-prop-2-en-1yl, but-2-en-1-yl, but-3- en-1-yl, 1-methyl-but-3-en-1-yl and 1-methyl-but-2en-1-yl. Alquinyl means, for example, propargyl, but-2-in-1-yl, but3-in-1-yl, 1-methyl-but-3-in-1-yl. The multiple bond can be located in each case at any position of the unsaturated radical. Cycloalkyl means a saturated, carbocyclic ring system with three to six carbon atoms, for example, cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl. Similarly, cycloalkenyl means a group
Petition 870180050694, of 06/13/2018, p. 10/104
6/89 monocyclic alkenyl with three to six carbon ring members, for example, cyclopropenyl, cyclobutenyl, cyclopentenyl and cyclohexenyl, the double bond being located in any position.
[005] Halogen represents fluorine, chlorine, bromine or iodine.
[006] Heterocyclyl means a saturated, partially saturated or completely unsaturated radical, containing 3 to 6 ring atoms, 1 to 4 of which come from the oxygen, nitrogen and sulfur group and which may additionally be ringed by a benzo ring. For example, heterocyclyl represents piperidinyl, pyrrolidinyl, tetrahydrofuranyl, dihydrofuranyl and oxetanil. Heteroaryl means a cyclic aromatic radical, containing 3 to 6 ring atoms, 1 to 4 of which come from the oxygen, nitrogen and sulfur group and which may additionally be ringed by a benzo ring. For example, heteroaryl represents benzimidazol-2-yl, furanyl, imidazolyl, isoxazolyl, isothiazolyl, oxazolyl, pyrazinyl, pyrimidinyl, pyridazinyl, pyridinyl, benzisoxazolyl, thiazolyl, pyrrolyl, pyrazolyl, 1,2, thiophenyl, 1,2 -oxadiazolyl, 1,2,5-oxadiazolyl, 1,3,4-oxadiazolyl, 1,2,4-triazolyl, 1,2,3-triazolyl, 1,2,5-triazolyl, 1,3,4-triazolyl , 1,2,4triazolyl, 1,2,4-thiadiazolyl, 1,3,4-thiadiazolyl, 1,2,3-thiadiazolyl, 1,2,5thiadiazolyl, 2H-1,2,3,4-tetrazolyl, 1H -1,2,3,4-tetrazolyl, 1,2,3,4oxatriazolyl, 1,2,3,5-oxatriazolyl, 1,2,3,4-thiatriazolyl and 1,2,3,5tiatriazolyl.
[007] If a group is replaced several times by radicals, then that group can be replaced by one or more radicals that are the same or different from those mentioned.
[008] The compounds of the general formula (I) can be present as stereoisomers depending on the type and bond of the substituents. If, for example, one or more asymmetric carbon atoms are present, then enantiomers and diastereomers can occur. Of
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7/89 likewise, stereoisomers occur, when n represents 1 (sulfoxides). Stereoisomers can be obtained from mixtures obtained in the preparation, by conventional separation methods, for example, by chromatographic separation processes. Likewise, stereoisomers can be selectively prepared through the use of stereoselective reactions using optically active starting materials and / or auxiliary agents. The invention also relates to all stereoisomers and their mixtures, which are comprised by the general formula (I), however, are not specifically defined.
[009] Preferred compounds of the general formula (I), in which
A represents N or CY,
B represents N or CH,
X represents nitro, halogen, cyano, rhodan, (C1-C6) -alkyl, halogeno- (C1-C6) -alkyl, (C2-C6) -alkenyl, halogen- (C2-C6) alkenyl, (C2-C6) -alkynyl, halogeno- (C3-C6) -alkynyl, (C3-C6) cycloalkyl, halogeno- (C3-C6) -cycloalkyl, (C1-C6) -alkyl-O- (C1-C6) alkyl, (C3- C6) -cycloalkyl- (C1-C6) -alkyl, halogeno- (C3-C6) -cycloalkyl (C1-C6) -alkyl, COR ¹ , OR ¹ , OCOR ¹ , OSO2R ² , S (O) nR ² , SO2OR ¹ , SO2N (R ¹ ) 2, NR ¹ SO2R ² , NR ¹ COR ¹ , (C1-C6) -alkyl-S (O) nR ² , (C1-C6) alkyl-OR ¹ , (C1-C6) - alkyl-OCOR ¹ , (C1-C6) -alkyl-OSO2R ² , (C1-C6) alkyl-CO2R ¹ , (C1-C6) -alkyl-SO2OR ¹ , (C1-C6) -alkyl-CON (R ¹ ) 2, (C1-C6) alkyl-SO2N (R ¹ ) 2, (C1-C6) -alkyl-NR ¹ COR ¹ or (C1-C6) -alkyl-NR ¹ SO2R ² , (C1-C6) -alkyl- heteroaryl, (C1-C6) -alkyl-heterocyclyl, with the last two radicals mentioned being replaced each by halogen radicals, (C1-C6) -alkyl, halogen- (C1-C6) -alkyl, S (O) n - (C1-C6) alkyl, (C1-C6) -alkoxy, halo- (C1-C6) -alkoxy and where the heterocyclyl carries n gr upos oxo,
Y represents hydrogen, nitro, halogen, cyano, rhodan, (C1-C6) -alkyl, halogen- (C1-C6) -alkyl, (C2-C6) -alkenyl, halogenPetition 870180050694, of 06/13/2018, pg. 10/124
8/89 (C2-Cs) -alkenyl, (C2-C6) -alkynyl, halo- (C2-C6) -alkynyl, (C3-C6) cycloalkyl, halo- (C3-C6) -cycloalkyl, (C3-C6 ) -cycloalkyl- (C1-C6) alkyl, halo- (C3-C6) -cycloalkyl- (C1-C6) -alkyl, COR ¹ , OR ¹ , COOR ⁱ , OSO2R ² , S (O) nR ² , SO2OR ⁱ , SO2N (R ⁱ ) 2, N (R ⁱ ) 2, NR ⁱ SO2R ² , NR ¹ COR ¹ , (C1-C6) -alkyl-S (O) nR ² , (C1-C6) -alkyl-OR ¹ , (C1-C6) -alkylOCOR ¹ , (C1-C6) -alkyl-OSO2R ² , (C1-C6) -alkyl-CO2R ¹ , (C1-Ce) -alkylSO2OR ¹ , (C1-C6) -alkyl-CON (R ¹ ) 2, (C1-C6) -alkyl-SO2N (R ¹ ) 2, (C1-C6) alkyl-NR ¹ COR ¹ , (C1-C6) -alkyl-NR ¹ SO2R ² , (C1-C6 ) -alkyl-phenyl, (C1C6) -alkyl-heteroaryl, (C1-C6) -alkyl-heterocyclyl, phenyl, heteroaryl or heterocyclyl, with the last six radicals mentioned being replaced each by radicals of the halogen, nitro, cyano group (C1C6) -alkyl, halogeno- (C1-C6) -alkyl, (C3-C6) -cycloalkyl, S (O) n- (C1C6) -alkyl, (C1-C6) -alkoxy, halogen- (C1-C6 ) -alkoxy, (C1-C6) -alkoxy- (C1C4) -alkyl and cyanomethyl and where heterocyclyl is to n oxo groups,
Z represents halogen, cyano, rhodane, halogen- (C1-Ce) alkyl, (C2-C6) -alkenyl, halogeno- (C2-C6) -alkenyl, (C2-C6) -alquinyl, halogeno- (C3-C6) -alkynyl, (C3-C6) -cycloalkyl, halo- (C3-Ce) cycloalkyl, (C3-C6) -cycloalkyl- (C1-C6) -alkyl, halogen- (C3-Ce) cycloalkyl- (C1-C6) -alkyl, COR ¹ , COOR ¹ , C (O) N (R ¹ ) 2, C (O) NR ¹ OR ¹ , OSO2R ² , S (O) nR ² , SO2OR ¹ , SO2N (R ¹ ) 2, NR ¹ SO2R ² , NR ¹ COR ¹ , (C1-C6) alkyl-S (O) nR ² , (C1-C6) -alkyl-OR ¹ , (C1-C6) -alkyl-OCOR ¹ , (C1-C6) alkyl-OSO2R ² , (C1-C6) -alkyl-CO2R ¹ , (C1-C6) -alkyl-SO2OR ¹ , (C1-C6) alkyl-CON (R ¹ ) 2, (C1-C6) -alkyl-SO2N (R ¹ ) 2, (C1-C6) -alkyl-NR ¹ COR ¹ , (C1-C6) -alkyl-NR ¹ SO2R ² , 1,2,4-triazole-1-yl or
Z can also represent hydrogen, (C1-Cs) -alkyl or (C1-C6) -alkoxy, if Y represents the radical S (O) nR ² ,
R represents CH2R ⁶ ,
CH2-heterocyclyl substituted by m oxo groups, (C2-Cs) -alkyl, (C3-C7) -cycloalkyl, halogen-C2-C6) -alkyl, (C2-C6) -alkenyl, halogen- (C2-C6) - alkenyl, (C2-C6) -alkynyl or
Petition 870180050694, of 06/13/2018, p. 10/13
9/89 halogeno- (C2-C6) -alkynyl in each case replaced by u radicals of the group consisting of nitro, cyano, hydroxy, oxo, SiR ⁵ 3, PO (OR ⁵ ) 2, S (O) n (C1- Cs) -alkyl, (C1-Ce) -alkoxy, halo- (C1-Ce) -alkoxy, N (R ³ ) 2, COR ³ , OCOR ³ , NR ³ COR ³ , NR ³ SO2R ⁴ , (C3-Ce ) -cycloalkyl, heteroaryl, heterocyclyl, phenyl, Q-heteroaryl, Q-heterocyclyl, Q-phenyl and Q-benzyl, with radicals (C3-Ce) -cycloalkyl, heteroaryl, heterocyclyl, phenyl, Q-heteroaryl, Q- heterocyclyl, Q-phenyl and Q-benzyl are substituted in each case by s substituents of the group consisting of methyl, ethyl, methoxy, cyano, nitro, trifluoromethyl and halogen and in which heterocyclyl and cycloalkyl carry n oxo groups,
Q represents O, S or NR ³ ,
R ¹ represents hydrogen, (C1-Ce) -alkyl, (C2-Ce) -alkenyl, (C2-Cs) -alkynyl, (C3-Ce) -cycloalkyl, (C3-C6) -cycloalkyl- (C1-Cs) -alkyl, (C1-Cs) -alkyl-O- (C1-Cs) -alkyl, phenyl, phenyl- (C1-Ce) -alkyl, heteroaryl, (C1-Ce) -alkyl-heteroaryl, heterocyclyl, (C1- Cs) -alkyl-heterocyclyl, (C1Ce) -alkyl-O-heteroaryl, (C1-Ce) -alkyl-O-heterocyclyl, (C1-Ce) -alkylNR ³ -heteroaryl or (C1-C6) -alkyl-NR ³ -heterocyclyl, the last 16 radicals mentioned being replaced by radicals of the group consisting of cyan, halogen, nitro, OR ³ , S (O) nR ⁴ , N (R ³ ) 2, NR ³ OR ³ , COR ³ , OCOR ³ , NR ³ COR ³ , NR ³ SO2R ⁴ , CO2R ³ , CON (R ³ ) 2 and (C1-C4) alkoxy- (C2-C6) -alkoxycarbonyl and in which the heterocyclyl carries n oxo groups,
R ² represents (C1-C6) -alkyl, (C2-C6) -alkenyl, (C2-C6) alkynyl, (C3-C6) -cycloalkyl, (C3-C6) -cycloalkyl- (C1-C6) -alkyl, (C1C6) -alkyl-O- (C1-C6) -alkyl, phenyl, phenyl- (C1-C6) -alkyl, heteroaryl, (C1C6) -alkyl-heteroaryl, heterocyclyl, (C1-C6) -alkyl-heterocyclyl, (C1-C6) alkyl-O-heteroaryl, (C1-C6) -alkyl-O-heterocyclyl, (C1-C6) -alkyl-NR ³ heteroaryl or (C1-C6) -alkyl-NR ³ -heterocyclyl these radicals are replaced by radicals in the group consisting of cyan, halogen, nitro, OR ³ , S (O) nR ⁴ , N (R ³ ) 2, NR ³ OR ³ , NR ³ SO2R ⁴ , COR ³ ,
Petition 870180050694, of 06/13/2018, p. 10/144
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OCOR ³ , NR ³ COR ³ , CO2R ³ , CON (R ³ ) 2 and (C1-C4) -alkoxy- (C2-Ce) alkoxycarbonyl and where heterocyclyl carries n oxo groups,
R ³ represents hydrogen, (C1-Ce) -alkyl, (C2-Ce) -alkenyl, (C2-Cs) -alkynyl, (C3-Ce) -cycloalkyl or (C3-C6) -cycloalkyl- (C1-Cs) alkyl,
R ⁴ represents (C1-Ce) -alkyl, (C2-Ce) -alkenyl or (C2-C6) alkynyl,
R ⁵ represents methyl or ethyl,
R ⁶ represents OCOOR ⁴ , NR ⁴ COOR ⁴ , S (O) n- (C1-Ce) -alkyl, S (O) n- (C1-Ce) -haloalkyl, nitro, cyano, SiR ⁵ 3, PO (OR ⁵ ) 2 or heterocyclyl, which carries m oxo groups, m represents 1 or 2, n represents 0, 1 or 2, s represents 0, 1, 2 or 3, u represents 1, 2, 3, 4 or 5,
Particularly preferred are compounds of the general formula (I), in which
A represents N or CY,
B represents N or CH,
X represents nitro, halogen, cyano, (C1-C6) -alkyl, halo- (C1-C6) -alkyl, (C3-C6) -cycloalkyl, OR ¹ , S (O) nR ² , (C1-C6) alkyl -S (O) n ^2, (C1-C6) -alkyl-OR ^1, (C 1 -C 6) CON (R ¹⁾ 2, (C1-C6) SO 2 N (R ¹⁾ 2, (C1 -C6) -NR ¹ COR ¹ , (C1-C6) -NR ¹ SO2R ² , (C1-C6) -heteroaryl, (C1-C6) -heterocyclyl, the last two radicals mentioned being replaced by halogen radicals, (C1- C6) -alkyl, halogen (C1-C6) -alkyl, S (O) n- (C1-C6) -alkyl, (C1-C6) -alkoxy, halogen- (C1-C6) alkoxy and in which the heterocyclyl bears n oxo groups,
Y represents nitro, halogen, cyano, (C1-C6) -alkyl, (C1C6) -haloalkyl, OR ¹ , S (O) nR ² , SO2N (R ¹ ) 2, N (R ¹ ) 2, NR ¹ SO2R ² , NR ¹ COR ¹ , (C1-C6) -alkyl-S (O) nR ² , (C1-C6) -alkyl-OR ¹ , (C1-C6) -alkPetition 870180050694, of 06/13/2018, p. 10/154
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CON (R ¹ ) 2, (C 1 -C 6) -alkyl-SO2N (R ¹ ) 2, (C 1 -C 6) -alkyl-NR ¹ COR ¹ , (C 1 -C) alkyl-NR ¹ SO ² R ² , (C ^1- Ce) -alkyl-phenyl, (C1-Ce) -alkyl-heteroaryl, (C1Ce) -alkyl-heterocyclyl, phenyl, heteroaryl or heterocyclyl, the last 6 radicals being replaced in each case by radicals of the halogen, nitro group , cyano, (C1-Ce) -alkyl, halogen- (C1-Ce) -alkyl, (C3-Ce) -cycloalkyl, S (O) n- (C1-Ce) -alkyl, (C1-Ce) -alkoxy , halogen- (C1Ce) -alkoxy, (C1-Ce) -alkoxy- (C1-C4) -alkyl and cyanomethyl and where heterocyclyl carries n oxo groups,
Z represents halogen, cyano, halogen- (C1-Ce) -alkyl, (C3-Ce) -cycloalkyl, S (O) nR ² , 1,2,4-triazole or Z can also represent hydrogen, methyl, methoxy or ethoxy , if Y represents the radical S (O) nR ² ,
R represents CH2R ^and ,
CH2-heterocyclyl, with heterocyclyl having oxo groups, (C2-Ce) -alkyl, (C3-C7) -cycloalkyl, halo- (C2-Ce) alkyl, (C2-Ce) -alkenyl, halogen- (C2- Ce) -alkenyl, (C2-Ce) -alkynyl or halo- (C2-Ce) -alkynyl each substituted by u radicals of the group consisting of nitro, cyano, hydroxy, oxo, SiR ⁵ 3, PO (OR ⁵ ) 2, S (O) n- (C1Ce) -alkyl, (C1-Ce) -alkoxy, halogen- (C1-Ce) -alkoxy, N (R ³ ) 2, COR ³ , OCOR ³ , NR ³ COR ³ , NR ³ SO2R ⁴ , (C3-Ce) -cycloalkyl, heteroaryl, heterocyclyl, phenyl, Q-heteroaryl, Q-heterocyclyl, Q-phenyl and Q-benzyl, with radicals (C3-Ce) -cycloalkyl, heteroaryl, heterocyclyl, phenyl , Q-heteroaryl, Q-heterocyclyl, Q-phenyl and Q-benzyl are each substituted by s substituents of the group consisting of methyl, ethyl, methoxy, cyano, nitro, trifluoromethyl and halogen and in which heterocyclyl and cycloalkyl carry n oxo groups ,
Q represents O, S or NR ³ ,
R ¹ represents hydrogen, (C1-Ce) -alkyl, (C2-Ce) -alkenyl, (C2-Ce) -haloalkenyl, (C2-Ce) -alquinyl, (C3-Ce) -cycloalkyl, (C3Petition 870180050694, de 06/13/2018, page 16/104
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C6) -cycloalkyl- (C1-C6) -alkyl, (C1-C6) -alkyl-O- (C1-C6) -alkyl, phenyl, phenyl- (C1-Cs) -aiquia, heteroaryl, heterocyclyl, (C1- Ce) -alkyleterocyclyl, (C1-C6) -alkyl-O-heteroaryl, (C1-C6) -alkyl-O-heterocyclyl, (C1-C6) -alkyl-NR ³ -heteroaryl or (C1-C6) -alkyl- NR ³ -heterocyclyl, with the last i6 radicals mentioned being replaced by radicals of the group consisting of cyan, halogen, nitro, OR ³ , S (O) nR ⁴ , N (R ³ ) 2, NR ³ OR ³ , COR ³ , OCOR ³ , NR ³ COR ³ , NR ³ SO2R ⁴ , CO2R ³ , CON (R ³ ) 2 e (C1-C4) -alkoxy- (C2-C6) -alkoxycarbonyl and where heterocyclyl carries n oxo groups,
R ² represents (C1-C6) -alkyl, (C3-C6) -cycloalkyl or (C3C6) -cycloalkyl- (C1-C6) -alkyl, the last three radicals mentioned being replaced each by radicals of the group consisting of halogen and OR ³ ,
R ³ represents hydrogen or (C 1 -C 6) -alkyl,
R ⁴ represents (C 1 -C 6) -alkyl,
R ⁵ represents methyl or ethyl,
R ⁶ represents OCOOR ⁴ , NR ⁴ COOR ⁴ , S (O) n- (C1-C6) -alkyl, S (O) n- (C1-C6) -haloalkyl, nitro, cyano, SiR ⁵ 3, PO (OR ⁵ ) 2, m represents i or 2, n represents 0, i or 2, s represents 0, i, 2 or 3, u represents i, 2, 3, 4 or 5.
