DIAMINOTRIAZINE DERIVATIVES AS HERBICIDES

Abstract

The present invention relates to diaminotriazine compounds of the formula (I) and to their use as herbicides. The present invention also relates to agrochemical compositions for crop protection and to a method for controlling unwanted vegetation.

##STR00001## wherein A is phenyl, which is substituted by fluorine in the ortho-position and which may additionally carry 1, 2, 3 or 4 identical or different substituents R.sup.A; R.sup.1, R.sup.2 are inter alia H, OH, S(O).sub.2NH.sub.2, ON, C.sub.1-C.sub.6-alkyl, C.sub.2-C.sub.6-alkenyl, C.sub.2-C.sub.6-alkynyl, (C.sub.3-C.sub.6-cycloalkyl)-C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.6-alkoxy, (C.sub.1-C.sub.6-alkoxy)-C.sub.1-C.sub.6-alkyl, (C.sub.1-C.sub.6-alkyl)-carbonyl, (C.sub.1-C.sub.6-alkoxy)carbonyl, (C.sub.1-C.sub.6-alkyl)sulfonyl, (C.sub.1-C.sub.6-alkylamino)carbonyl, di(C.sub.1-C.sub.6-alkyl)aminocarbonyl, (C.sub.1-C.sub.6-alkylamino)sulfonyl, di(C.sub.1-C.sub.6-alkyl)aminosulfonyl and (C.sub.1-C.sub.6-alkoxy)sulfonyl, etc. X is NR.sup.3aR.sup.3b, OR.sup.3c or S(O).sub.kR.sup.3d, wherein R.sup.3a, R.sup.3b, R.sup.3c or R.sup.3d are independently of one another are selected from the group consisting of H, CN, S(O).sub.2NH.sub.2, C.sub.1-C.sub.6-alkyl, C.sub.2-C.sub.6-alkenyl, C.sub.2-C.sub.6-alkynyl, C.sub.3-C.sub.6-cycloalkyl, (C.sub.3-C.sub.6-cycloalkyl)-C.sub.1-C.sub.6-alkyl, (C.sub.1-C.sub.6-alkoxy)-C.sub.1-C.sub.6-alkyl, (C.sub.1-C.sub.6-alkyl)-carbonyl, (C.sub.1-C.sub.6-alkoxy)carbonyl, (C.sub.1-C.sub.6-alkyl)sulfonyl, C.sub.1-C.sub.6-alkylamino)carbonyl, di(C.sub.1-C.sub.6-alkyl)aminocarbonyl, (C.sub.1-C.sub.6-alkylamino)sulfonyl, di(C.sub.1-C.sub.6-alkyl)aminosulfonyl and (C.sub.1-C.sub.6-alkoxy)sulfonyl, etc. including their agriculturally acceptable salts.

Claims

1-18. (canceled)