[00i0] In all the formulas mentioned below, the substituents and symbols, as long as not defined otherwise, have the same meaning as described in formula (I).
[00ii] Compounds according to the invention can be prepared, for example, according to the method specified in scheme i through catalyzed reaction based on a benzoic acid (II) chloride with a 5-amino-iHi, 2, 4-triazole or 5-amino-iHtetrazole (III):
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Layout 1
(Ni) (H) (i) [0012] The benzoic acid chlorides of formula (II), respectively, the benzoic acids which serve as the base, are fundamentally known and can be prepared, for example, according to the methods described in US 6,376,429 B1, EP
1,585,742 A1 and EP 1,202,978 A1.
[0013] Compounds according to the invention can also be prepared according to the method specified in scheme 2 by reacting a benzoic acid of formula (IV) with a 5 amino-1-H-1,2,4- triazole or 5-amino-1H-tetrazole (III):
Layout 2
h ₂ n The X Activation N N ’R H O, (in) (iv) (i) [0014] For activation can be used reagents
dehydrants, which are conventionally used for amidation reactions, such as, for example, 1,1'-carbonyldiimidazole (CDI), dicyclohexylcarbodiimide (DCC), 2,4,6-trioxides of 2,4, 6-tripropyl1,3,5,2,4,6-trioxatrifosfinanos (T3P) and so on.
[0015] Compounds according to the invention can also be prepared according to the method specified in scheme 3 by reacting an N- (1H-1,2,4-triazol-5-yl) benzamide, N- (1Htetrazole -5-yl) benzamide, N- (1H-1,2,4-triazol-5-yl) nicotinamide or N- (1Htetrazol-5-yl) nicotinamide:
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Layout 3
[0016] For this reaction mentioned in scheme 3, alkylating agents such as halides, alkyl sulfonates or dialkyl sulfates can be used.
[0017] It may be convenient to modify the reaction steps in their order. Thus, benzoic acids, which carry a sulfoxide, must not be converted into their acid chlorides without further ado. Here it is advisable to prepare the amide initially at the thioether stage and then oxidize the thioether to the sulfoxide.
[0018] The 5-amino-1H-tetrazoles of formula (III) can be prepared in a manner analogous to methods known in the literature. For example, 5-amino-1-R-tetrazoles can be prepared according to the method described in the Journal of the American Chemical Society (1954), 76, 923-924 from amino-tetrazole:
H
N i
N.
NaOH / RX
R NH, y ²
N /
[0019] In the formula mentioned above, R represents, for example, an alkyl radical.
[0020] 5-amino-1-R-tetrazoles can be synthesized, for example, as described, for example, in the Journal of the American Chemical Society (1954), 76, 88-89:
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R NH 7 h ^H h ' ^N V
H
NaNOj / HCI
NH, / W
N ' ^N <, [0021] The 5-amino-1H-triazoles of formula (III) can be prepared in a manner analogous to methods known in the literature. For example, 5-amino-1-R-triazoles can be prepared according to the method described in Zeitschrift für Chemie (1990), 30 (12), 436 - 437 from aminotriazole:
NNH,
NH.
NaOH / RX [0022] The 5-amino-1-R-triazoles can also be synthesized, for example, as described in Chemische Berichte (1964), 97 (2), 396-404:
HCOOH
R NH.
w
Ny. N [0023] The 5-amino-1-R-triazoles can also be synthesized, for example, as described in Angewandte Chemie (1963), 75, 918:
NH-
OEt f \ ^N ^ N [0024] Collections of compounds of formula (I) and / or their salts, which can be synthesized according to the reactions mentioned above, can also be prepared in parallel, and this can occur manual, partially automated
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16/89 or completely automated. In this case, it is possible, for example, to automate the conduct of the reaction, the processing or the purification of the products or intermediate steps. Altogether, among these is understood a procedure, as described, for example, by D. Tiebes in Combinatorial Chemistry - Synthesis, Analysis, Screeening (editor Günther Jung), Verlag Wiley 1999, on pages 1 to 34.
[0025] For the parallel conduct of the reaction and processing, a series of commercially available equipment can be used, for example, Calypso reaction blocks (Calypso reaction blocks) from Barnstead International, Dubuque, Iowa 520040797, USA or reaction stations (reaction stations) from Radleys, Shirehill, Saffron Walden, Essex, CB 11 3AZ, England or MultiPROBE Automated Workstations from Perkin Elmar, Waltham, Massachusetts 02451, USA. For the parallel purification of compounds of the general formula (I) and their salts, respectively, of intermediate products obtained in the preparation, there are, among others, chromatography devices available, for example, from the company ISCO, Inc., 4700 Superior Street, Lincoln, NE 68504, USA.
[0026] The listed equipment leads to a modular procedure, in which the individual operation steps are automated, between the operation steps, however, manual operations must be performed. These can be avoided by using partially or fully integrated automation systems, in which the respective automation modules are served, for example, by robots. Such automation systems can be referred, for example, by the company Caliper, Hopkinton MA 01748, USA.
[0027] The performance of some or several synthesis steps can be supported by the use of reagents with support
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17/89 polymeric / sequestering resins. The scientific literature describes a series of test protocols, for example, ChemFiles, Vol. 4, No. 1, Polymer-Supported Scavengers and Reagents for Synthesis SolutionPhase (Sigma-Aldrich).
[0028] In addition to the methods described here, the preparation of compounds of the general formula (I) and their salts can be carried out completely or partially by methods supported by solid phases. For this purpose, some intermediate stages or all intermediate stages of the synthesis or a synthesis adapted to the corresponding procedure are bonded to a synthetic resin. Synthesis methods supported by solid phases are sufficiently described in the scientific literature, for example, Barry A. Bunin in The Combinatorial Index, Verlag Academic Press, 1998 and Combinatorial Chemistry - Synthesis, Analysis, Screeening (editor Günther Jung), Verlag Wiley, 1999 The use of synthesis methods supported by solid phases allows a series of protocols known from the literature, which in turn can be executed manually or automated. The reactions can be carried out, for example, using IRORI technology in micro-reactors (microreactors) from the company Nexus Biosystems, 12140 Community Road, Poway, CA92064, USA.
[0029] The execution of some or several synthesis steps both in solid and liquid phases can be supported by the use of microwave technology. A number of test protocols are described in the scientific literature, for example, in Microwaves in Organic and Medicinal Chemistry (editor C. O. Kappe and a. Stadler), Verlag Wiley, 2005.
[0030] The preparation according to the processes described here, provides compounds of formula (I) and their salts in the form of collections of substances, which are mentioned in libraries. The purpose of the present invention is also libraries, which contain at least
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[0031] The compounds of the formula (I) according to the invention (and / or their salts), hereinafter referred to together as compounds according to the invention, have an excellent herbicidal efficacy against a wide spectrum of important mono-weeds and annual dicots. Perennial weeds also difficult to fight, which sprout from rhizomes, roots or other permanent organs, are well covered by the active substances.
[0032] The object of the present invention, therefore, is also a process for combating unwanted plants or for regulating plant growth, preferably in plant cultures, in which one or more compound (s) is (are) applied (s) in plants (for example, weeds, such as single or dicot weeds or unwanted crop plants), in seed (for example, grains, seeds or vegetative propagating organs, such as tubers or parts of shoots with buds) or in the area in which the plants grow (for example, in the cultivated area). In that case, the compounds according to the invention can be applied, for example, in the pre-seeding process (optionally also through incorporation into the soil), in the pre-emergence or post-emergence process. Individually, mention should be made, for example, of representatives of mono- and dicotyledonous weed flora, which can be controlled by the compounds according to the invention, without mentioning a restriction on certain species.
[0033] Monocotyledon weeds of the genera: Aegilops, Agropyron, Agrostis, Alopecurus, Apera, Avena, Brachiaria, Bromus, Cenchrus, Commelina, Cynodon, Cyperus, Dactiloctenium, Digitaria, Echinochloa, Eleocharis, Eleusine, Eragrl , Heteranthera, Imperata, Ischaemum, Leptochloa, Lolium,
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Monochoria, Panicum, Paspalum, Phalaris, Phleum, Poa, Rottboellia, Sagittaria, Scirpus, Setaria, Sorghum.
[0034] Dicotyledonous weeds of the genera: Abutilon, Amaranthus, Ambrosia, Anoda, Anthemis, Aphanes, Artemisia, Atriplex, Bellis, Bidens, Capsella, Carduus, Cassia, Centaurea, Chenopodium, Cirsium, Convolvulus, Datura, Desmodium, Emex, Erysimum , Euphorbia, Galeopsis, Galinsoga, Galium, Hibiscus, Ipomoea, Kochia, Lamium, Lepidium, Lindernia, Matricaria, Mentha, Mercurialis, Mullugo, Myosotis, Papaver, Pharbitis, Plantago, Polygonum, Portulaca, Ranunculus, Raphanus, Rorippa, Rorippa, Rorippa, Rorippa, Rumippa , Salsola, Senecio, Sesbania, Sida, Sinapis, Solanum, Sonchus, Sphenoclea, Stellaria, Taraxacum, Thlaspi, Trifolium, Urtica, Veronica, Viola, Xanthium.
[0035] If the compounds according to the invention are applied to the earth's surface before germination, then either the emergence of eda4 seedlings is completely prevented or the weeds grow to the leaf germination stage, however, then adjust their growth and finally die completely after three to four weeks.
[0036] When applying the active substances to the green parts of the plants in the post-emergence process, after the treatment, a growth stop occurs and the weeds remain in the growth stage present at the moment of application or die completely after a certain period. time, so that in this way, harmful competition from weeds for crop plants is removed very early and permanently. [0037] Although the compounds according to the invention have an excellent herbicidal activity against mono- and dicotyledonous weeds, crop plants of economically important crops, such as, for example, crops
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20/89 dicotyledons of the genera Arachis, Beta, Brassica, Cucumis, Cucurbita, Helianthus, Daucus, Glycine, Gossypium, Ipomoea, Lactuca, Linum, Lycopersicon, Nicotiana, Phaseolus, Pisum, Solanum, Vicia or monocotyledonous cultures of the All genus, Allium Asparagus, Avena, Hordeum, Oryza, Panicum, Saccharum, Secale, Sorghum, Triticale, Triticum, Zea, in particular, Zea and Triticum, depending on the structure of the respective compound according to the invention or its amount of application, are just a little or not even harmed. For these reasons, the present compounds are very well suited for selectively combating the growth of unwanted plants in plant cultures, such as useful agricultural plantations or ornamental plantations.
[0038] In addition, the compounds according to the invention (depending on their structure and the amount of application) have excellent growth-regulating properties in crop plants. These penetrate regulating the plant's own metabolism and, with this, they can be used for the target control of phytonutrients and to facilitate harvesting, such as, for example, by triggering desiccation and stifling growth. In addition, the compounds are also suitable for the control and general inhibition of unwanted vegetative growth, without thereby killing the plants. An inhibition of vegetative growth is of great importance in many mono- and dicotyledonous cultures, since, for example, the formation of the support, by this means, can be reduced or completely prevented.
[0039] Based on their herbicidal and plant growth regulating properties, the active substances can also be used to combat weeds in crops of genetically modified or modified plants through conventional mutagenesis. Transgenic plants stand out, via
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21/89 as a rule, for particular advantageous properties, for example, for resistance against certain pesticides, mainly certain herbicides, resistance against plant diseases or plant disease pathogens, such as certain insects or microorganisms, such as fungi, bacteria or virus. Other particular properties refer, for example, to the material collected with respect to quantity, quality, storability, composition and special constitutive substances. In this way, transgenic plants are known to have a higher degree of starch or modified starch quality or those with different fatty acid composition from the harvested material.
[0040] With respect to transgenic crops, preference is given to the application of the compounds according to the invention in economically important transgenic crops of useful and ornamental plants, for example, cereals, such as wheat, barley, rye, oats, millet, rice and corn or also beet, cotton, soy, rapeseed, potato, tomato, pea and other vegetable varieties. The compounds according to the invention can preferably be used as herbicides in useful plant cultures, which are resistant to the phytotoxic effects of the herbicides or have been transformed into genetically resistant.
[0041] The application of the compounds according to the invention or their salts is preferred in economically important transgenic crops of useful and ornamental plants, for example, cereals, such as wheat, barley, rye, oats, millet, rice, cassava and corn or also in beet, cotton, soy, rapeseed, potato, tomato, pea and other vegetable varieties. Preferably, the compounds according to the invention can be used as herbicides in useful plant cultures, which are resistant to the phytotoxic effects of the herbicides or have been
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[0042] Conventional methods for the production of new plants, which have modified properties compared to existing plants, consist, for example, in classic cultivation processes and in the production of mutants. Alternatively, new plants with modified properties can be produced with the aid of genetic engineering processes (see, for example, EPA-0221044, EP0131624). They have been described, for example, in several cases
- genetic modifications of crop plants for the purpose of modifying the starch synthesized in plants (for example, WO 92/011376, WO 92/014827, WO 91/019806),
- transgenic crop plants, which are resistant to certain glufosinate-type herbicides (compare, for example, EP-A-0.242.236 A, EP-A-0.242.246) or glyphosate (WO 92/000377) or sulfonylureas (EP-A-0257993, US-A-5,013,659),
- transgenic crop plants, for example, cotton, with the ability to produce Bacillus thuringiensis toxins (Bt toxin), which make plants resistant to certain pests (EP-A-0142924, EP-A-0193259),
- transgenic crop plants with modified fatty acid composition (WO 91/013972),
- crop plants genetically modified with new constituent or secondary substances, for example, new phytoalexins, which cause greater resistance to diseases (EPA 0309862, EPA0464461),
- genetically modified plants with reduced photorespiration, which have higher yields and greater tolerance to stress (EPA0305398),
- transgenic crop plants, which produce proteins
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23/89 pharmaceutically or diagnostically important (molecular pharming),
- transgenic crop plants, which stand out for higher yields or better quality,
- transgenic crop plants, which stand out for a combination, for example, of the new properties mentioned above (gene stacking).
[0043] Numerous techniques of molecular biology, with which new transgenic plants with modified properties can be produced, are, in principle, known; see, for example, I. Potrykus and G. Spangenberg (editors) Gene Transfer to Plants, Springer Lab Manual (1995), Springer Verlag Berlin, Heidelberg or Christou, Trends in Plant Science 1 (1996) 423-431).
[0044] For such genetic manipulations, nucleic acid molecules can be introduced into plasmids, which allow for mutagenesis or sequential modification through recombination of DNA sequences. With the aid of standard processes, for example, base changes can be made, partial sequences removed or natural or synthetic sequences added. For the ligation of the DNA fragments, adapters or linkers can be connected to the fragments; see, e.g., Sambrook et al, 1989, Molecular Cloning, A Laboratory Manual, 2nd edition , Cold Spring Harbor Laboratory Press, Cold Spring Harbor, NY; or Winnacker Gene und Klone, VCH Weinheim 2nd edition 1996.
[0045] The production of plant cells with reduced activity of a gene product can be achieved, for example, through the expression of at least one corresponding antisense RNA, a positive sense RNA to obtain a co-suppression effect or the expression of at least one ribozyme constructed
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24/89 correspondingly, which specifically dissociates transcripts from the aforementioned gene product. For this purpose, on the one hand, DNA molecules may be used, which comprise the entire coded sequence of a gene product, including flanking sequences optionally present, as well as DNA molecules, which comprise only parts of the coding sequence, and these parts must long enough to have an anti-sense effect on cells. Possible is also the use of DNA sequences, which have a high degree of homology in relation to the coding sequences of a gene product, but are not completely identical.
[0046] In the expression of nucleic acid molecules in plants, the synthesized protein can be located in each desired compartment of the plant cell. But to obtain the location in a particular compartment, for example, the coding region can be linked with DNA sequences, which ensure the location in a given compartment. Such sequences are known to the specialist (see, for example, Braun et al., EMBO J. 11 (1992), 3219-3227; Wolter et al., Proc. Natl. Acad. Sci. USA 85 (1988), 846-850; Sonnewald et al., Plant J. 1 (1991), 95106). The expression of nucleic acid molecules can also be performed on the organelles of plant cells.
[0047] Transgenic plants can be regenerated to form whole plants using known techniques. In the case of transgenic plants, it may be, in principle, plants of any species of plant, that is, both monocotyledonous and dicotyledonous plants.
[0048] Thus, transgenic plants can be obtained, which have modified properties through overexpression, suppression or inhibition of homologous (= natural) genes or sequences
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25/89 gene expression or heterologous (= foreign) genes or gene sequences.
[0049] Preferably, the compounds according to the invention can be used in transgenic cultures, which are resistant to growth substances, such as, for example, dicamba or to herbicides, which inhibit the enzymes of essential plants, for example, acetolactate synthases (ALS), EPSP synthases, glutamino synthases (GS) or hydroxyphenylpyruvate dioxigenases (HPPD), respectively, to the herbicides of the group of sulfonylureas, glyphosate, glufosinate or benzoylisoxazoles and analogous active substances.
[0050] When applying the active substances according to the invention in transgenic cultures, there are, in addition to the effects to be observed in other cultures in relation to weeds, often effects, which are specific to the application in the respective transgenic culture, for example example, a modified or specially extended weed spectrum, which can be combated, modified application amounts, which can be used for application, preferably good combining ability with herbicides, to which the transgenic crop is resistant, as well as influence of growth and yield of transgenic crop plants.
[0051] The purpose of the invention, therefore, is also to use the compounds according to the invention as herbicides to combat weeds in transgenic crop plants.
[0052] The compounds according to the invention can be applied in the form of spray powders, emulsifiable concentrates, spray solutions, dusting powders or granules in conventional preparations. The object of the invention is, therefore, also herbicidal and plant growth regulating compositions, which contain the compounds according to
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[0053] The compounds according to the invention can be formulated differently, depending on which biological and / or chemical-physical parameters are predetermined. Formulation possibilities include, for example: spray powders (WP), water-soluble powders (SP), water-soluble concentrates, emulsifiable concentrates (EC), emulsions (EW), such as oil-in-water and water-in emulsions -Oil, spray solutions, suspension concentrates (SC), oil or water based dispersions, oil miscible solutions, capsule suspensions (CS), dusting powders (DP), disinfectants, granules for spreading and soil, granules (GR) in the form of microgranules, atomization granules, coating and adsorption, water dispersible granules (WG), water-soluble granules (SG), ultra low volume formulations (ULV), microcapsules and waxes. These individual types of formulations are in principle known and are described, for example, in: Winnacker-Küchler, Chemische Technologie, Volume 7, C. Hanser Verlag Munich, 4th edition 1986; Wade van Valkenburg, Pesticide Formulations, Marcel Dekker, NY, 1973; K. Martens Spray Drying Handbook, 3rd edition, 1979, G. Goodwin Ltd. London.
[0054] The auxiliaries necessary formulations, such as inert materials, surfactants, solvents and other addictive substances are also known and are described, for example, in: Watkins, Handbook of Insecticide Dust Diluents and Carriers, 2nd Edition, Darland Books, Caldwell NJ; Hv Olphen, Introduction to Clay Colloid Chemistry; 2nd edition, J. Wiley & Sons,
NY; C. Marsden, Solvents Guide; 2nd edition, Interscience, NY 1963; McCutcheon's Detergents and Emulsifiers Annual, MC Publ. Corp., Ridgewood NJ; Sisley and Wood, Encyclopedia of Surface
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Active Agents, Chem. Publ. Co. Inc., NY 1964; Schonfeldt, Grenzflàchenaktive Àthilenoxidaddukte, Wiss. Verlagsgesell., Stuttgart 1976; Winnacker-Küchler, Chemische Technologie, Volume 7, C. Hanser Verlag Munich, 4th edition 1986.
[0055] Based on these formulations, combinations can also be prepared with other substances with pesticidal action, such as, for example, insecticides, acaricides, herbicides, fungicides, as well as with protectors, fertilizers and / or growth regulators, for example, in the form of a ready formulation or as a tank mix. Suitable protectors are, for example, mefenpir-diethyl, cyprosulfamide, isoxadifen-ethyl, cloquintocet-mexila and diclormid.
[0056] Spray powders are preparations uniformly dispersible in water which, in addition to the active substance, in addition to a diluent or inert material, also contain surfactants of an ionic and / or non-ionic nature (humectants, dispersants), for example, polyoxyethylated alkylphenols , polyoxyethylated fatty alcohols, polyoxyethylated fatty amines, fatty alcohol polyglycolic ether sulphates, alkanesulphonates, alkylbenzenesulphonates, sodium ligninosulphonate, sodium 2,2'-dinaftilmethan-6,6'-disulphonate, also dibutylnaphthalensulfonensulphonatesulfonatesulfonatesulfonatesulfonates. To prepare the spray powders, the herbicidal active substances are finely ground, for example, in conventional equipment, such as hammer mills, forced air mills and air jet mills and are simultaneously or subsequently mixed with the formulating auxiliary agents .
[0057] Emulsifiable concentrates are produced by dissolving the active substance in an organic solvent, for example, butanol, cyclohexanone, dimethylformamide, xylene or also high-boiling aromatic compounds or hydrocarbons or mixtures of organic solvents with the addition of one or more surfactants in
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28/89 ionic and / or non-ionic nature (emulsifiers). As emulsifiers, for example, calcium alkylarylsulfonate salts, such as calcium dodecylbenzenesulfonate or nonionic emulsifiers, such as polyglycolic fatty acid ester, polyarylalkyl polyglycolic ether, polyglycolic ether of fatty alcohol, condensation products of propylene oxide ethylene oxide, alkyl polyether, sorbic esters, such as, for example, sorbitanograxide acid ester or polyoxyethylene sorbitan esters, such as, for example, polyoxyethylene sorbitanograxide acid ester.
[0058] Dusting powders are obtained by grinding the active substance with finely dispersed solid substances, for example talc, natural clays, such as kaolin, bentonite and pyrophyllite or with infusoria earth.
[0059] Suspension concentrates can be water or oil based. They can be prepared, for example, by wet milling using commercially available pearl mills and optionally adding surfactants, such as, for example, already mentioned above in other types of formulations. [0060] Emulsions, for example, oil-in-water (EW) emulsions can be prepared, for example, by means of agitators, colloid mills and / or static mixers using aqueous organic solvents and optionally surfactants, such as, for example, example, are already mentioned above in the other types of formulations.
[0061] Granules can be prepared either by spraying the active substance on inert granular material capable of adsorption or by applying the active substance concentrates by means of adhesives, for example, polyvinyl alcohol, sodium polyacrylate or also mineral oils, on the surface of carriers, such as sand, kaolinite or granulated inert material. Suitable active substances can be granulated in a conventional manner for
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29/89 preparation of fertilizer granules - if desired, mixed with fertilizers -.
[0062] Water-dispersible granules are prepared, as a rule, according to conventional processes, such as spray drying, fluid bed granulation, disc granulation, mixing with high-speed machines and extrusion without solid inert material.
[0063] To produce granules disks, fluidizing bed, extrusion and spraying, see, for example, processes in SprayDrying-Handbook, 3rd edition , 1979, G. Goodwin Ltd., London, JE Browning, Agglomeration, Chemical and Engineering 1967 147 and following pages, Perry's Chemical Engineer's Handbook, 5th edition, McGraw-Hill, New York 1973, pages 8-57.
[0064] For other particularities for formulating preparations to protect plants, see, for example, GC Klingman, Weed Control as a Science, John Wiley and Sons, Inc., New York, 1961, pages 81-96 and JD Freyer, SA Evans, Weed Control Handbook 5th edition, Blackwell Scientific Publications, Oxford, 1968, pages 101-103.
[0065] Agrochemical preparations usually contain 0.1 to 99% by weight, in particular 0.1 to 95% by weight, of compounds according to the invention. In spray powders, the concentration of active substance matters, for example, from about 10 to 90% by weight, the rest to 100% by weight, consists of component of conventional formulations. In emulsifiable concentrates, the concentration of the active substance can matter in about 1 to 90, preferably 5 to 80% by weight. Formulations in powder form contain 1 to 30% by weight, of active substance, preferably, in general, 5 to 20% by weight, of active substance, spray solutions contain about 0.05 to 80, preferably 2 to 50% in weight of
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30/89 active substance. In water-dispersible granules, the active substance content depends, in part, on whether the effective compound is present in liquid or solid form and which auxiliary granulation agents, fillers and other materials are used. In water-dispersible granules, the active substance content is, for example, between 1 and 95% by weight, preferably between 10 and 80% by weight.
[0066] In addition, the active substance formulations mentioned optionally contain adhesives, humectants, dispersants, emulsifiers, penetrating agents, preservatives, frost and solvent protection agents, fillers, carriers and dyes, defoamers, evaporation inhibitors. and conventional pH value and viscosity influencing agents in each case.
[0067] Based on these formulations, combinations can also be prepared with other substances with pesticidal action, such as, for example, insecticides, acaricides, herbicides, fungicides, as well as with protectors, fertilizers and / or growth regulators, for example, in the form of a ready formulation or as a tank mix.
[0068] As participants in combinations for the compounds according to the invention in mixing formulations or tank mixtures, for example, known active substances, which are based on an inhibition of, for example, acetolactate synthase, acetyl -CoA-carboxylase, cellulose synthase, enolpyruvylshikimat-3-phosphate synthase, glutamine synthetase, phydroxyphenylpyruvate dioxigenase, phytendesaturase, photosystem I, photosystem II, protoporphyrinogen oxidase, as described, for example, in 441-445 (1986) or the Pesticide Manual, 15th edition, the British Crop Protection Council and the Royal
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Soc. Of Chemistry, 2009 and literature cited there. As known herbicides or plant growth regulators, which can be combined with the compounds according to the invention, the following active substances can be cited, for example, (the compounds are designated or by the common name according to the International Organization for Standardization (ISO) or chemical name or code number) and always comprise all forms of application, such as acids, salts, esters and isomers, such as stereoisomers and optical isomers. In this case, for example, one and in part also several forms of application are mentioned:
acetochlor, acibenzolar, acibenzolar-S-methyl, acifluorfen, acifluorfen-sodium, aclonifen, alachlor, alidochlor, aloxidim, aloxidim-sodium, ametrin, amicarbazone, amidochlor, amidosulfuron, aminocycliraclor, aminopyridyl, aminopyridyl, aminopyridyl, aminopyridyl, aminopyridyl, aminopyridyl, aminopyridyl asulam, atrazine, azafenidin, azimsulfuron, aziprotrin, beflubutamide, benazolin, benazolin-ethyl, bencarbazone, benfluralin, benfuresate, bensulide, bensulfuron, bensulfuron-methyl, bentazone, benzfendoline, benzaphiloxy, benzobicyclone, benzaphiloxy, benzobicyclone bilanafos-sodium, bispyribac, bispyribac-sodium, bromacil, bromobutide, bromophenoxy, bromoxynil, bromuron, buminafos, busoxinone, butachlor, butafenacil, butamiphos, butenachlor, butralin, butroxidim, butylate, carboxymethyl, carthenetron, carthenethamide, carthenethamide, carthenethamide, carboxymethyl cloramben, clorazifop, clorazifopbutila, clorbromuron, clorbufam, chlorfenac, chlorfenac-sodium, clorfenprop, chlorflurenol, chlorflurenol-methyl, chloridazo n, chlorimuron, chlorimuron-ethyl, chlormequat chloride, chlornitrofen, chlorophthalim, chlortaldimethyl, chlorotoluron, chlororsulfuron, cinidon, cinidon-ethyl, cinmetilin, cinosulfuron, cletodim, clodinafop, clodinafop-propone, clodinafop-propone, clodina-propone chloransulam, cloransulammethyl, cumiluron, cyanamide, cyanazine, cyclanilide, cyclate,
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32/89 ciclosulfamuron, cicloxidim, cicluron, ci-halofop, ci-halofop-butyl, cyperquat, cyprazine, cyprazole, 2,4-D, 2,4-DB, daimuron / dimron, dalapon, daminozide, dazomet, n-decanol , desmedifam, desmetrin, detosyl pyrazolate (DTP), dialate, dicamba, diclobenyl, dichlorprop, dichlorprop-P, diclofop, diclofop-methyl, diclofop-P-methyl, diclosulam, diethyl, diethyl-ethyl, difenoxuron, difenoxuron, difenoxuron, difenzoxurl , diflufenzopyr-sodium, dimefuron, dikegulac-sodium, dimefuron, dimepiperate, dimetachlor, dimetametrin, dimethenamide, dimethenamide-P, dimetipin, dimetrasulfuron, dinitramine, dinoseb, dinoterb, diphenamide, dipropetrine, diquat, diquat, diquat, diquat, diquat, diquat, diquat, diquat, diquat, diquat, diquat, diquat, diquat, diquat, diquat, diquat, diquat, diquat, diquat, diquat, diquat, diquat, diquat, diquat. , eglinazin-ethyl, endotal, EPTC, esprocarb, etalfluralin, etametsulfuron, etametsulfuron-methyl, etefon, etidimuron, ethiozine, etofumesate, ethoxyfen, ethoxyphenyl-ethyl, ethoxysulfuron, etobenzanide, F5331, this -fluor-5- [4- (3-fluorpropyl) -4,5-dihydro-5-oxo1H-tetrazol-1-yl] -phenyl] -ethanesulfo namida, F-7967, i.e. 3- [7-chloro-5fluor-2- (trifluoromethyl) -1H-benzimidazol-4-yl] -1-methyl-6 (trifluoromethyl) pyrimidin-2,4 (1 H, 3H) -dione, fenoprop, fenoxaprop, fenoxaprop-P, fenoxaprop-ethyl, fenoxaprop-P-ethyl, phenoxasulfone, fentrazamide, fenuron, flamprop, flamprop-M-isopropyl, flamprop-Mmetila, flazasulfuron, florasulam, fluazifop, fluazifop, fluazifop , fluazifop-butyl, fluazifop-P-butyl, fluazolate, flucarbazone, flucarbazon-sodium, flucetosulfuron, flucloraline, flufenacet (thiafluamide), flufenpir, flufenpirethyl, flumetralin, flumetsulam, flumiclorin, flumicloracin, flumicloracin fluoroglycofen, fluoroglycophen-ethyl, flupoxam, flupropacil, flupropanate, flupirsulfuron, flupirsulfuron-methyl-sodium, flurenol, flurenol-butyl, fluridone, flurochloridone, fluroxipir, fluroxipir-meptil, fluroxipetam, flurprim, flurprim, flurprimet foramsulfuron, forclorfenuron, phosamine, furyloxifen, gibberellic acid, glufosin to, glufosinate-ammonium, glufosinate-P, glufosinate-P-ammonium, glufosinate-PPetition 870180050694, of 06/13/2018, p. 37/104
33/89 sodium, glyphosate, glyphosate-isopropylammonium, H-9201, i.e., O- (2,4-dimethyl-6-nitrophenyl) -O-ethyl-isopropylphosphoramidothioate, halosafen, halosulfuron, halosulfuron-methyl, haloxifop-P, haloxifop-P haloxifopetoxiethyl, haloxifop-P-ethoxyethyl, haloxifop-methyl, haloxifop-P-methyl, hexazinone, HW-02, that is, 1- (dimethoxyphosphoryl) -ethyl (2,4dichlorophenoxy) acetate, imazametabenz, imazametabenz-methyl, imazamoxoxy, imazamoxy -ammonium, imazapic, imazapyr, imazapyrisopropylammonium, imazaquin, imazaquin-ammonium, imazetapyr, imazetapiramonium, imazosulfuron, inabenfide, indanofan, indaziflam, indolacetic acid (IAA), 4-indol-3-ylulfonic acid (IAA) -methyl-sodium, ioxynil, ipfencarbazone, isocarbamide, isopropaline, isoproturon, isouron, isoxaben, isoxaclortol, isoxaflutol, isoxapyrifop, KUH-043, that is, 3 - ({[5- (difluormethyl) -1-methyl-3 (trifluoromethyl) -1-methyl-3 (-1 ) -1H-pyrazol-4-yl] methyl} sulfonyl) -5,5-dimethyl-4,5-dihydro-1,2oxazole, karbutilate, ketospiradox, lactofen, lenacil, linuron, hydraz maleic acid, MCPA, MCPB, MCPB-methyl, -ethyl and -sodium, mecoprop, mecoprop-sodium, mecoprop-butotyl, mecoprop-P-butotyl, mecopropP-dimethylammonium, mecoprop-P-2-ethyl-hexyl, mecoprop -P-potassium, mefenacet, mefluidide, mepiquat chloride, mesosulfuron, mesosulfuron-methyl, mesotrione, metabenztiazuron, metam, metamifop, metamitron, metazachlor, metazasulfuron, metazol, methypyrosulfuron, methoxymethylone, methoxymethyl, methoxymethyl, methoxymethyl, methoxymethyl, methoxymethoxy , metolachlor, S-metolachlor, metosulam, methoxyuron, metribuzin, metsulfuron, metsulfuron-methyl, molinate, monalide, monocarbamide, monocarbamide dihydrogen sulfate, monolinuron, monosulfuron, monosulfuronic ester, monuron, MT 128 N - [(2E) -3chloroprop-2-en-1-yl] -5-methyl-N-phenylpyridazin-3-amine, MT-5950, i.e., N- [3-chloro-4- (1-methylethyl ) -phenyl] -2-methylpentanamide, NGGC-011, naproanilide, napropamide, naptalam, NC-310, that is, 4- (2.4 Petition 870180050694, of 13/06/2018, p. 38/104
34/89 dichlorobenzoyl) -1-methyl-5-benzyloxypyrazole, neburon, nicosulfuron, nipyraclofen, nitralin, nitrophen, sodium nitrophenolate (isomeric mixture), nitrofluorfen, nonanoic acid, norflurazon, orbencarbone, oxadiazone, oxaziclomefon, oxifluorfen, paclobutrazol, paraquat, paraquat dichloride, pelargonic acid (nonanoic acid), pendimethalin, pendralin, penoxsulam, pentanochlor, pentoxazone, perfluidone, petoxamide, phenisofam, pphenamphenol, pphenamphenol, pphenamphenol, pphenamphenol, pimmedamin , pyrifenop-butyl, pretilachlor, primisulfuron, primisulfuron-methyl, probenazole, profluazole, prociazine, prodiamine, prifluralin, profoxidim, prohexadione, prohexadionacalcium, prohydroprosmone, prometone, prometrin, propachizine, propaquiz, propanaz, propanaz, propanaz, propanazole , propisochlor, propoxycarbazon, propoxycarbazon-sodium, propyrisulfurone, propizamide, prosulfaline, prosulfocarb, prosulfuron, prinachlor, piracloni l, piraflufen, piraflufenetila, pirasulfotol, pyrazolinate (pyrazolate), pirazosulfuron, pirazosulfuron-ethyl, pyrazoxifen, piribambenz, piribambenz-isopropila, piribambenz-propyl, piribenzoxim, pyributicarb, pyridafol, pyridimide, pyridimide, pyridimide, pyridimide , piritiobac-sodium, pyroxasulfone, pyroxosulam, quinclorac, quinmerac, quinoclamine, quizalofop, quizalofop-ethyl, quizalofop-P, quizalofop-Petila, quizalofop-P-tefuril, rimsulfuron, saflufenacid, szimetrex, szimetrex, setretez, -106279, that is, methyl- (2R) 2 ({7- [2-chloro-4- (trifluoromethyl) phenoxy] -2-naphthyl} oxy) propanoate, sulcotrione, sulfalate (CDEC), sulfentrazon, sulfometuron, sulfometuron- methyl, sulfosate (glyphosate-trimesium), sulfosulfuron, SIN523, SIP-249, that is, 1-ethoxy-3-methyl-1-oxobut-3-en-2-yl-5- [2-chloro-4 (trifluoromethyl ) phenoxy] -2-nitrobenzoate, SIP-300, i.e., 1- [7-fluor-3-oxo4- (prop-2-in-1-yl) -3,4-dihydro-2H-1, 4-benzoxazin-6-yl] -3-propyl-2tioxo midazolidin-4,5-dione, tebutam, tebutiuron, tecnazene,
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35/89 tefuriltrione, tembotrione, tepraloxidim, terbacil, terbucarb, terbuclor, terbumeton, terbutilazine, terbutrin, tenilchlor, thiafluamide, thiazafluron, thiazopyr, tidiazimine, tidiazuron, thencarbazone, thencarbazone, thencarbazone, thencarbazone , tralcoxidim, triafamon, trialate, triasulfuron, triaziflam, triazophenamide, tribenuron, tribenuron-methyl, trichloroacetic acid (TCA), triclopyr, tridifan, trietazine, trifloxisulfuron, trifloxysulfuron, trifloxon, trifloxon, trifluorine, trifloxon , tritosulfuron, tsitodef, uniconazole, uniconazole-P, vernolate, ZJ0862, i.e., 3,4-dichloro-N- {2 - [(4,6-dimethoxypyrimidin-2yl) oxy] benzyl} aniline, as well as the following compounds :


[0069] For the application, the formulations present in the commercially available form are optionally diluted in an
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36/89 conventional, for example, in the case of spray powders, emulsifiable concentrates, dispersions and granules dispersible in water, by means of water. Preparations in the form of powder, granules for the soil or spreading, as well as sprinkling solutions, are conventionally no longer diluted with other inert substances before application. With external conditions, such as temperature, humidity, the nature of the herbicide used and others, the amount of application required for the compounds of formula (I) varies. This can oscillate within wide limits, for example, between 0.001 and 1.0 kg / ha or more active substance, preferably it is, however, between 0.005 and 750 g / ha.