19. A diaminotriazine compound of formula (I) ##STR00021## wherein A is phenyl, which is substituted by fluorine in the ortho-position and which may additionally carry 1, 2, 3 or 4 identical or different substituents R.sup.A selected from the group consisting of halogen, OH, CN, amino, NO.sub.2, C.sub.1-C.sub.6-alkyl, C.sub.2-C.sub.6-alkenyl, C.sub.2-C.sub.6-alkynyl, C.sub.1-C.sub.6-alkoxy, C.sub.2-C.sub.6-alkenyloxy, C.sub.2-C.sub.6-alkynyloxy, (C.sub.1-C.sub.6-alkoxy)-C.sub.1-C.sub.6-alkyl, (C.sub.1-C.sub.6-alkoxy)-C.sub.1-C.sub.6-alkoxy, (C.sub.1-C.sub.6-alkoxy)-C.sub.2-C.sub.6-alkenyl, (C.sub.1-C.sub.6-alkoxy)-C.sub.2-C.sub.6-alkynyl, C.sub.1-C.sub.6-alkylthio, (C.sub.1-C.sub.6-alkyl)sulfinyl, (C.sub.1-C.sub.6-alkyl)sulfonyl, (C.sub.1-C.sub.6-alkyl)amino, di(C.sub.1-C.sub.6-alkyl)amino, (C.sub.1-C.sub.6-alkyl)-carbonyl, (C.sub.1-C.sub.6-alkoxy)-carbonyl, (C.sub.1-C.sub.6-alkyl)-carbonyloxy, C.sub.3-C.sub.6-cycloalkyl, C.sub.3-C.sub.6-cycloalkoxy, (C.sub.3-C.sub.6-cycloalkyl)-C.sub.1-C.sub.4-alkyl, and (C.sub.3-C.sub.6-cycloalkyl)-C.sub.1-C.sub.4-alkoxy, where the aliphatic and cycloaliphatic parts of the 22 aforementioned radicals are unsubstituted, partly or completely halogenated and where the cycloaliphatic parts of the last 4 mentioned radicals may carry 1, 2, 3, 4, 5 or 6 methyl groups; R.sup.1 is selected from the group consisting of H, OH, S(O).sub.2NH.sub.2, CN, C.sub.1-C.sub.6-alkyl, C.sub.2-C.sub.6-alkenyl, C.sub.2-C.sub.6-alkynyl, (C.sub.3-C.sub.6-cycloalkyl)-C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.6-alkoxy, (C.sub.1-C.sub.6-alkoxy)-C.sub.1-C.sub.6-alkyl, (C.sub.1-C.sub.6-alkyl)-carbonyl, (C.sub.1-C.sub.6-alkoxy)carbonyl, (C.sub.1-C.sub.6-alkyl)sulfonyl, (C.sub.1-C.sub.6-alkylamino)carbonyl, di(C.sub.1-C.sub.6-alkyl)aminocarbonyl, (C.sub.1-C.sub.6-alkylamino)sulfonyl, di(C.sub.1-C.sub.6-alkyl)aminosulfonyl and (C.sub.1-C.sub.6-alkoxy)sulfonyl, where the aliphatic and cycloaliphatic parts of the 14 aforementioned radicals are unsubstituted, partly or completely halogenated, phenyl, phenyl-C.sub.1-C.sub.6-alkyl, phenylsulfonyl, phenylaminosulfonyl, phenylcarbonyl and phenoxycarbonyl, wherein phenyl in the last 6 mentioned radicals are unsubstituted or substituted by 1, 2, 3, 4 or 5 identical or different substituents selected from the group consisting of halogen, CN, NO.sub.2, C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-haloalkyl, C.sub.1-C.sub.6-alkoxy and C.sub.1-C.sub.6-haloalkoxy; R.sup.2 is selected from the group consisting of H, OH, S(O).sub.2NH.sub.2, CN, C.sub.1-C.sub.6-alkyl, C.sub.2-C.sub.6-alkenyl, C.sub.2-C.sub.6-alkynyl, (C.sub.3-C.sub.6-cycloalkyl)-C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.6-alkoxy, (C.sub.1-C.sub.6-alkoxy)-C.sub.1-C.sub.6-alkyl, (C.sub.1-C.sub.6-alkyl)carbonyl, (C.sub.1-C.sub.6-alkoxy)carbonyl, (C.sub.1-C.sub.6-alkyl)sulfonyl, (C.sub.1-C.sub.6-alkylamino)carbonyl, di(C.sub.1-C.sub.6-alkyl)aminocarbonyl, (C.sub.1-C.sub.6-alkylamino)sulfonyl, di(C.sub.1-C.sub.6-alkyl)aminosulfonyl and (C.sub.1-C.sub.6-alkoxy)sulfonyl, where the aliphatic and cycloaliphatic parts of the 14 aforementioned radicals are unsubstituted, partly or completely halogenated, phenyl, phenylsulfonyl, phenylaminosulfonyl, phenyl-C.sub.1-C.sub.6 alkyl, phenoxy, phenylcarbonyl and phenoxycarbonyl, wherein phenyl in the last 6 mentioned radicals is unsubstituted or substituted by 1, 2, 3, 4 or 5 identical or different substituents selected from the group consisting of halogen, CN, NO.sub.2, C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-haloalkyl, C.sub.1-C.sub.6-alkoxy and C.sub.1-C.sub.6-haloalkoxy; X is NR.sup.3aR.sup.3b, OR.sup.3c Or S(O).sub.kR.sup.3d, wherein R.sup.3a, R.sup.3b, R.sup.3c or R.sup.3d are independently of one another are selected from the group consisting of H, CN, S(O).sub.2NH.sub.2, C.sub.1-C.sub.6-alkyl, C.sub.2-C.sub.6-alkenyl, C.sub.2-C.sub.6-alkynyl, C.sub.3-C.sub.6-cycloalkyl, (C.sub.3-C.sub.6-cycloalkyl)-C.sub.1-C.sub.6-alkyl, (C.sub.1-C.sub.6-alkoxy)-C.sub.1-C.sub.6-alkyl, (C.sub.1-C.sub.6-alkyl)-carbonyl, (C.sub.1-C.sub.6-alkoxy)carbonyl, (C.sub.1-C.sub.6-alkyl)sulfonyl, (C.sub.1-C.sub.6-alkylamino)carbonyl, di(C.sub.1-C.sub.6-alkyl)aminocarbonyl, (C.sub.1-C.sub.6-alkylamino)sulfonyl, di(C.sub.1-C.sub.6-alkyl)aminosulfonyl and (C.sub.1-C.sub.6-alkoxy)sulfonyl, where the aliphatic and cycloaliphatic parts of the 14 aforementioned radicals are unsubstituted, partly or completely halogenated, phenyl, phenylsulfonyl, phenyl-C.sub.1-C.sub.6 alkyl, phenylaminosulfonyl, phenylcarbonyl and phenoxycarbonyl, wherein phenyl in the last 6 mentioned radicals is unsubstituted or substituted by 1, 2, 3, 4 or 5 identical or different substituents selected from the group consisting of halogen, CN, NO.sub.2, C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-haloalkyl, C.sub.1-C.sub.6-alkoxy and C.sub.1-C.sub.6-haloalkoxy, or R.sup.3a, R.sup.3b together with the nitrogen atom, to which they are bound, form an N-bound, mono- or bicyclic heterocyclic radical, which may have 1, 2, 3 or 4 further heteroatoms which are selected from N, O and S, which is unsubstituted or substituted by one or more identical or different substituents selected from the group consisting of halogen, CN, NO.sub.2, C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-haloalkyl, C.sub.1-C.sub.6-alkoxy and C.sub.1-C.sub.6-haloalkoxy, one of R.sup.a, R.sup.b may also be OH, C.sub.1-C.sub.6-alkoxy, C.sub.3-C.sub.6-cycloalkoxy, (C.sub.3-C.sub.6-cycloalkyl)-C.sub.1-C.sub.4-alkoxy, C.sub.2-C.sub.6-alkenyloxy, C.sub.2-C.sub.6-alkynyloxy, (C.sub.1-C.sub.6-alkoxy)-C.sub.1-C.sub.6-alkoxy, where the aliphatic and cycloaliphatic parts of the 6 aforementioned radicals are unsubstituted, partly or completely halogenated, or phenoxy, which is unsubstituted or substituted by 1, 2, 3, 4 or 5 identical or different substituents selected from the group consisting of halogen, CN, NO.sub.2, C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-haloalkyl, C.sub.1-C.sub.6-alkoxy and C.sub.1-C.sub.6-haloalkoxy; k is 0, 1 or 2, including their agriculturally acceptable salts.