[0070] The following examples illustrate the invention:
A. Chemical examples
1. Synthesis of 2-chloro-4- (methylsulfonyl) -N- (1- (2-methoxyethyl) tetrazol-5-yl) benzamide (Example Table No. 1-12) [0071] 176 mg (0 , 75 mmol) of 2-chloro-4- (methylsulfonyl) benzoyl chloride, 145 mg (1.0 mmol) of 5-amino-1- (2-methoxyethyl) -tetrazole in 2 ml of pyridine, are stirred at 60 ^o C for 12 hours. Then is added 0.1 ml of water, stirred at 60 ° C for 30 minutes and added to 2N HCl and EE. The separated organic phase is again washed with 2N HCl and sodium chloride solution, dried over Na2SO4, concentrated and purified by means of RP-HPLC (acetonitrile / water). Yield: 66 mg (23%).
Synthesis of 5-amino-1 - (2-methoxyethyl) -tetrazole [0072] A mixture of 2.33 g (10 mmol) of S-methylisothiosemicarbazide hydroiodate and 751 mg (10 mmol) of 2-methoxyethylamine are heated in 10 ml of ethanol for so long at reflux, until no methylmercaptan is released. Then, concentrate as widely as possible, successively, with stirring, add 10 ml of water, 0.3 ml of concentrated nitric acid and 1.7 g (10
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37/89 mmol) of silver nitrate in 2 ml of water. After stirring for 10 minutes, 0.5 ml of concentrated hydrochloric acid is added, the precipitate is aspirated, washed with 3 ml of water and the filtrate is added to 1.5 ml of concentrated hydrochloric acid. At <5 ° C, the mixture is added to 0.7 g (10 mmol) of sodium nitrite in 2 ml of water and then this is adjusted to pH 10 with 20% caustic soda. Then, the mixture is heated to 60 ° C for 30 minutes and after cooling with acetic ester, it is extracted. The organic phase is washed 3 times with saturated sodium chloride solution, dried, concentrated and the residue is absorbed with little acetic ester and filtered. Beije crystals, yield of 590 mg (40%). NMR (DMSO-d ₆ ): 6.62 (brs, 2H), 4.26 (t, 2H), 3.65 (t, 2H), 3.23 (s, 3H).
Table 1:
Compounds of formula (I) according to the invention, in which A represents CY, B represents N and R represents 2-methoxyethyl
No. X Y Z Physical data ( ¹ H-NMR, DMSO-de, 400 MHz) 1-1 F H Cl 1-2 F H Br 1-3 F H SChMe 1-4 F H SO ₂ Et 1-5 F H cf ₃1-6 Cl H F 1-7 Cl H Cl 8.13 (s, 1H), 7.72(d, 1H), 7.61 (dd, 1H),4.55 (t, 2H), 3.78(t, 2H), 3.22 (s, 3H)
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No. X Y Z Physical data ( ¹ H-NMR, DMSO-d6, 400 MHz) 1-8 Cl H Br 9.90 (bs, 1H), 7,697.65 (m, 2H), 7.49(dd, 1H), 4.63 (t, 2H),3.83 (t, 2H), 3.36(s, 3H) 1-9 Cl H I 9.67 (bs, 1H), 7.85(s, 1H), 7.77 (dd, 1H),7.51 (d, 1H), 4.60(t, 2H), 3.82 (t, 2H),3.36 (s, 3H) 1-10 Cl H SMe 1-11 Cl H SOMe 1-12 Cl H SO2Me 8.04 (d, 1H), 7.98(dd, 1H), 7.83 (s, 1H),4.56 (t, 2H), 3.78(t, 2H), 3.37 (s, 3H),3.22 (s, 3H) 1-13 Cl H SO ₂ CH ₂ Cl 1-14 Cl H SEt 1-15 Cl H SO ₂ Et 1-16 Cl H CF3 9.84 (bs, 1H), 7.90(d, 1H), 7.74 (s, 1H),7.68 (d, 1H), 4.62(t, 2H), 3.83 (t, 2H),3.37 (s, 3H) 1-17 Cl H CN 1-18 Cl H NMe ₂1-19 Cl H NHAc 1-20 Cl H pyrrole-1-ila 1-21 Cl H pyrrolidin-1-ila 1-22 Cl H pyrazol-1-ila
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No. X Y Z Physical data ( ¹ H-NMR, DMSO-d6, 400 MHz) 1-23 Cl H 1,2,4-triazole-1-ila 9.62 (bs, 1H), 8.66(s, 1H), 8.15 (s, 1H),7.98 (d, 1H), 7.92(s, 1H), 7.76 (d, 1H),4.62 (t, 2H), 3.84(t, 2H), 3.39 (s, 3H) 1-24 Cl H 4-methyl-3-trifluoromethyl-1,2,4-triazolin-5-on-1-ila 1-25 Br H F 1-26 Br H Cl 9.79 (bs, 1H), 7,687.64 (m, 2H), 7.45(dd, 1H), 4.63 (t, 2H),3.83 (t, 2H), 3.36(s, 3H) 1-27 Br H Br 1-28 Br H SMe 9.8 (bs, 1H), 7.65(d, 1H), 7.45 (d, 1H),7.26 (dd, 1H), 4.65(t, 2H), 3.84 (t, 2H),3.36 (s, 3H), 2.52(s, 3H) 1-29 Br H SO ₂ Me 1-30 Br H SO ₂ Et 1-31 Br H CF3 1-32 OMe H SO ₂ Me 1-33 SMe H F
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No. X Y Z Physical data ( ¹ H-NMR, DMSO-d6, 400 MHz) 1-34 SMe H Cl 10.65 (bs, 1H), 7.83(d, 1H), 7.31 (d, 1H),7.28 (dd, 1H), 4.63(t, 2H), 3.83 (t, 2H),3.34 (s, 3H), 2.49(s, 3H) 1-35 SO ₂ Me H Cl 1-36 SMe H Br 1-37 SO ₂ Me H Br 1-38 SMe H SMe 1-39 SO ₂ Me H SMe 1-40 SO ₂ Me H SOMe 1-41 SO ₂ Me H SO ₂ Me 1-42 SMe H CF3 10.6 (bs, 1H), 7.95(d, 1H), 7.57 (s, 1H),7.54 (d, 1H), 4.67(t, 2H), 3.85 (t, 2H),3.34 (s, 3H), 2.53(s, 3H) 1-43 SOMe H CF3 1-44 SO ₂ Me H CF3 8.18 (s, 1H), 8.15(d, 1H), 7.97 (d, 1H), 4.42 (m, 2H), 3.71 (m, 2H), 3.54 (s, 3H),3.21 (s, 3H) 1-45 SO ₂ Et H Cl 1-46 SO ₂ Et H Br 1-47 SO ₂ Et H SMe 1-48 SO ₂ Et H SOMe 1-49 SO ₂ Et H SO ₂ Me 1-50 SO ₂ Et H CF3
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No. X Y Z Physical data ( ¹ H-NMR, DMSO-de, 400 MHz) 1-51 SO2NMePH H Cl 1-52 SO ₂ NMe ₂ H CF3 1-53 NO2 H F 1-54 NO2 H Cl 1-55 NO2 H Br 1-56 NO2 H I 1-57 NO2 H CN 1-58 NO2 H SO ₂ Me 1-59 NO2 H SO ₂ Et 1-60 NO2 H CF3 10.3 (bs, 1H), 8.44(s, 1H), 8.02 (d, 1H),7.82 (d, 1H), 4.63(t, 2H), 3.86 (t, 2H),3.44 (s, 3H) 1-61 Me H F 1-62 Me H OCF3 1-63 Me H Cl 1-64 Me H Br 1-65 Me H SO ₂ Me 1-66 Me H SO ₂ CH ₂ Cl 1-67 Me H SO ₂ Et 1-68 Me H CF3 1-69 CH ₂ SMe H Br 10.05 (bs, 1H), 7,587.52 (m, 3H), 4.65(t, 2H), 3.96 (s, 2H),3.83 (t, 2H), 3.34(s, 3H), 2.05 (s, 3H)
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No. X Y Z Physical data ( ¹ H-NMR, DMSO-d6, 400 MHz) 1-70 CH2SO2Mand H Br 9.80 (bs, 1H), 7,727.68 (m, 2H), 7.59(d, 1H), 4.74 (s, 2H),4.62 (t, 2H), 3.81(t, 2H), 3.35 (s, 3H),2.98 (s, 3H) 1-71 CH2SO2Mand H CF3 1-72 Et H F 1-73 Et H Cl 1-74 Et H Br 1-75 Et H SO ₂ Me 1-76 Et H SO ₂ CH ₂ Cl 1-77 Et H SEt 1-78 Et H SO ₂ Et 1-79 Et H CF3 1-80 CF3 H Cl 10.05 (bs, 1H), 7.76(s, 1H), 7.70 (d, 1H),7.67 (d, 1H), 4.61(t, 2H), 3.82 (t, 2H),3.33 (s, 3H) 1-81 CF3 H Br 1-82 CF3 H SO ₂ Me 1-83 CF3 H SO ₂ NMe ₂ 10.5 (bs, 1H), 8.14(s, 1H), 8.08 (d, 1H),7.89 (d, 1H), 4.63(t, 2H), 3.81 (t, 2H),3.34 (s, 3H), 2.80(s, 6H) 1-84 CF3 H CF3 1-85 NO2 NH2 F 1-86 NO2 NHMe F
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No. X Y Z Physical data ( ¹ H-NMR, DMSO-d6, 400 MHz) 1-87 NO2 NMe2 F 1-88 NO2 Me Cl 1-89 NO2 NH2 Cl 1-90 NO2 NHMe Cl 1-91 NO2 NMe2 Cl 1-92 NO2 NH2 Br 1-93 NO2 NHMe Br 1-94 NO2 NMe2 Br 1-95 NO2 NH2 CF3 1-96 NO2 NMe2 CF3 1-97 NO2 NH2 SO2Me 1-98 NO2 NH2 SO2Et 1-99 NO2 NHMe SO2Me 1-100 NO2 NMe2 SO2Me 1-101 NO2 NMe2 SO2Et 1-102 NO2 NH2 1H-1,2,4-triazole-1-ila 1-103 NO2 NHMe 1H-1,2,4-triazole-1-ila 1-104 NO2 NMe2 1H-1,2,4-triazole-1-ila 1-105 Me SMe H 1-106 Me SOMe H 1-107 Me SO2Me H 1-108 Me SEt H 1-109 Me SOEt H 1-110 Me SO2Et H 1-111 Me S (CH2) 2OMe H 1-112 Me SO (CH2) 2OMe H 1-113 Me SO2 (CH2) 2OMe H 1-114 Me F F 1-115 Me SEt F
Petition 870180050694, of 06/13/2018, p. 48/104
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No. X Y Z Physical data ( ¹ H-NMR, DMSO-d6, 400 MHz) 1-116 Me SOEt F 1-117 Me SO2Et F 1-118 Me Me Cl 9.75 (brs, 1H), 7.35(d, 1H), 7.34 (d, 1H), 4.62 (t, 2H), 3.82 (t, 2H), 3.34 (s, 3H),2.46 (s, 3H), 2.40(s, 3H) 1-119 Me NH2 Cl 1-120 Me NHMe Cl 1-121 Me NMe2 Cl 1-122 Me O (CH2) 2OMe Cl 1-123 Me O (CH2) 3OMe Cl 9.84 (bs, 1H), 7.35(d, 1H), 7.32 (d, 1H),4.62 (t, 2H), 4.00(t, 2H), 3.83 (t, 2H),3.64 (t, 2H), 3.38(s, 3H), 3.35 (s, 3H),2.49 (s, 3H), 2.11 (m, 2H) 1-124 Me O (CH2) 4OMe Cl 1-125 Me O (CH2) 2SMe Cl 11.45 (bs, 1H), 7.51(d, 1H), 7.39 (d, 1H),4.54 (t, 2H), 4.07(t, 2H), 3.75 (t, 2H),3.22 (s, 3H), 2.92(t, 2H), 2.40 (s, 3H),2.16 (s, 3H) 1-126 Me O (CH2) 2SEt Cl 1-127 Me O (CH2) 3SMe Cl
Petition 870180050694, of 06/13/2018, p. 49/104
45/89
No. X Y Z Physical data ( ¹ H-NMR, DMSO-d6, 400 MHz) 1-128 Me OCH ₂ CONMe ₂ Cl 10.27 (brs, 1H), 7.39(d, H), 7.32 (d, 1H),4.63 (t, 2H), 4.60(s, 2H), 3.84 (t, 2H),3.35 (s, 3H), 3.06(s, 3H), 3.01 (s, 3H),2.41 (s, 3H) 1-129 Me O (CH ₂ ) ₂ CONMe ₂ Cl 1-130 Me O (CH ₂ ) ₂ - NH (CO) NMe ₂ Cl 1-131 Me O (CH2) 2NH (CO) N HCO ₂ Et Cl 1-132 Me O (CH2) 2NHCO2Mand Cl 1-133 Me OCH ₂ NHSO ₂ cPr Cl 1-134 Me O (CH ₂ ) -5- (2,4-dimethyl-2,4-dihydro) -3H-1,2,4-triazole-3-one Cl 1-135 Me O (CH ₂ ) -3,5-dimethyl-1,2-oxazol-4-yl Cl 1-136 Me F Cl 1-137 Me Cl Cl 1-138 Me SMe Cl 1-139 Me SOMe Cl 1-140 Me SO ₂ Me Cl 1-141 Me SEt Cl 1-142 Me SOEt Cl 1-143 Me SO ₂ Et Cl 1-144 Me S (CH ₂ ) ₂ OMe Cl 1-145 Me SO (CH ₂ ) ₂ OMe Cl
Petition 870180050694, of 06/13/2018, p. 50/104
46/89
No. X Y Z Physical data ( ¹ H-NMR, DMSO-d6, 400 MHz) 1-146 Me SO2 (CH2) 2OMe Cl 1-147 Me NH2 Br 1-148 Me NHMe Br 1-149 Me NMe2 Br 1-150 Me OMe Br 9.94 (bs, 1H), 7.53(d, 1H), 7.27 (d, 1H),4.62 (t, 2H), 3.85(s, 3H), 3.83 (t, 2H),3.34 (s, 3H), 3.22(s, 3H), 2.51 (s, 3H) 1-151 Me OEt Br 1-152 Me O (CH2) 2OMe Br 9.86 (bs, 1H), 7.52(d, 1H), 7.25 (d, 1H),4.62 (t, 2H), 4.10(t, 2H), 3.84-3.78(m, 4H), 3.47 (s, 3H),3.36 (s, 3H), 2.53(s, 3H) 1-153 Me O (CH2) 3OMe Br 9.81 (bs, 1H), 7.52(d, 1H), 7.24 (d, 1H),4.61 (t, 2H), 4.01(t, 2H), 3.83 (t, 2H),3.65 (t, 2H), 3.38(s, 3H), 3.35 (s, 3H),2.50 (s, 3H), 2.13(m, 2H)
Petition 870180050694, of 06/13/2018, p. 51/104
47/89
No. X Y Z Physical data ( ¹ H-NMR, DMSO-d6, 400 MHz) 1-154 Me O (CH2) 2SMe Br 11.46 (bs, 1H), 7.65(d, 1H), 7.32 (d, 1H),4.54 (t, 2H), 4.05(t, 2H), 3.75 (t, 2H),3.22 (s, 3H), 2.93(t, 2H), 2.41 (s, 3H),2.17 (s, 3H) 1-155 Me O (CH2) 2SEt Br 11.45 (bs, 1H), 7.65(d, 1H), 7.32 (d, 1H),4.54 (t, 2H), 4.03(t, 2H), 3.75 (t, 2H),3.22 (s, 3H), 2.96(t, 2H), 2.63 (q, 2H),2.41 (s, 3H), 1.22(t, 3H) 1-156 Me O (CH2) 3SMe Br 1-157 Me OCH2CONMe2 Br 10.32 (bs, 1H), 7.49(d, 1H), 7.32 (d, 1H),4.62 (t, 2H), 4.57(s, 2H), 3.83 (t, 2H),3.35 (s, 3H), 3.05(s, 3H), 3.01 (s, 3H),2.38 (s, 3H) 1-158 Me O (CH2) -5-pyrrolidin-2-one Br 1-159 Me SMe Br 1-160 Me SOMe Br 1-161 Me SO2Me Br
Petition 870180050694, of 06/13/2018, p. 52/104
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No. X Y Z Physical data ( ¹ H-NMR, DMSO-d6, 400 MHz) 1-162 Me SEt Br 9.22 (bs, 1H), 7.64(d, 1H), 7.28 (d, 1H),4.60 (t, 2H), 3.82(t, 2H), 3.35 (s, 3H),2.88 (q, 2H), 2.79(s, 3H), 1.24 (t, 3H) 1-163 Me SOEt Br 9.60 (bs, 1H), 7.56(d, 1H), 7.41 (d, 1H),4.60 (t, 2H), 3.82(t, 2H), 3.35 (s, 3H),3.29-3.34 (m, 1H),3.10-3.15 (m, 1H),2.82 (s, 3H), 1.42(t, 3H) 1-164 Me SO ₂ Et Br 9.38 (bs, 1H), 7.78(d, 1H), 7.46 (bs, 1H),4.60 (t, 2H), 3.82(t, 2H), 3.50 (q, 2H),3.37 (s, 3H), 2.85(s, 3H), 1.39 (t, 3H) 1-165 Me SMe I 1-166 Me SOMe I 1-167 Me SO ₂ Me I 1-168 Me SEt I 1-169 Me SOEt I 1-170 Me SO ₂ Et I
Petition 870180050694, of 06/13/2018, p. 53/104