20. The compound of claim 19, wherein A is phenyl, which carries a fluorine atom in the 2-position of the phenyl ring and which further carries 1, 2, 3 or 4 identical or different substituents R.sup.A.

21. The compound of claim 20, wherein R.sup.A is halogen, CN, C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-alkoxy, C.sub.1-C.sub.6-haloalkyl, C.sub.3-C.sub.6-cycloalkyl, C.sub.3-C.sub.6-cycloalkoxy, (C.sub.3-C.sub.6-cycloalkyl)methoxy, C.sub.2-C.sub.6-alkynyl, C.sub.2-C.sub.6-alkenyl, C.sub.2-C.sub.6-alkynyloxy, C.sub.2-C.sub.6-alkenyloxy or C.sub.1-C.sub.6-haloalkoxy.

22. The compound of claim 21, wherein A is phenyl, which carries a fluorine atom in the 2-position of the phenyl ring and which further carries 1, 2, 3 or 4 substituents selected from the group consisting of F, Cl, CN, CF.sub.3, methyl, vinyl, ethynyl, cyclopropyl, methoxy, ethoxy, isopropyloxy, allyloxy, propargyloxy, cyclopropyloxy, cyclobutyloxy, cyclopentyloxy, (cyclopropyl)methoxy and 2-butyloxy.