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No. X Y Z Physical data ( ¹ H-NMR, DMSO-d6, 400 MHz) 1-171 Me Cl CF3 9.95 (brs, 1H), 7.68(d, H), 7.56 (d, 1H),4.64 (t, 2H), 3.83(t, 2H), 3.36 (s, 3H),2.59 (s, 3H) 1-172 Me SMe CF3 7.74 (d, H), 7.68(d, 1H), 4.48 (m, 2H),3.74 (m, 2H), 3.22(s, 3H), 2.70 (s, 3H),2.30 (s, 3H) 1-173 Me SOMe CF3 7.90 (s, 2H), 4.59(t, 2H), 3.76 (t, 2H),3.24 (s, 3H), 3.06(s, 3H), 2.88 (s, 3H) 1-174 Me SO ₂ Me CF3 7.89 (d, 1H), 7.82(d, 1H), 4.37 (m, 2H),3.71 (m, 2H), 3.37(s, 3H), 3.22 (s, 3H),2.75 (s, 3H) 1-175 Me SEt CF3 1-176 Me SOEt CF3 1-177 Me SO ₂ Et CF3 1-178 Me S (CH ₂ ) ₂ OMe CF3 1-179 Me S (O) (CH ₂ ) ₂ OMe CF3 1-180 Me SO ₂ (CH ₂ ) ₂ OMe CF3 1-181 Me SMe OMe 1-182 Me SOMe OMe 1-183 Me SO ₂ Me OMe 1-184 Me SEt OMe 1-185 Me SOEt OMe 1-186 Me SO ₂ Et OMe
Petition 870180050694, of 06/13/2018, p. 54/104
50/89
No. X Y Z Physical data ( ¹ H-NMR, DMSO-d6, 400 MHz) 1-187 Me Me SMe 9.75 (brs, 1H), 7.45(d, 1H), 7.08 (d, 1H),4.63 (t, 2H), 3.83(t, 2H), 3.35 (s, 1H),2.50 (s, 3H), 2.46(s, 3H), 2.32 (s, 3H) 1-188 Me Me SO ₂ Me 9.90 (brs, 1H), 8.02(d, 1H), 7.51 (d, 1H),4.64 (t, 2H), 3.83(t, 2H), 3.35 (s, 1H),3.13 (s, 3H), 2.70(s, 3H), 2.48 (s, 3H) 1-189 Me Me SEt 1-190 Me Me SO ₂ Et 1-191 Me 4,5-dihydro-1,2-oxazol-3-yl SO ₂ Me 1-192 Me 4,5-dihydro-1,2-oxazol-3-yl SO ₂ Et 1-193 Me 5-cyanomethyl-4,5-dihydro-1,2-oxazol-3-yl SO2Me 1-194 Me 5-cyanomethyl-4,5-dihydro-1,2-oxazol-3-yl SO2Et 1-195 Me NH2 SO ₂ Me 1-196 Me NHMe SO ₂ Me
Petition 870180050694, of 06/13/2018, p. 55/104
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No. X Y Z Physical data ( ¹ H-NMR, DMSO-d6, 400 MHz) 1-197 Me NMe2 SO2Me 9.95 (brs, 1H), 7.99(d, 1H), 7.51 (d, 1H),4.64 (t, 2H), 3.84(t, 2H), 3.37 (s, 1H),3.27 (s, 3H), 2.92(s, 6H), 2.50 (s, 3H) 1-198 Me NHEt SO2Me 1-199 Me NHnPr SO2Me 1-200 Me NHiPr SO2Me 9.87 (brs, 1H), 7.80(d, 1H), 7.12 (d, 1H),4.64 (t, 2H), 3.83(t, 2H), 3.77(sept, 1H), 3.36(s, 1H), 3.11 (s, 3H),2.41 (s, 3H), 1.22(d, 6H) 1-201 Me NHcPr SO2Me 9.71 (brs, 1H), 7.75(d, 1H), 7.06 (d, 1H),6.25 (bs, 1H), 4.64(t, 2H), 3.83 (t, 2H),3.36 (s, 1H), 3.00(s, 3H), 2.84 (m, 1H),2.60 (s, 3H), 0.81(m, 2H), 0.61 (m, 2H) 1-202 Me NHiBu SO2Me 1-203 Me NHCH2cPr SO2Me
Petition 870180050694, of 06/13/2018, p. 56/104
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No. X Y Z Physical data ( ¹ H-NMR, DMSO-d6, 400 MHz) 1-204 Me NH (CH2) 2OMe SO2Me 9.95 (bs, 1H), 7.81(d, 1H), 7.15 (d, 1H),4.64 (t, 2H), 3.84 (t,2H), 3.60 (t, 2H),3.42 (t, 2H), 3.40 (s,3H), 3.36 (s, 3H),3.20 (s, 3H), 2.43 (s,3H) 1-205 Me NH (CH2) 2OEt SO2Me 1-206 Me NH (CH2) 3OMe SO2Me 1-207 Me NHCH2CH (OMe)Me SO2Me 1-208 Me NHCH2CH (OMe)CH2OMe SO2Me 1-209 Me NH (CH2) 3OEt SO2Me 1-210 Me NHCH2-tetrahydrofuran-2-ila SO2Me 9.91 (bs, 1H), 7.81(d, 1H), 7.15 (d, 1H),4.64 (t, 2H), 4.15(m, 1H), 3.91(dd, 1H), 3.84 (t, 2H),3.79 (dd, 1H), 3.43(dd, 1H), 3.36 (s, 3H),3.24 (s, 3H), 3.18(dd, 1H), 2.43 (s, 3H),2.09-1.90 (m, 3H),1.72-1.63 (m, 1H) 1-211 Me NHCH2- (4-Me-[1.3] dioxolan-2-ila) SO2Me 1-212 Me NH (CH2) 2- (4-Me-[1.3] dioxolan-2-ila) SO2Me
Petition 870180050694, of 06/13/2018, p. 57/104
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No. X Y Z Physical data ( ¹ H-NMR, DMSO-d6, 400 MHz) 1-213 Me NHCH2-[1.3] dioxan-2-yl SO2Me 1-214 Me NHCH2CONHEt SO2Me 1-215 Me pyrazol-1-ila SO2Me 11.80 (brs, 1H), 8.11(d, 1H), 8.01 (d, 1H),7.99 (d, 1H), 7.88(d, 1H), 6.59 (t, 1H),4.58 (t, 2H), 3.77(t, 2H), 3.22 (s, 3H),3.05 (s, 3H), 1.90(s, 3H) 1-216 Me 3,5-Me2-pyrazole-1-ila SO2Me 1-217 Me 1,2,3-triazol-1-yl SO2Me 1-218 Me 1,2,4-triazol-1-yl SO2Me 1-219 Me OH SO2Me 1-220 Me OMe SO2Me 10.2 (brs, 1H), 7.91(d, 1H), 7.50 (d, 1H),4.65 (t, 2H), 3.98(s, 1H), 3.84 (t, 2H),3.37 (s, 3H), 3.26(s, 3H), 2.53 (s, 3H) 1-221 Me OMe SO2Et 1-222 Me OEt SO2Me 1-223 Me OEt SO2Et 1-224 Me OiPr SO2Me 1-225 Me OiPr SO2Et 1-226 Me O (CH2) 2OMe SO2Me 1-227 Me O (CH2) 2OMe SO2Et 1-228 Me O (CH2) 3OMe SO2Me 1-229 Me O (CH2) 3OMe SO2Et 1-230 Me O (CH2) 4OMe SO2Me
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No. X Y Z Physical data ( ¹ H-NMR, DMSO-d6, 400 MHz) 1-231 Me O (CH2) 4OMe SO2Et 1-232 Me O (CH2) 2SMe SO2Me 1-233 Me O (CH2) ₂ SEt SO2Me 1-234 Me O (CH2) 3SMe SO2Me 1-235 Me The (CH2) ₂ NHSO2M and SO2Me 1-236 Me The (CH2) ₂ NHSO2M and SO2Et 1-237 Me OCH2 (CO) NMe2 SO2Me 10.5 (brs, 1H), 7.94(d, 1H), 7.55 (d, 1H),4.82 (s, 2H), 4.67(t, 2H), 3.83 (t, 2H),3.40 (s, 3H), 3.36(s, 3H), 3.04 (s, 3H),2.95 (s, 3H), 2.53(s, 3H) 1-238 Me OCH2 (CO) NMe2 SO2Et 1-239 Me OCH2-tetrahydrofuran-2-ila SO2Me 1-240 Me OCH2-tetrahydrofuran-2-ila SO2Et 1-241 Me [1.4] dioxan-2-ilmetoxy SO2Me 1-242 Me [1.4] dioxan-2-ilmetoxy SO2Et 1-243 Me F SMe 1-244 Me F SO2Me
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No. X Y Z Physical data ( ¹ H-NMR, DMSO-d6, 400 MHz) 1-245 Me Cl SO2Me 10.05 (brs, 1H), 8.11(d, H), 7.61 (d, 1H),4.64 (t, 2H), 3.84(t, 2H), 3.36 (s, 3H),3.32 (s, 3H), 2.61(s, 3H) 1-246 Me SMe SO2Me 7.99 (d, 1H), 7.74(d, 1H), 4.49 (t, 2H),3.74 (t, 2H), 3.52(s, 3H), 3.23 (s, 3H),2.69 (s, 3H), 2.38(s, 3H) 1-247 Me SOMe SO2Me 1-248 Me SO2Me SO2Me 11.80 (brs, 1H), 8.28(d, 1H), 8.08 (d, 1H),4.59 (t, 2H), 3.77(t, 2H), 3.60 (s, 1H),3.58 (s, 3H), 3.23(s, 3H), 2.72 (s, 3H) 1-249 Me SO2Me SO2Et 1-250 Me SEt SO2Me 1-251 Me SOEt SO2Me 1-252 Me SO2Et SO2Me 1-253 Me S (CH2) 2OMe SO2Me 1-254 Me SO (CH2) 2OMe SO2Me 1-255 Me SO2 (CH2) 2OMe SO2Me 1-256 CH2SMe OMe SO2Me 1-257 CH2OMe OMe SO2Me 1-258 CH2O (CH2) 2OMe NH (CH2) 2OEt SO2Me 1-259 CH2O (CH2) 2OMe NH (CH2) 3OEt SO2Me
Petition 870180050694, of 06/13/2018, p. 60/104
56/89
No. X Y Z Physical data ( ¹ H-NMR, DMSO-de, 400 MHz) 1-260 CH2O (CH2) 3OMe OMe SO ₂ Me 1-261 CH ₂ O (CH ₂ ) ₂ OMe NH (CH ₂ ) ₂ OMe SO ₂ Me 1-262 CH ₂ O (CH ₂ ) ₂ OMe NH (CH ₂ ) 3OMe SO ₂ Me 1-263 Et NH (CH ₂ ) ₂ OMe SO ₂ Me 1-264 Et OMe SO ₂ Me 1-265 Et OMe SO ₂ Et 1-266 Et OEt SO ₂ Me 1-267 Et OEt SO ₂ Et 1-268 Et OiPr SO ₂ Me 1-269 Et OiPr SO ₂ Et 1-270 Et O (CH ₂ ) ₂ OMe SO ₂ Me 1-271 Et O (CH ₂ ) ₂ OMe SO ₂ Et 1-272 Et O (CH ₂ ) 3OMe SO2Me 1-273 Et O (CH ₂ ) 3OMe SO2Et 1-274 Et F SO2Me 1-275 Et SMe Cl 1-276 Et SOMe Cl 1-277 Et SO ₂ Me Cl 1-278 Et SMe Br 1-279 Et SOMe Br 1-280 Et SO ₂ Me Br 1-281 Et SMe I 1-282 Et SOMe I 1-283 Et SO ₂ Me I 1-284 Et SMe CF3 1-285 Et SOMe CF3 1-286 Et SO ₂ Me CF3 1-287 Et SMe SO2Me 1-288 Et SOMe SO2Me
Petition 870180050694, of 06/13/2018, p. 61/104
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No. X Y Z Physical data ( ¹ H-NMR, DMSO-d6, 400 MHz) 1-289 Et SO ₂ Me SO2Me 1-290 nPr SMe Cl 1-291 nPr SOMe Cl 1-292 nPr SO ₂ Me Cl 1-293 nPr SMe CF3 1-294 nPr SOMe CF3 1-295 nPr SO ₂ Me CF3 1-296 iPr SMe Cl 1-297 iPr SOMe Cl 1-298 iPr SO ₂ Me Cl 1-299 iPr SMe CF3 1-300 iPr SOMe CF3 1-301 iPr SO ₂ Me CF3 1-302 cPr SMe CF3 1-303 cPr SO ₂ Me CF3 1-304 CF3 O (CH ₂ ) ₂ OMe F 1-305 CF3 O (CH ₂ ) 3OMe F 1-306 CF3 OCH ₂ CONMe ₂ F 1-307 CF3 [1.4] dioxan-2-ilmetoxy F 1-308 CF3 O (CH ₂ ) ₂ OMe Cl 1-309 CF3 O (CH ₂ ) 3OMe Cl 1-310 CF3 OCH ₂ CONMe ₂ Cl 1-311 CF3 [1.4] dioxan-2-ilmetoxy Cl 1-312 CF3 O (CH ₂ ) ₂ OMe Br 1-313 CF3 O (CH ₂ ) ₂ OMe Br 1-314 CF3 O (CH2) 3OMe Br 1-315 CF3 OCH2CONMe2 Br 1-316 CF3 [1.4] dioxan-2-ilmetoxy Br 1-317 CF3 O (CH2) 2OMe I
Petition 870180050694, of 06/13/2018, p. 62/104
58/89
No. X Y Z Physical data ( ¹ H-NMR, DMSO-d6, 400 MHz) 1-318 CF3 O (CH2) 3OMe I 1-319 CF3 OCH2CONMe2 I 1-320 CF3 [1.4] dioxan-2-ilmetoxy I 1-321 CF3 F SO2Me 1-322 CF3 F SO2Et 1-323 CF3 O (CH ₂ ) ₂ OMe SO2Me 1-324 CF3 O (CH ₂ ) ₂ OMe SO2Et 1-325 CF3 O (CH ₂ ) 3OMe SO2Me 1-326 CF3 O (CH ₂ ) 3OMe SO2Et 1-327 CF3 OCH ₂ CONMe ₂ SO2Me 1-328 CF3 OCH ₂ CONMe ₂ SO2Et 1-329 CF3 [1.4] dioxan-2-ilmetoxy SO2Me 1-330 CF3 [1.4] dioxan-2-ilmetoxy SO2Et 1-331 F SMe CF3 1-332 F SOMe CF3 1-333 F SO ₂ Me CF3 1-334 Cl SMe H 1-335 Cl SOMe H 1-336 Cl SO ₂ Me H 1-337 Cl SEt H 1-338 Cl SOEt H 1-339 Cl SO ₂ Et H 1-340 Cl S (CH ₂ ) ₂ OMe H 1-341 Cl SO (CH ₂ ) ₂ OMe H 1-342 Cl SO2 (CH2) 2OMe H
Petition 870180050694, of 06/13/2018, p. 63/104
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No. X Y Z Physical data ( ¹ H-NMR, DMSO-d6, 400 MHz) 1-343 Cl SMe Me 7.40-7.42 (m, 1H),7.08-7.10 (m, 1H),4.30-4.60 (m, 2H),3.70-3.75 (m, 2H),3.35-3.50 (m, 2H),2.54 (s, 3H), 2.29(s, 3H) 1-344 Cl SOMe Me 9.52 (bs, 1H), 7.62(d, 1H), 7.30 (d, 1H),4.60 (t, 2H), 3.82(t, 2H), 3.37 (s, 3H),2.98 (s, 3H), 2.78(s, 3H) 1-345 Cl SO ₂ Me Me 9.45 (bs, 1H), 7.69(d, 1H), 7.39 (d, 1H),4.59 (t, 2H), 3.82(t, 2H), 3.40 (s, 3H),3.29 (s, 3H), 2.83(s, 3H) 1-346 Cl SEt Me 1-347 Cl SOEt Me 1-348 Cl SO ₂ Et Me 1-349 Cl Me Cl 9.71 (brs, 1H), 7.49(d, 1H), 7.42 (d, 1H),4.62 (t, 2H), 3.83(t, 2H), 3.35 (s, 3H),2.53 (s, 3H)
Petition 870180050694, of 06/13/2018, p. 64/104
60/89
No. X Y Z Physical data ( ¹ H-NMR, DMSO-d6, 400 MHz) 1-350 Cl CH2-pyrrolidin-2-on-1-ila Cl 9.8 (brs, 1H), 7.60(d, 1H), 7.50 (d, 1H),4.83 (s, 2H), 4.61(t, 2H), 3.83 (t, 2H),3.38 (s, 1H), 3.13(m, 2H), 2.39 (m, 2H),1.96 (m, 2H) 1-351 Cl CH ₂ (4-methyl-3-isopropoxy-1,2,4-triazolin-5-on-1-yl) Cl 1-352 Cl CH2 (4-methyl-3-trifluoroethoxy-1,2,4-triazolin-5-on-1-ila) Cl 1-353 Cl NH2 Cl 9.55 (brs, 1H), 7.32(d, 1H), 7.01 (d, 1H),4.71 (s, 2H), 4.61(t, 2H), 3.82 (t, 2H),3.35 (s, 3H) 1-354 Cl NHAc Cl 1-355 Cl NHCON (Me) OMe Cl 1-356 Cl NHCH ₂ CONHEt Cl 1-357 Cl NHCH ₂ CONHiPr Cl 1-358 Cl NHCHMet Cl 1-359 Cl imidazolidin-2-on-1-ila Cl 11.4 (brs, 1H), 7.49(d, 1H), 7.42 (d, 1H),6.02 (brs, 1H), 4.64(t, 2H), 3.85-3.68(m, 6H), 3.33 (s, 3H)
Petition 870180050694, of 06/13/2018, p. 65/104
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No. X Y Z Physical data ( ¹ H-NMR, DMSO-d6, 400 MHz) 1-360 Cl 1-methyl-1,2,4-triazolidin-3,5-dion-4-ila) Cl 10.6 (brs, 1H), 9.8(brs, 1H), 7.70(d, 1H), 7.54 (d, 1H),4.65 (t, 2H), 3.83(t, 2H), 3.35 (s, 3H),3.33 (s, 3H) 1-361 Cl OMe Cl 9.85 (bs, 1H), 7.48(d, 1H), 7.45 (d, 1H),4.62 (t, 2H), 3.94(s, 3H), 3.83 (t, 2H),3.36 (s, 3H) 1-362 Cl OEt Cl 9.90 (bs, 1H), 7.46(d, 1H), 7.44 (d, 1H),4.63 (t, 2H), 4.13(q, 2H), 3.83 (t, 2H),3.36 (s, 3H), 1.48(t, 3H) 1-363 Cl OPr Cl 1-364 Cl O-allila Cl 1-365 Cl OCH2CHF2 Cl 1-366 Cl O (CH2) 2OMe Cl 9.32 (bs, 1H), 7.47(d, 1H), 7.45 (d, 1H),4.59 (t, 2H), 4.21(t, 2H), 3.81 (q, 2H),3.46 (s, 3H), 3.36(s, 3H) 1-367 Cl O (CH2) 3OMe Cl
Petition 870180050694, of 06/13/2018, p. 66/104
62/89
No. X Y Z Physical data ( ¹ H-NMR, DMSO-d6, 400 MHz) 1-368 Cl OCH ₂ (CO) NMe ₂ Cl 9.95 (brs, 1H), 7.80(d, 1H), 7.44 (d, 1H),4.68 (s, 2H), 4.60(t, 2H), 3.83 (t, 2H),3.36 (s, 1H) 3.09(s, 3H), 3.01 (s, 3H) 1-369 Cl O (CH ₂ ) -5-pyrrolidin-2-one Cl 1-370 Cl Cl Cl 9.95 (brs, 1H), 7.58(d, 1H), 7.54 (d, 1H),4.64 (t, 2H), 3.84(t, 2H), 3.37 (s, 1H) 1-371 Cl SMe Cl 1-372 Cl SOMe Cl 1-373 Cl SO ₂ Me Cl 1-374 Cl SEt Cl 1-375 Cl SOEt Cl 1-376 Cl SO ₂ Et Cl 1-377 Cl Me Br 1-378 Cl CH ₂ (4-methyl-3-isopropoxy-1,2,4-triazolin-5-on-1-yl) Br 1-379 Cl CH ₂ (4-methyl-3-trifluoroethoxy-1,2,4-triazolin-5-on-1-yl) Br 1-380 Cl NHAc Br 1-381 Cl NHCON (Me) OMe Br 1-382 Cl NHCH ₂ CONHEt Br 1-383 Cl NHCH ₂ CONHiPr Br
Petition 870180050694, of 06/13/2018, p. 67/104
63/89
No. X Y Z Physical data ( ¹ H-NMR, DMSO-d6, 400 MHz) 1-384 Cl NHCHMet Br 1-385 Cl OMe Br 9.49 (bs, 1H), 7.62(d, 1H), 7.40 (d, 1H),4.60 (t, 2H), 3.92(s, 3H), 3.82 (t, 2H),3.37 (s, 3H), 1-386 Cl OEt Br 1-387 Cl OPr Br 1-388 Cl OAllila Br 1-389 Cl OCH2CHF2 Br 1-390 Cl O (CH2) 2OMe Br 11.71 (bs, 1H), 7.81(d, 1H), 7.40 (d, 1H),4.56 (t, 2H), 4.24(t, 2H), 3.77 (t, 2H),3.74 (t, 2H), 3.35(s, 3H), 3.23 (s, 3H) 1-391 Cl O (CH2) 3OMe Br 1-392 Cl OCH2 (CO) NMe2 Br 1-393 Cl O (CH2) -5-pyrrolidin-2-one Br 1-394 Cl Cl Br 1-395 Cl SMe Br 1-396 Cl SOMe Br 1-397 Cl SO2Me Br 1-398 Cl SEt Br 1-399 Cl SOEt Br 1-400 Cl SO2Et Br 1-401 Cl Me SMe 1-402 Cl Me SO2Me 1-403 Cl Me SO2Et 1-404 Cl CO2H SO2Me
Petition 870180050694, of 06/13/2018, p. 68/104
64/89
No. X Y Z Physical data ( ¹ H-NMR, DMSO-d6, 400 MHz) 1-405 Cl COOMe SO ₂ Me 1-406 Cl CONMe2 SO ₂ Me 1-407 Cl CONMe (OMe) SO ₂ Me 1-408 Cl CH ₂ N (OMe) Et SO ₂ Me 1-409 Cl CH ₂ OMe SO ₂ Me 1-410 Cl CH ₂ OMe SO ₂ Et 1-411 Cl CH ₂ OEt SO ₂ Me 1-412 Cl CH ₂ OEt SO ₂ Et 1-413 Cl CH ₂ OiPr SO ₂ Me 1-414 Cl CH2Ocpentilla SO ₂ Me 1-415 Cl CH2OCH2CHF2 SO ₂ Me 1-416 Cl CH2OCH2CF3 SMe 9.74 (bs, 1H), 7.70(d, 1H), 7.27 (d, 1H),4.99 (s, 2H), 4.61(t, 2H), 4.27 (q, 2H),3.72 (t, 2H), 3.29(s, 3H), 3.22 (s, 3H) 1-417 Cl CH2OCH2CF3 SO2Me 7.99 (d, 1H), 7.75(d, 1H), 5.24 (s, 2H),4.37 (t, 2H), 3.92(q, 2H), 3.81 (t, 2H),3.35 (s, 3H), 2.55(s, 3H) 1-418 Cl CH2OCH2CF3 SO ₂ Et 1-419 Cl CH2OCH2CF2CHF2 SO ₂ Me 1-420 Cl CH ₂ O (CH ₂ ) ₂ OMe SO ₂ Me 1-421 Cl CH ₂ PO3Me ₂ SO ₂ Me 1-422 Cl CH2O-tetrahydrofuran-3-ila SO2Me
Petition 870180050694, of 06/13/2018, p. 69/104
65/89
No. X Y Z Physical data ( ¹ H-NMR, DMSO-d6, 400 MHz) 1-423 Cl CH2O-tetrahydrofuran-3-ila SO ₂ Et 1-424 Cl CH2OCH2-tetrahydrofuran-2-ila SO ₂ Me 9.65 (bs, 1H), 8.18(d, 1H), 7.77 (d, 1H),5.20 (s, 2H), 4.61(t, 2H), 4.08 (m, 1H),3.83 (t, 2H), 3,823.58 (m, 4H), 3.37(s, 3H), 3.33 (s, 3H),2.0-1.8 (m, 3H), 1.631.5 (m, 1H), 1-425 Cl CH2OCH2-tetrahydrofuran-2-ila SO2Et 1-426 Cl CH2OCH2-tetrahydrofuran-3-ila SO2Me 1-427 Cl CH2OCH2-tetrahydrofuran-3-ila SO2Et 1-428 Cl 4,5-dihydro-1,2-oxazol-3-yl SMe 1-429 Cl 4,5-dihydro-1,2-oxazol-3-yl SO2Me 1-430 Cl 4,5-dihydro-1,2-oxazol-3-yl SO ₂ Et 1-431 Cl 5-cyanomethyl-4,5-dihydro-1,2-oxazol-3-yl SO2Me
Petition 870180050694, of 06/13/2018, p. 70/104
66/89
No. X Y Z Physical data ( ¹ H-NMR, DMSO-d6, 400 MHz) 1-432 Cl 5-cyanomethyl- 4,5-dihydro-1,2-oxazol-3 ila SO2Et 10.35 (bs, 1H), 8.14(d, 1H), 7.93 (d, 1H),5.16 (m, 1H), 4.65(t, 2H), 3.84 (t, 2H),3.73 (dd, 1H), 3.38(s, 3H), 3.37 (q, 2H),3.27 (dd, 1H), 2.95(dd, 1H), 2.85(dd, 1H), 1.31 (t, 3H) 1-433 Cl 5- (MeOCH2) -4.5-dihydro-1,2-oxazol-3-yl SO2Me 1-434 Cl 5- (MeOCH2) -4.5-dihydro-1,2-oxazol-3-yl SO2Et 1-435 Cl 5-Me-5-(MeOCH2) -4.5-dihydro-1,2-oxazol-3-yl SO2Me 1-436 Cl 5-Me-5-(MeOCH2) -4.5-dihydro-1,2-oxazol-3-yl SO2Et 1-437 Cl NH2 SO2Me 1-438 Cl NHMe SO2Me 1-439 Cl NMe2 SO2Me 1-440 Cl NH (CH2) 2OMe SO2Me 1-441 Cl NH (CH2) 2OMe SO2Et 1-442 Cl NH (CH2) 2OEt SO2Me 1-443 Cl NH (CH2) 3OMe SO2Me 1-444 Cl NH (CH2) 3OMe SO2Et 1-445 Cl NH (CH2) 4OMe SO2Me
Petition 870180050694, of 06/13/2018, p. 71/104
67/89
No. X Y Z Physical data ( ¹ H-NMR, DMSO-d6, 400 MHz) 1-446 Cl NH (CH2) 4OMe SO ₂ Et 1-447 Cl pyrazol-1-ila SO ₂ Me 1-448 Cl OMe SO ₂ Me 1-449 Cl OMe SO ₂ Et 1-450 Cl OEt SO2Me 9.41 (bs, 1H), 8.02(d, 1H), 7.56 (bd, 1H),4.61 (t, 2H), 4.32(q, 2H), 3.84 (t, 2H),3.39 (s, 3H), 3.29(s, 3H), 1.42 (t, 3H) 1-451 Cl OEt SO ₂ Et 1-452 Cl OPr SO2Me 9.56 (bs, 1H), 8.02(d, 1H), 7.55 (bd, 1H),4.62 (t, 2H), 4.22(t, 2H), 3.84 (t, 2H),3.39 (s, 3H), 3.28(s, 3H), 1.95(quin, 2H), 1.09(t, 3H) 1-453 Cl OPr SO2Et 11.86 (bs, 1H), 7.93(d, 1H), 7.71 (d, 1H),4.58 (t, 2H), 4.15(t, 2H), 3.78 (t, 2H),3.51 (q, 2H), 3.24(s, 3H), 1.88 (sex, 2H), 1.13 (t, 3H), 1.05 (t, 3H) 1-454 Cl OiPr SO ₂ Me 1-455 Cl OiPr SO ₂ Et
Petition 870180050694, of 06/13/2018, p. 72/104
68/89
No. X Y Z Physical data ( ¹ H-NMR, DMSO-d6, 400 MHz) 1-456 Cl OAllila SO ₂ Me 9.35 (bs, 1H), 8.03(d, 1H), 7.58 (bd, 1H),6.19 (m, 1H), 5.51(dd, 1H), 5.37(dd, 1H), 4.75 (d, 2H),4.61 (t, 2H), 3.84(t, 2H), 3.40 (s, 3H),3.28 (s, 3H) 1-457 Cl Oallila SO ₂ Et 1-458 Cl Opropargila SO2Me 9.63 (bs, 1H), 8.03(d, 1H), 7.61 (bd, 1H),4.92 (s, 2H), 4.63(t, 2H), 3.84 (t, 2H),3.40 (s, 3H), 3.32(s, 3H), 2.66 (t, 1H) 1-459 Cl Opropargila SO ₂ Et 1-460 Cl O (CH2) 2F SO2Me 9.50 (bs, 1H), 8.04(d, 1H), 7.52 (bd, 1H),3.89-3.91 (m, 1H),4.77-4.79 (m, 1H),4.62 (t, 2H), 4.55(bs, 1H), 4.48(bs, 1H), 3.84 (t, 2H),3.40 (s, 3H), 3.31(s, 3H) 1-461 Cl O (CH2) 2F SO ₂ Et 1-462 Cl O (CH2) 2Cl SO2Me 9.56 (bs, 1H), 8.04(d, 1H), 7.52 (bd, 1H),4.62 (t, 2H), 4.51(t, 2H), 3.95 (t, 2H),3.84 (t, 2H), 3.41(s, 3H), 3.32 (s, 3H)
Petition 870180050694, of 06/13/2018, p. 73/104
69/89
No. X Y Z Physical data ( ¹ H-NMR, DMSO-d6, 400 MHz) 1-463 Cl O (CH ₂ ) ₂ Cl SO ₂ Et 9.61 (bs, 1H), 8.02(d, 1H), 7.60 (bd, 1H),4.62 (t, 2H), 4.50(t, 2H), 3.94 (t, 2H),3.84 (t, 2H), 3.48(q, 2H), 3.40 (s, 3H),1.28 (t, 3H) 1-464 Cl OCH2cPr SO ₂ Me 9.42 (bs, 1H), 8.02(d, 1H), 7.55 (d, 1H),4.61 (t, 2H), 4.09(d, 2H), 3.83 (t, 2H),3.39 (s, 3H), 3.33(s, 3H), 1.40-1.49(m, 1H), 0.65-0.70(m, 2H), 0.45-0.50(m, 2H) 1-465 Cl OCH2cPr SO2Et 9.50 (bs, 1H), 8.00(d, 1H), 7.56 (d, 1H),4.62 (t, 2H), 4.08(d, 2H), 3.84 (t, 2H),3.51 (q, 2H), 3.38(s, 3H), 1.42-1.46(m, 1H), 1.27 (t, 3H),0.65-0.70 (m, 2H),0.44-0.48 (m, 2H)
Petition 870180050694, of 06/13/2018, p. 74/104
70/89
No. X Y Z Physical data ( ¹ H-NMR, DMSO-d6, 400 MHz) 1-466 Cl OCH2CBU SO2Me 9.41 (bs, 1H), 8.02(d, 1H), 7.55 (d, 1H),4.62 (t, 2H), 4.24(d, 2H), 3.84 (t, 2H),3.39 (s, 3H), 3.27(s, 3H), 2.89-2.98(m, 1H), 2.13-2.21(m, 2H), 1.90-2.05(m, 4H) 1-467 Cl OCH2CBU SO2Et 1-468 Cl O (CH2) 2OMe SO2Me 7.76 (d, 1H), 7.47(d, 1H), 4.33 (t, 2H),4.27 (t, 2H), 3.77 (q, 2H), 3.71 (t, 2H), 3.36 (s, 6H), 3.29(s, 3H) 1-469 Cl O (CH2) 2OMe SO2Et 1-470 Cl O (CH2) 2OEt SO2Me 1-471 Cl O (CH2) 3OMe SO2Me 1-472 Cl O (CH2) 3OMe SO2Et 1-473 Cl O (CH2) 4OMe SO2Me 1-474 Cl O (CH2) 4OMe SO2Et
Petition 870180050694, of 06/13/2018, p. 75/104
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No. X Y Z Physical data ( ¹ H-NMR, DMSO-d6, 400 MHz) 1-475 Cl O (CH2) 2OCF3 SO2Me 11.88 (bs, 1H), 7.97(d, 1H), 7.75 (d, 1H),4.57 (q, 2H), 4.544.56 (m, 2H), 4,434.48 (m, 2H), 3.78(t, 2H), 3.40 (s, 3H),3.24 (s, 3H) 1-476 Cl O (CH2) 2OCF3 SO2Et 11.88 (bs, 1H), 7.96(d, 1H), 7.76 (d, 1H),4.58 (t, 2H), 4,534.56 (m, 2H), 4,434.46 (m, 2H), 3.78(t, 2H), 3.42 (q, 2H),3.24 (s, 3H), 1.15(t, 3H) 1-477 Cl O (CH2) 2SMe SO2Me 1-478 Cl O (CH2) 2SEt SO2Me 1-479 Cl O (CH2) 3SMe SO2Me 1-480 Cl OCH2-tetrahydrofuran-2-ila SO2Me 1-481 Cl OCH2-tetrahydrofuran-2-ila SO2Et 1-482 Cl [1.4] dioxan-2-ilmetoxy SO2Me 1-483 Cl [1.4] dioxan-2-ilmetoxy SO2Et
Petition 870180050694, of 06/13/2018, p. 76/104
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No. X Y Z Physical data ( ¹ H-NMR, DMSO-d6, 400 MHz) 1-484 Cl OCH2 (CO) NMe2 SO2Me 10.6 (brs, 1H), 8.02(d, 1H), 7.63 (d, 1H),4.94 (s, 2H), 4.64(t, 2H), 3.84 (t, 2H),3.44 (s, 3H), 3.37(s, 3H), 3.03 (s, 3H),2.93 (s, 3H) 1-485 Cl OCH2 (CO) NMe2 SO2Et 10.7 (bs, 1H), 8.00(d, 1H), 7.63 (d, 1H),4.93 (s, 2H), 4.65(t, 2H), 3.83 (t, 2H),3.64 (q, 2H), 3.36(s, 3H), 3.02 (s, 3H),2.94 (s, 3H), 1.26(t, 3H) 1-486 Cl F SMe 1-487 Cl Cl SO2Me 9.9 (brs, 1H), 8.21(d, 1H), 7.74 (d, 1H),4.63 (t, 2H), 3.84(t, 2H), 3.39 (s, 3H),3.33 (s, 3H) 1-488 Cl SMe SO2Me 11.9 (brs, 1H), 8.15(d, 1H), 7.94 (d, 1H),4.58 (t, 2H), 3.78(t, 2H), 3.59 (s, 3H),3.24 (s, 3H), 2.50(s, 3H)
Petition 870180050694, of 06/13/2018, p. 77/104
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No. X Y Z Physical data ( ¹ H-NMR, DMSO-d6, 400 MHz) 1-489 Cl SOMe SO2Me 11.8 (brs, 1H), 8.05(d, 1H), 7.89 (d, 1H),4.42 (t, 2H), 3.73(t, 2H), 3.51 (s, 3H),3.22 (s, 3H), 3.18(s, 3H), 1-490 Cl SÜ2Me SO2Me 12.0 (brs, 1H), 8.39(d, 1H), 8.27 (d, 1H),4.59 (t, 2H), 3.78(t, 2H), 3.67 (s, 3H),3.58 (s, 3H), 3.24(s, 3H), 1-491 Br OMe Br 9.80 (brs, 1H), 7.65(d, 1H), 7.30 (d, 1H),4.65 (t, 2H), 3.92(s, 3H), 3.84 (t, 2H),3.36 (s, 3H) 1-492 Br O (CH2) 2OMe Br 1-493 Br O (CH2) 3OMe Br 1-494 Br OMe SO2Me 9.60 (brs, 1H), 7.89(d, 1H), 7.23 (d, 1H),4.66 (t, 2H), 4.06(s, 3H), 3.82 (t, 2H),3.41 (s, 3H), 3.22(s, 3H) 1-495 Br OMe SO2Et 1-496 Br OEt SO2Me 1-497 Br OEt SO2Et 1-498 Br OPr SO2Me 1-499 Br OPr SO2Et 1-500 Br O (CH2) 2OMe SO2Me 1-501 Br O (CH2) 2OMe SO2Et
Petition 870180050694, of 06/13/2018, p. 78/104
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No. X Y Z Physical data ( ¹ H-NMR, DMSO-d6, 400 MHz) 1-502 Br O (CH2) 3OMe SO2Me 1-503 Br O (CH2) 3OMe SO2Et 1-504 Br O (CH2) 4OMe SO2Me 1-505 Br O (CH2) 4OMe SO2Et 1-506 Br [1.4] dioxan-2-ilmetoxy SO2Me 1-507 Br [1.4] dioxan-2-ilmetoxy SO2Et 1-508 I O (CH2) 2OMe SO2Me 1-509 I O (CH2) 2OMe SO2Et 1-510 I O (CH2) 3OMe SO2Me 1-511 I O (CH2) 3OMe SO2Et 1-512 I O (CH2) 4OMe SO2Me 1-513 I O (CH2) 4OMe SO2Et 1-514 I [1.4] dioxan-2-ilmetoxy SO2Me 1-515 I [1.4] dioxan-2-ilmetoxy SO2Et 1-516 OH SO2Me CF3 1-517 OMe SMe CF3 7.76 (d, H), 7.68(d, 1H), 4.53 (t, 2H),3.96 (s, 3H), 3.77(t, 2H), 3.24 (s, 3H),2.44 (s, 3H) 1-518 OMe SOMe CF3 7.76 (d, 1H), 7.68(d, 1H), 4.53 (t, 2H),3.96 (s, 3H), 3.77(t, 2H), 3.24 (s, 3H),2.44 (s, 3H) 1-519 OMe SO2Me CF3 1-520 OMe SEt CF3 1-521 OMe SOEt CF3
Petition 870180050694, of 06/13/2018, p. 79/104
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No. X Y Z Physical data ( ¹ H-NMR, DMSO-d6, 400 MHz) 1-522 OMe SO ₂ Et CF3 1-523 OMe S (CH ₂ ) 2OMe CF3 1-524 OMe SO (CH ₂ ) ₂ OMe CF3 1-525 OMe SO ₂ (CH ₂ ) ₂ OMe CF3 1-526 OMe CH ₂ N (SO ₂ Me) Et Cl 1-527 OMe NHCOMe Cl 10.26 (bs, 1H), 7.99(d, 1H), 7.38 (d, 1H),4.57 (t, 2H), 3.95(s, 3H), 3.80 (t, 2H),3.30 (s, 3H), 2.30(bs, 3H) 1-528 OMe NHCOEt Cl 1-529 OMe NHCOiPr Cl 1-530 OMe NHCOcycPr Cl 1-531 OMe NHCOCHCMe2 Cl 1-532 OMe NHCOPh Cl 1-533 OMe SMe Cl 1-534 OMe SOMe Cl 1-535 OMe SO2Me Cl 1-536 OMe SEt Cl 1-537 OMe SOEt Cl 1-538 OMe SO2Et Cl 1-539 OMe S (CH2) 2OMe Cl 1-540 OMe SO (CH2) 2OMe Cl 1-541 OMe SO2 (CH2) 2OMe Cl 1-542 OEt SMe Cl 1-543 OEt SOMe Cl 1-544 OEt SO2Me Cl 1-545 OCH2C-P1- SMe CF3 1-546 OCH2C-P1- SOMe CF3 1-547 OCH ₂ c-Pr SO2Me CF3 1-548 OCH ₂ c-Pr SEt CF3