23. The compound of claim 19, wherein R.sup.1 is selected from the group consisting of H, CN, C.sub.1-C.sub.6-alkyl, (C.sub.1-C.sub.6-alkoxy)-C.sub.1-C.sub.6-alkyl, (C.sub.1-C.sub.6-alkyl)carbonyl, (C.sub.1-C.sub.6-alkyl)sulfonyl, C.sub.1-C.sub.6-alkoxy, (C.sub.1-C.sub.6-alkoxy)carbonyl, (C.sub.1-C.sub.6-alkylamino)carbonyl, di(C.sub.1-C.sub.6-alkyl)aminocarbonyl, (C.sub.1-C.sub.6-alkylamino)sulfonyl, di(C.sub.1-C.sub.6-alkyl)aminosulfonyl, where the aliphatic parts of the 10 aforementioned radicals are unsubstituted, partly or completely halogenated, phenyl, phenylcarbonyl and phenyl-C.sub.1-C.sub.6 alkyl, wherein phenyl in the last 3 mentioned radical is unsubstituted or substituted by 1, 2, 3, 4, or 5 identical or different substituents selected from the group consisting of halogen, CN, NO.sub.2, C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-haloalkyl, C.sub.1-C.sub.6-alkoxy and C.sub.1-C.sub.6-haloalkoxy.

24. The compound of claim 19, wherein R.sup.2 is selected from the group consisting of H, CN, C.sub.1-C.sub.6-alkyl, (C.sub.1-C.sub.6-alkoxy)-C.sub.1-C.sub.6-alkyl, (C.sub.1-C.sub.6-alkyl)carbonyl, (C.sub.1-C.sub.6-alkyl)sulfonyl, (C.sub.1-C.sub.6-alkoxy)carbonyl, (C.sub.1-C.sub.6-alkylamino)carbonyl, di(C.sub.1-C.sub.6-alkyl)aminocarbonyl, (C.sub.1-C.sub.6-alkylamino)sulfonyl, di(C.sub.1-C.sub.6-alkyl)aminosulfonyl, where the aliphatic parts of the 9 aforementioned radicals are unsubstituted, partly or completely halogenated, phenyl, phenylcarbonyl and C.sub.1-C.sub.6 alkylphenyl, wherein phenyl in the last 3 mentioned radical is unsubstituted or substituted by 1, 2, 3, 4, or 5 identical or different substituents selected from the group consisting of halogen, CN, NO.sub.2, C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-haloalkyl, C.sub.1-C.sub.6-alkoxy and C.sub.1-C.sub.6-alkoxy.

25. The compound of claim 19, wherein R.sup.2 is selected from the group consisting of H, CN, C.sub.1-C.sub.6-alkyl, (C.sub.1-C.sub.6-alkoxy)-C.sub.1-C.sub.6-alkyl, (C.sub.1-C.sub.6-alkyl)carbonyl or (C.sub.1-C.sub.6-alkyl)sulfonyl, where the aliphatic parts of the 4 aforementioned radicals unsubstituted partly or completely halogenated.

26. The compound of claim 19, wherein R.sup.1 is H.

27. The compound of claim 19, wherein R.sup.2 is H.

28. The compound of claim 19, wherein X is OR.sup.3c, wherein R.sup.3c is selected from the group consisting of H, C.sub.1-C.sub.6-alkyl, C.sub.3-C.sub.6-cycloalkyl, (C.sub.1-C.sub.6-alkoxy)-C.sub.1-C.sub.6-alkyl, (C.sub.1-C.sub.6-alkyl)-carbonyl, (C.sub.1-C.sub.6-alkoxy)carbonyl, (C.sub.1-C.sub.6-alkyl)sulfonyl, where the aliphatic parts of the 6 aforementioned radicals are unsubstituted, partly or completely halogenated, phenyl, phenylsulfonyl or phenyl-C.sub.1-C.sub.6 alkyl, wherein phenyl in the last 3 mentioned radicals is unsubstituted or substituted by 1, 2, 3, 4 or 5 identical or different substituents selected from the group consisting of halogen, CN, NO.sub.2, C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-haloalkyl, C.sub.1-C.sub.6-alkoxy and C.sub.1-C.sub.6-haloalkoxy.