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No. X Y Z Physical data ( ¹ H-NMR, DMSO-de, 400 MHz) 1-549 OCH2C-P1- SOEt CF3 1-550 OCH2C-P1- SO2Et CF3 1-551 OCH2C-Pr S (CH2) 2OMe CF3 1-552 OCH2C-P1- SO (CH2) 2OMe CF3 1-553 OCH2C-Pr SO2 (CH2) 2OMe CF3 1-554 OCH2C-Pr SMe Cl 1-555 OCH2C-Pr SOMe Cl 1-556 OCH2C-Pr SO2Me Cl 1-557 OCH2C-Pr SEt Cl 1-558 OCH2C-Pr SOEt Cl 1-559 OCH2C-Pr SO2Et Cl 1-560 OCH2C-Pr S (CH2) 2OMe Cl 1-561 OCH2C-Pr SO (CH2) 2OMe Cl 1-562 OCH2C-Pr SO2 (CH2) 2OMe Cl 1-563 OCH2C-Pr SMe SO2Me 1-564 OCH2C-Pr SOMe SO2Me 1-565 OCH2C-Pr SO2Me SO2Me 1-566 OCH2C-Pr SEt SO2Me 1-567 OCH2C-Pr SOEt SO2Me 1-568 OCH2C-Pr SO2Et SO2Me 1-569 OCH2C-Pr S (CH2) 2OMe SO2Me 1-570 OCH2C-Pr SO (CH2) 2OMe SO2Me 1-571 OCH2C-Pr SO2 (CH2) 2OMe SO2Me 1-572 OSO2Me SMe CF3 11.87 (brs, 1H), 7.98(d, H), 7.94 (d, 1H),4.57 (t, 2H), 3.78(t, 2H), 3.61 (s, 3H),3.24 (s, 3H), 2.52(s, 3H) 1-573 OSO2Me SOMe CF3 1-574 OSO2Me SO2Me CF3 1-575 SMe SMe H
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No. X Y Z Physical data ( ¹ H-NMR, DMSO-d6, 400 MHz) 1-576 SO ₂ Me SO ₂ Me H 1-577 SMe SMe F 1-578 SMe SEt F 1-579 SO ₂ Me NHEt Cl 1-580 SMe OCH2CHF2 Br 1-581 SO ₂ Me F CF3 1-582 SO ₂ Me NH2 CF3 1-583 Cl SMe CF3 11.9 (brs, 1H), 7.98(d, 1H), 7.93 (d, 1H),4.59 (t, 2H), 3.78(t, 2H), 3.24 (s, 3H),2.45 (s, 3H) 1-584 Cl SOMe CF3 11.9 (brs, 1H), 8.07(s, 2H), 4.59 (t, 2H),3.78 (t, 2H), 3.24(s, 3H), 3.16 (s, 3H) 1-585 Cl SO2Me CF3 12.0 (brs, 1H), 8.21(2d, 2H), 4.59 (t, 2H),3.78 (t, 2H), 3.54(s, 3H), 3.24 (s, 3H) 1-586 Cl OCHF2 SO2Me 10.95 (bs, 1H), 8.11(d, 1H) 7.74 (bd, 1H),6.84 (t, 1H), 4.64(t, 2H), 3.84 (t, 2H),3.40 (s, 3H), 3.28(s, 3H) 1-587 Cl OCHF2 SO2Et 10.05 (bs, 1H), 8.09(d, 1H), 7.75 (bd, 1H),6.86 (t, 1H), 4.64(t, 2H), 3.84 (t, 2H),3.40 (q, 2H), 3.40(s, 3H), 1.30 (t, 3H)
Petition 870180050694, of 06/13/2018, p. 82/104
78/89
No. X Y Z Physical data ( ¹ H-NMR, DMSO-d6, 400 MHz) 1-588 Me O (CH2) 2SOEt Br 9.41 (bs, 1H), 7.53(d, 1H), 7.23 (d, 1H),4.60 (t, 2H), 4,314.42 (m, 2H), 3.83(t, 2H), 3.37 (s, 3H),3.23-3.30 (m, 1H),3.02-3.09 (m, 1H),2.83-2.94 (m, 2H),2.54 (s, 3H), 1.42(t, 3H) 1-589 Me O (CH2) 2SO2Et Br 9.58 (bs, 1H), 7.55(d, 1H), 7.24 (d, 1H),4.62 (t, 2H), 4.35(t, 2H), 3.83 (t, 2H),3.50 (t, 2H), 3.37(s, 3H), 3.29 (q, 2H),2.53 (s, 3H), 1.48(t, 3H) 1-590 Cl O (CH2) 2SMe Cl 9.71 (bs, 1H), 7.47(s, 2H), 4.61 (t, 2H),4.21 (t, 2H), 3.82(t, 2H), 3.36 (s, 3H),2.98 (t, 2H), 2.22(s, 3H) 1-591 Et SEt CF3 7.70 (d, 1H), 7.57(d, 1H), 4.63 (t, 2H),3.83 (t, 2H), 3.34(s, 3H), 3.27 (q, 2H),2.80 (q, 2H), 1.29 -1.23 (m, 6H)
Petition 870180050694, of 06/13/2018, p. 83/104
79/89
No. X Y Z Physical data ( ¹ H-NMR, DMSO-de, 400 MHz) 1-592 Et SOEt CF3 7.74 - 7.62 (m, 2H),4.62 (t, 2H), 3.83(t, 2H), 3.63 (m, 1H),3.52 - 3.25 (m, 2H),3.35 (s, 3H), 2.95(m, 1H), 1.46 (t, 3H),1.29 (t, 3H) 1-593 Et SO2Et CF3 7.91 (d, 1H), 7.76(m, 1H), 4.61 (t, 2H),3.83 (t, 2H), 3.50 -3.13 (m, 7H), 1.50(t, 3H), 1.34 (t, 3H) 1-594 cPr SOMe CF3 1-595 Et SEt Cl 1-596 Et SOEt Cl 1-597 Et SO2Et Cl 1-598 OMe SMe CHF2 8.21 (d, 1H), 7.64(d, 1H), 7.23 (t, 1H),4.60 (t, 2H), 4.12(s, 3H), 3.82 (t, 2H),3.35 (s, 3H), 2.46(s, 3H) in CDCl3 1-599 OMe SOMe CHF2 1-600 OMe SO2Me CHF2 1-601 OMe SEt CHF2 1-602 OMe SOEt CHF2 1-603 OMe SO2Et CHF2 1-604 OMe S (CH2) 2OMe CHF2 1-605 OMe SO (CH2) 2OMe CHF2 1-606 OMe SO2 (CH2) 2OMe CHF2 1-607 CH2OMe SMe Cl 1-608 CH2OMe SOMe Cl
Petition 870180050694, of 06/13/2018, p. 84/104
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No. X Y Z Physical data ( ¹ H-NMR, DMSO-de, 400 MHz) 1-609 CH2OMe SO2Me Cl 1-610 CH2OMe SEt Cl 1-611 CH ₂ OMe SOEt Cl 1-612 CH ₂ OMe SO2Et Cl 1-613 CH ₂ OMe S (CH2) 2OMe Cl 1-614 CH ₂ OMe SO (CH2) 2OMe Cl 1-615 CH ₂ OMe SO2 (CH2) 2OMe Cl 1-616 CH ₂ OMe SMe CF3 1-617 CH ₂ OMe SOMe CF3 1-618 CH ₂ OMe SO2Me CF3 1-619 CH ₂ OMe SEt CF3 1-620 CH ₂ OMe SOEt CF3 1-621 CH ₂ OMe SO2Et CF3 1-622 CH ₂ OMe S (CH2) 2OMe CF3 1-623 CH ₂ OMe SO (CH2) 2OMe CF3 1-624 CH ₂ OMe SO2 (CH2) 2OMe CF3 1-625 CH2OMe SMe SO2Me 1-626 CH2OMe SOMe SO2Me 1-627 CH2OMe SO2Me SO2Me 1-628 CH2OMe SEt SO2Me 1-629 CH2OMe SOEt SO2Me 1-630 CH2OMe SO2Et SO2Me 1-631 CH2OMe S (CH2) 2OMe SO2Me 1-632 CH2OMe SO (CH2) 2OMe SO2Me 1-633 CH2OMe SO2 (CH2) 2OMe SO2Me 1-634 Et SEt SO2Me 1-635 Et SOEt SO2Me 1-636 Et SO2Et SO2Me 1-637 Cl S (CH2) 2OMe Cl 1-638 Cl SO (CH2) 2OMe Cl 1-639 Cl SO2 (CH2) 2OMe Cl 1-640 Cl SEt SO2Me
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No. X Y Z Physical data ( ¹ H-NMR, DMSO-de, 400 MHz) 1-641 Cl SOEt SO ₂ Me 1-642 Cl SO ₂ Et SO ₂ Me 1-643 Cl S (CH ₂ ) ₂ OMe SO ₂ Me 1-644 Cl SO (CH ₂ ) ₂ OMe SO ₂ Me 1-645 Cl SO ₂ (CH ₂ ) ₂ OMe SO ₂ Me 1-646 Cl SEt cf ₃1-647 Cl SOEt cf ₃1-648 Cl SO ₂ Et cf ₃1-649 Cl S (CH ₂ ) ₂ OMe cf ₃1-650 Cl SO (CH ₂ ) ₂ OMe cf ₃1-651 Cl SO ₂ (CH ₂ ) ₂ OMe cf ₃
Table 2:
Compounds of formula (I) according to the invention, in which A represents CY
No. B R X Y Z Physical data ( ¹ H-NMR, DMSO-de, 400 MHz) 2-1 N (CH ₂ ) ₂ OH Me SO ₂ Me cf ₃ 7.81 (d, H), 7.72 (d, 1H),4.35 (brs, 1H), 4.15(t, 2H), 3.72 (t, 2H), 3.35(s, 3H), 2.74 (s, 3H) 2-2 N (CH ₂ ) ₂ OEt Me SO ₂ Me cf ₃ 11.8 (brs, 1H), 8.07(d, H), 8.03 (d, 1H), 4.58(t, 2H), 3.79 (t, 2H), 3.49(s, 3H), 3.41 (q, 2H),2.76 (s, 3H), 1.02 (t, 3H)
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No. B R X Y Z Physical data ( ¹ H-NMR, DMSO-d6, 400 MHz) 2-3 CH (CH ₂ ) ₂ OMe Me SO ₂ Me CF3 2-4 N (CH ₂ ) ₂ OBn Me SO2Me CF3 7.90 (d, 1H), 7.82(d, 1H), 7.34-7.21(m, 5H), 4.524.47 (s, 2H), 3.83 (t, 2H),3.39 (s, 3H), 2.72 (s, 3H) 2-5 N CH2CMe2OMe Me SO2Me CF3 11.6 (brs, 1H), 7.96(d, H), 7.84 (d, 1H), 4.34(s, 2H), 3.40 (s, 3H),3.13 (s, 3H), 2.75(s, 3H), 1.13 (s, 6H) 2-6 N (CH2) 3OMe Me SO2Me CF3 7.97 (d, 1H), 7.92 (d, 1H),4.30 (m, 2H), 3.39(s, 3H), 3.29 (m, 2H),3.21 (s, 3H), 2.76(s, 3H), 2.05 (m, 2H) 2-7 N CH2CN Me SO2Me CF3 8.15 (d, 1H), 8.11(d, 1H), 5.79 (s, 2H),3.45 (s, 3H), 2.75 (s, 3H) 2-8 N (CH2) 2NMe2 Me SO2Me CF3 7.88 (d, 1H), 7.82(d, 1H), 4.27 (m, 2H),3.71 (m, 2H), 3.36(s, 3H), 2.75 (m, 2H),2.15 (s, 6H) 2-9 N CH ₂ SiMe3 Me SO2Me CF3 7.95-7.89 (m, 2H), 3.73(s, 2H), 3.39 (s, 3H),2.76 (s, 3H), 0.13 (s, 9H) 2-10 N (CH ₂ ) ₂ SiMe3 2-11 N CH ₂ PO (OEt) 3 2-12 N CH ₂ SMe
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No. B R X Y Z Physical data ( ¹ H-NMR, DMSO-d ₆ , 400 MHz) 2-13 N (CH ₂ ) ₂ SMe Me SO ₂ Me cf ₃ 11.9 (brs, 1H), 8.06(s, 2H), 4.58 (t, 2H), 3.44(s, 3H), 3.02 (t, 2H), 2.76(s, 3H), 2.07 (s, 3H) 2-14 N (CH ₂ ) ₂ SOMe Me SO ₂ Me cf ₃ 8.13 (d, 1 H), 8.06(d, 1 H), 4.85-4.78(m, 2H), 3.48-3.38(m, 2H), 3.44 (s, 3H),2.77 (s, 3H), 2.63 (s, 3H) 2-15 N (CH ₂ ) ₂ SO ₂ Me Me SO ₂ Me cf ₃ 7.98 (brs, 2H), 4.73(t, 2H), 3.81 (t, 2H), 3.40(s, 3H), 3.05 (s, 3H),2.76 (s, 3H) 2-16 N (CH ₂ ) ₂ CN Me SO ₂ Me cf ₃2-17 N (CH ₂ ) ₂ NO ₂ Me SO ₂ Me cf ₃2-18 N CH ₂ (2-oxopyrrolidin-1-yl) Me SO ₂ Me cf ₃2-19 N CH ₂ CMeOMe Me SO ₂ Me cf ₃ 11.71 (brs, 1H), 8.07(d, H), 8.00 (d, 1H), 4.54(dd, 1 H), 4.40 (dd, 1 H),3.78 (m, 1H), 3.44(s, 3H), 3.16 (s, 3H),2.76 (s, 3H), 1.14 (d, 3H)
Table 3:
Compounds of formula (I) according to the invention, in which A represents N
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No. B R X Z Physical data ( ¹ H-NMR, DMSO-d6, 400 MHz) 3-1 CH C2H4OMe Me CF3 3-2 N C2H4OMe Me CF3 10.6 (brs, 1H), 8.17(d, 1H), 7.68 (d, 1H),4.69 (t, 2H), 3.85(t, 2H), 3.36 (s, 3H),2.84 (s, 3H) 3-3 N C2H4OMe iPr CF3 3-4 CH C2H4OMe CH2OMe CF3 3-5 N C2H4OMe CH2OMe CF3 11.8 (brs, 1H), 8.34(d, 1H), 8.02 (d, 1H),4.78 (s, 2H), 4.51 (t, 2H), 3.77 (t, 2H),3.28 (s, 3H), 3.23(s, 3H) 3-6 N C2H4OMe CH2OEt CF3 3-7 N C2H4OMe CH2OiPr CF3 3-8 CH C2H4OMe CH2O (CH2) 2OMand CF3 3-9 N C2H4OMe CH2O (CH2) 2OMand CF3 3-10 N C2H4OMe CH2O (CH2) 3OMand CF3 3-11 N C2H4OMe CH2OCH2CF3 CF3 3-12 N C2H4OMe CH2OCH2cPr CF3 3-13 N C2H4OMe CH2 (3-Me-imidazo-lin-2-on-1-ila) CF3
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No. B R X Z Physical data ( ¹ H-NMR, DMSO-d6, 400 MHz) 3-14 N C2H4OMe CH2 (3-methoxy-4-methyl-1,2,4-triazolin-5-on-1-ila) CF3 12.17 (brs, 1H), 8.24(d, 1H), 7.77 (d, 1H),5.28 (s, 2H), 4.73(t, 2H), 4.05 (s, 3H),3.78 (t, 2H), 3.27(s, 3H), 3.12 (s, 3H) 3-15 N C2H4OMe CH ₂ SMe CF3 3-16 CH C2H4OMe Cl CF3 3-17 N C2H4OMe Cl CF3 11.99 (brs, 1H), 8.55(brs, 1H), 8.20(brs, 1H), 4.37 (m, 2H),3.72 (m, 2H), 2.39 (s, 3H) 3-18 N C2H4OMe Br CF3 3-19 N C2H4OMe Br CF3 3-20 N C2H4OMe SMe CF3 8.37 (d, 1H), 7.62(d, 1H), 4.59 (m, 2H),3.78 (m, 2H), 3.23 (s, 3H), 3-21 N C2H4OMe F F 3-22 N C2H4OMe F F 3-23 CH C2H4OMe Cl Cl 3-24 N C2H4OMe Cl Cl 9.95 (bs, 1H), 8.16(d, 1H), 7.46 (d, 1H),4.61 (t, 2H), 3.83(t, 2H), 3.39 (s, 3H) 3-25 CH C2H4OMe Me Cl 3-26 N C2H4OMe Me Cl 3-27 N C2H4OMe SMe Cl 3-28 N C2H4OMe SO ₂ Me Cl 3-29 CH C2H4OMe Cl SMe 3-30 N C2H4OMe Cl SMe 3-31 CH C2H4OMe Me SO ₂ Me 3-32 N C2H4OMe Me SO ₂ Me
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No. B R X Z Physical data ( ¹ H-NMR, DMSO-d6, 400 MHz) 3-33 N C2H4OMe SMe SMe 3-34 N C2H4OMe SO2Me SO2Me
B. Examples of formulations
a) A dusting powder is obtained, in which 10 parts by weight of a compound of the formula (I) and / or its salts and 90 parts by weight of talc as an inert substance are mixed and crushed in a percussion mill .
b) A wettable powder, easily dispersible in water, is obtained, in which 25 parts by weight, of a compound of the formula (I) and / or its salts, 64 parts by weight, of quartz containing kaolinite as an inert substance, 10 parts in weight, potassium ligninosulfonate and 1 part weight, sodium oleoylmethyltaurinate as a humectant and dispersant, are mixed and ground in a pin mill.
c) A dispersion concentrate easily dispersible in water is obtained, in which 20 parts by weight of a compound of the formula (I) and / or its salts are mixed with 6 parts by weight of alkylphenol polyglycolic ether (®Triton X 207) , 3 parts by weight, isotridecanol polyglycolic ether (8 EO) and 71 parts by weight, paraffinic mineral oil (boiling range, for example, from about 255 to above 277 ^o C) and ground in a friction mill of balls for a fineness less than 5 microns.
d) An emulsifiable concentrate is obtained from 15 parts by weight of a compound of the formula (I) and / or its salts, 75 parts by weight of cyclohexanone as a solvent and 10 parts by weight of oxetylated nonylphenol as emulsifier.
e) A water-dispersible granulate is obtained, in which parts by weight, of a compound of formula (I) and / or its salts,
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87/89 parts by weight, calcium lignosulfonate, parts by weight, sodium lauryl sulfate, parts by weight, polyvinyl alcohol and parts by weight, kaolin are mixed, ground in a pin mill and the powder is granulated in a fluidizing bed through water atomization as a granulation liquid.
f) A water-dispersible granulate is also obtained, in which parts by weight of a compound of the formula (I) and / or its salts, parts by weight of 2,2'-dinaftymethane-6,6'-disulfonate sodium, parts by weight, sodium oleoylmethyltaurinate, parts by weight, polyvinyl alcohol, parts by weight, calcium carbonate and parts by weight, water are homogenized in a colloid mill and pre-crushed, then these they are ground in a pearl mill and the suspension obtained in this way is sprayed in a spray tower by means of a nozzle and dried.
C. Biological examples
1. Herbicidal effect against weeds in preemergence [0073] Seeds of weed plants or plants of mono- or dicotyledonous culture are placed in wooden fiber pots in sandy clay and covered with soil. The compounds according to the invention, formulated in the form of wettable powders (WP) or as emulsion concentrates (EC) are then applied as a suspension or aqueous emulsion on the surface of the earth covered with a
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88/89 amount of water converted from 600 to 800 liters / ha, adding 0.2% of humectant. After treatment, the pots are placed in the greenhouse and maintained in good growing conditions for the test plants. The visual assessment of the damage to the test plants is carried out after a test time of 3 weeks, compared to untreated controls (herbicidal effect in percent (%): 100% effect = the plants died, 0% de effect = just like the control plants). In this case, for example, the compounds
from n ^the 1-16, 1-44, 1-60, 1 -125, 1 -154, 1-162, 1-163, 1-174, 1-187, 1- 191, 1-197, 1-200, 1-204, 1-215, 1-245, , 1-246, 1-248, 1-343, 1-345, 1- 361, 1-366, 1-368, 1-417, 1-450, 1-452, 1-453, 1-456, 1-458, 1-460, 1- 463, 1-464, 1-465, 1-468, 1-475, 1-476, 1-488, 1-494, 1-517, 1-572, 1-
583, 2-2, 2-4, 2-5, 2-6, 2-7, 2-19, 3-2 and 3-16 with an application amount of 320 g / ha, show in each case an effect at least 90% against Abutilon theophrasti, Amaranthus retroflexus, Matricaria inodora, Stellaria media, Veronica persica and Viola tricolor.
2. Herbicidal effect against weeds in postemergence [0074] Seeds of weed plants or plants of mono- or dicotyledonous culture are placed in wooden fiber pots in sandy clay, covered with soil and grown in the greenhouse in good conditions. growth. Two to three weeks after sowing, the test plants are treated at the stage of a leaf. The compounds according to the invention formulated in the form of wettable powders (WP) or as emulsion concentrates (EC) are then sprayed as a suspension or aqueous emulsion with a recalculated water application amount of 600 to 800 liters / ha, adding 0.2% humectant to the green parts of the plants. After approximately 3 weeks of resting time of the test plants in the greenhouse under optimal growth conditions, the
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89/89 effect of the preparations is evaluated in comparison with untreated controls (herbicidal effect in percent (%): 100% effect = the plants died, 0% effect = just like the control plants). In this case, for example, compounds No. 1-23, 1-44, 1-125, 1128, 1,154, 1-157, 1-162, 1-188, 1-197, 1-200, 1-215 , 1-220, 1-245, 1246, 1-344, 1-345, 1-350, 1-366, 1-368, 1-417, 1-450, 1-453, 1-456, 1460, 1 -465, 1-468, 1-475, 1-487, 1-488, 1-494, 1-517, 1-518, 1-583, 22, 2-4, 2-5, 2-6, 2 -19, 3-2, 3-5 and 3-23, with an application amount of 80 g / ha, show in each case an effect of at least 90% against Abutilon theophrasti, Matricaria inodora, Pharbitis purpureum, Stellaria media, Veronica Persica and Viola tricolor.
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1/5

权利要求:
Claims (13)
[1]
1. N- (tetrazol-5-yl) - or N- (triazol-5-yl) arylcarboxylic acid amides, characterized by the fact that they have formula (I) or their salts in which
A represents N or CY,
B represents N or CH,
X represents nitro, halogen, (Ci-Cej-alkyl, OR ¹ , OSO2R ² , S (O) nR ² or (Ci-C6) -alkyl-OR ¹ ,
Y represents hydrogen, halogen, (Ci-Cej-alkyl, OR ¹ , S (O) nR ² , (Ci-C6) -alkyl-OR ¹ or N (R ¹ ) ₂ ,
Z represents halogen, halo- (C1-C6) -alkyl, S (O) _n R ² or heteroaryl, with heteroaryl being a cyclic aromatic radical, containing from 3 to 6 ring atoms, being from 1 to 4 of which are from the group consisting of oxygen, nitrogen and sulfur, or Z can also represent hydrogen or (Ci-Cej-alkyl, if Y represents the radical S (O) _n R ² ,
R represents CH2R ⁶ or (C2-C6) -alkyl, which is replaced by u radicals of the group consisting of (C1-Cej-alkoxy or Q-benzyl,
Q represents O,
R ¹ represents hydrogen, (Ci-Cej-alkyl, (Ci-Ce) halogenoalkyl, (C2-C6) -alkenyl, (C2-C6) -alkynyl, (Ci-Cej-alkyl-O (Ci-Cej-alkyl, (C3-C6) -cycloalkyl- (C1-C6) -alkyl, the last 6 radicals mentioned being replaced by radicals of the group consisting of halogen, OR ³ , S (O) _n R ⁴ or CON (R ³ ) 2,
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[2]
2/5
R ² represents (Ci-Cs) -alkia,
R ³ represents (Ci-Cs) -aiquiia,
R ⁴ represents (Ci-Cs) -aiquiia,
R ⁶ represents cyan, n represents 0, 1 or 2, s represents 0, 1, 2 or 3, i represents 1,2, 3, 4 or 5.
2. N- (tetrazoi-5-ii) - or N- (triazoi-5-ii) arylcarboxylic acid amides, according to claim 1, characterized by the fact that:
A represents N or CY,
B represents N or CH,
X represents nitro, haiogen, (C1-C6) -aiquia, OR ¹ , OSO2R ² , S (O) nR ² or (C1-C6) -aiquii-OR ¹ ,
Y represents hydrogen, haiogen, (C1-C6) -aiquia, OR ¹ , S (O) nR ² , N (R ¹ ) 2 or (C1-C6) -aiquii-OR ¹ ,
Z represents haiogen, haiogen- (C1-C6) -aiquiia, S (O) nR ² or 1,2,4-triazoi-1-iia, or Z can also represent hydrogen or (C1C6) -aiquiia, if Y represents the roots S (O) nR ² ,
R represents CH2R ⁶ or (C2-C6) -aiquiia, which is replaced by u radicals of the group consisting of (C1-C6) -oxy or Q-benzoyl,
Q represents O,
R ¹ represents hydrogen, (C1-C6) -aiquia, (C2-C6) -aiquieniia, (C2-C6) -aiquiniia, (C3-C6) -cycaiaii- (C1-C6) -aiquiia, (C1-C6) -aiquii-O (C1-C6) -aiquiia, with the last 5 radicals mentioned being replaced by radicals of the group consisting of haiogen, OR ³ , S (O) nR ⁴ or CON (R ³ ) 2,
R ² represents (C1-C6) -aiquia,
R ³ represents (C1-C6) -aiquia,
R ⁴ represents (C1-C6) -aiquia,
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[3]
3/5
R ⁶ represents cyan, n represents 0, 1 or 2, s represents 0, 1, 2 or 3, i represents 1,2, 3, 4 or 5.
3. N- (tetrazol-5-yl) - or N- (triazol-5-yl) arylcarboxylic acid amides, according to claim 1 or 2, characterized by the fact that:
A represents N or CY,
B represents N or CH,
X represents nitro, halogen, (C1-C6) -alkyl, OR ¹ , S (O) nR ² or (C1-C6) -alkyl-OR ¹ ,
Y represents hydrogen, halogen, (C1-C6) -alkyl, OR ¹ , S (O) nR ² , N (R ¹ ) 2 or (C1-C6) -alkyl-OR ¹ ,
Z represents halogen, halogen- (C1-C6) -alkyl, S (O) nR ² or 1,2,4-triazol-1-yl, or Z can also represent hydrogen or methyl, if Y represents the radical S (O ) nR ² ,
R represents CH2R ⁶ or (C2-C6) -alkyl, which is replaced by u radicals of the group consisting of (C1-C6) -alkoxy and Q-benzyl,
Q represents O,
R ¹ represents hydrogen, (C1-C6) -alkyl, (C2-C6) -alkenyl, (C2-C6) -alkynyl, (C3-C6) -cycloalkyl- (C1-C6) -alkyl, (C1-C6) -alkyl-O (C1-C6) -alkyl, with the last 5 radicals mentioned being replaced by radicals from the group consisting of halogen, OR ³ , S (O) nR ⁴ or CON (R ³ ) 2,
R ² represents (C1-C6) -alkyl,
R ³ represents (C1-C6) -alkyl,
R ⁴ represents (C1-C6) -alkyl, n represents 0, 1 or 2, s represents 0, 1, 2 or 3, i represents 1, 2, 3, 4 or 5.
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[4]
4/5
4. Herbicidal composition, characterized by the fact that it comprises a compound of formula (I), as defined in any one of claims 1 to 3.
[5]
5. Herbicidal composition, according to claim 4, characterized by the fact that it is in mixture with auxiliary formulation agents.
[6]
6. Herbicidal composition according to claim 4 or 5, characterized by the fact that it comprises another active pesticidally effective compound from the group of insecticides, acaricides, herbicides, fungicides, protectors and growth regulators.
[7]
7. Herbicidal composition according to claim 6, characterized by the fact that it comprises a protector.
[8]
Herbicidal composition according to claim 7, characterized by the fact that it comprises cyprosulfamide, cloquintocet-mexila, mefenpir-diethyl or isoxadifen-ethyl.
[9]
Herbicidal composition according to any one of claims 6 to 8, characterized in that it comprises another herbicide.
[10]
10. Process for combating unwanted plants, characterized in that it comprises applying an effective amount of a compound of the formula (I), as defined in any one of claims 1 to 3, or of a herbicidal composition, as defined in any one of claims 4 to 9, at the plants or at the site of the growth of unwanted plants.
[11]
11. Use of compounds of formula (I), as defined in any of claims 1 to 3, or herbicidal compositions, as defined in any of claims 4 to 9, characterized by the fact that it is for combating unwanted plants .
[12]
12. Use according to claim 11, characterized
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5/5 by the fact that the compounds of the formula (I) are used to combat unwanted plants in useful plant cultures.
[13]
13. Use according to claim 12, characterized by the fact that the useful plants are useful transgenic plants.
Petition 870180050694, of 06/13/2018, p. 99/104

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法律状态:
2017-05-30| B06F| Objections, documents and/or translations needed after an examination request according art. 34 industrial property law|

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2018-04-24| B07A| Technical examination (opinion): publication of technical examination (opinion)|

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2018-07-03| B09A| Decision: intention to grant|

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2018-07-17| B16A| Patent or certificate of addition of invention granted|

优先权:

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申请号 | 申请日 | 专利标题

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EP11176378|2011-08-03|

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PCT/EP2012/064863|WO2013017559A1|2011-08-03|2012-07-30|N-- and n-arylcarboxamides and use thereof as herbicides|

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