29. The compound of claim 19, wherein X is S(O).sub.kR.sup.3d, wherein R.sup.3d is selected from the group consisting of H, CN, C.sub.1-C.sub.6-alkyl, C.sub.3-C.sub.6-cycloalkyl, C.sub.3-C.sub.6-cycloalkyl-C.sub.1-C.sub.6-alkyl, (C.sub.1-C.sub.6-alkoxy)-C.sub.1-C.sub.6-alkyl, (C.sub.1-C.sub.6-alkyl)-carbonyl, (C.sub.1-C.sub.6-alkoxy)carbonyl, (C.sub.1-C.sub.6-alkyl)sulfonyl, where the aliphatic parts of the 7 aforementioned radicals are unsubstituted, partly or completely halogenated, phenyl, phenylsulfonyl or phenyl-C.sub.1-C.sub.6 alkyl, wherein phenyl in the last 3 mentioned radicals is unsubstituted or substituted by 1, 2, 3, 4 or 5 identical or different substituents selected from the group consisting of halogen, CN, NO.sub.2, C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-haloalkyl, C.sub.1-C.sub.6-alkoxy and C.sub.1-C.sub.6-haloalkoxy, and k is 0, 1 or 2.

30. The compound of claim 19, wherein X is NR.sup.3aR.sup.3b, wherein R.sup.3aR.sup.3b are independently of one another H, CN, S(O).sub.2NH.sub.2, C.sub.1-C.sub.6-alkyl, C.sub.2-C.sub.6-alkenyl, C.sub.2-C.sub.6-alkynyl, C.sub.3-C.sub.6-cycloalkyl, C.sub.3-C.sub.6-cycloalkyl-C.sub.1-C.sub.6-alkyl, (C.sub.1-C.sub.6-alkoxy)-C.sub.1-C.sub.6-alkyl, (C.sub.1-C.sub.6-alkyl)-carbonyl, (C.sub.1-C.sub.6-alkoxy)carbonyl, (C.sub.1-C.sub.6-alkyl)sulfonyl, C.sub.1-C.sub.6-alkylamino)carbonyl, di(C.sub.1-C.sub.6-alkyl)aminocarbonyl, (C.sub.1-C.sub.6-alkylamino)sulfonyl, di(C.sub.1-C.sub.6-alkyl)aminosulfonyl and (C.sub.1-C.sub.6-alkoxy)sulfonyl where the aliphatic parts of the 15 aforementioned radicals are unsubstituted, partly or completely halogenated, phenyl, phenylsulfonyl or phenyl-C.sub.1-C.sub.6 alkyl, wherein phenyl in the last 3 mentioned radicals is unsubstituted or substituted by 1, 2, 3, 4 or 5 identical or different substituents selected from the group consisting of halogen, CN, NO.sub.2, C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-haloalkyl, C.sub.1-C.sub.6-alkoxy and C.sub.1-C.sub.6-haloalkoxy, one of R.sup.a, R.sup.b may also be OH, C.sub.1-C.sub.6-alkoxy, C.sub.3-C.sub.6-cycloalkoxy, (C.sub.1-C.sub.6-alkoxy)-C.sub.1-C.sub.6-alkoxy, where the aliphatic and cycloaliphatic parts of the 3 aforementioned radicals are unsubstituted, partly or completely halogenated, or R.sup.3a, R.sup.3b together with the nitrogen atom, to which they are bound, form an N-bound saturated or unsaturated mono- or bicyclic heterocyclic radical, which may have 1, 2, 3 or 4 further heteroatoms which are selected from N, O and S, which is substituted or unsubstituted by one or more identical or different substituents selected from the group consisting of halogen, CN, NO.sub.2, C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-haloalkyl, C.sub.1-C.sub.6-alkoxy, (C.sub.1-C.sub.6-alkoxy)-C.sub.1-C.sub.6-alkyl and C.sub.1-C.sub.6-haloalkoxy.

31. The compound of claim 30, wherein X is NR.sup.3aR.sup.3b, wherein R.sup.3aR.sup.3b together with the nitrogen atom, to which they are bound, form an N-bound saturated or unsaturated mono- or bicyclic heterocyclic radical, which is selected from the group consisting of 1-aziridinyl, 1-azetidinyl, 1-piperidinyl, 1-pyrrolidinyl, azepan-1-yl, azocan-1-yl, morpholin-4-yl, isoxazolidine-2-yl, oxazolidine-3-yl, piperazine-1-yl, octahydroisoindol-2-yl, octahydroindol-1-yl, octahydro-2H-quinolin-1-yl, azabicyclo[2.2.1]heptan-3-yl and azabicyclo[2.2.1]heptan-7-yl, where the aforementioned radicals are unsubstituted or substituted by one or more identical or different substituents selected from the group consisting of halogen, CN, NO.sub.2, C.sub.1-C.sub.2-alkyl, C.sub.1-C.sub.2-haloalkyl, (C.sub.1-C.sub.2-alkoxy)-C.sub.1-C.sub.2-alkyl, C.sub.1-C.sub.2-alkoxy and C.sub.1-C.sub.2-haloalkoxy.

32. The compound of claim 30, wherein R.sup.1 is H; R.sup.2 is H; and A is phenyl, which carries a fluorine atom in the 2-position of the phenyl ring and which further carries 1, 2, 3 or 4 identical or different substituents R.sup.A.

33. A halotriazine compound of formula (II) ##STR00022## wherein X is as defined in claim 19; R.sup.2 is H, C.sub.1-C.sub.6-alkyl, C.sub.2-C.sub.6-alkenyl, C.sub.2-C.sub.6-alkynyl, (C.sub.3-C.sub.6-cycloalkyl)-C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.6-alkoxy, (C.sub.1-C.sub.6-alkoxy)-C.sub.1-C.sub.6-alkyl, (C.sub.1-C.sub.6-alkyl)-carbonyl, (C.sub.1-C.sub.6-alkoxy)carbonyl, (C.sub.1-C.sub.6-alkyl)sulfonyl, (C.sub.1-C.sub.6-alkylamino)carbonyl, di(C.sub.1-C.sub.6-alkyl)aminocarbonyl, (C.sub.1-C.sub.6-alkylamino)sulfonyl, di(C.sub.1-C.sub.6-alkyl)aminosulfonyl and (C.sub.1-C.sub.6-alkoxy)sulfonyl, where the aliphatic and cycloaliphatic parts of the 14 aforementioned radicals are unsubstituted, partly or completely halogenated, phenyl, phenyl-C.sub.1-C.sub.6-alkyl, phenylsulfonyl, phenylcarbonyl and phenoxycarbonyl, wherein phenyl in the last 5 mentioned radicals are unsubstituted or substituted by 1, 2, 3, 4 or 5 identical or different substituents selected from the group consisting of halogen, CN, NO.sub.2, C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-haloalkyl, C.sub.1-C.sub.6-alkoxy and C.sub.1-C.sub.6-haloalkoxy; and Hal is halogen;

34. An agrochemical composition comprising a herbicidal active amount of at least one compound as claimed in claim 19 and at least one inert liquid and/or solid carrier and, if appropriate, at least one surface-active substances.

35. A method of controlling undesired vegetation, which comprises allowing a herbicidally active amount of at least one compound as claimed in claim 19 to act on plants, their environment or on seed.

36. A method for desiccation/defoliation of plants, which comprises allowing a herbicidally active amount of at least one compound as claimed in claim 19 to act on plants, their environment or on seed.

37. The method of claim 35, wherein A is phenyl, which carries a fluorine atom in the 2-position of the phenyl ring and which further carries 1, 2, 3 or 4 identical or different substituents R.sup.A.

38. The method of claim 37, wherein R.sup.A is halogen, CN, C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-alkoxy, C.sub.1-C.sub.6-haloalkyl, C.sub.3-C.sub.6-cycloalkyl, C.sub.3-C.sub.6-cycloalkoxy, (C.sub.3-C.sub.6-cycloalkyl)methoxy, C.sub.2-C.sub.6-alkynyl, C.sub.2-C.sub.6-alkenyl, C.sub.2-C.sub.6-alkynyloxy, C.sub.2-C.sub.6-alkenyloxy or C.sub.1-C.sub.6-haloalkoxy.

Description

A PREPARATION EXAMPLES

Example 1: 6-(2-methylpyrrolidin-1-yl)-N4-(2,3,4,5,6-pentafluorophenyl)-1,3,5-triazine-2,4-diamine

[0881] ##STR00017##

1.1: 4-chloro-6-(2-methylpyrrolidin-1-yl)-1,3,5-triazin-2-amine

[0882] ##STR00018##

[0883] To a solution of cyanuric chloride (5 g, 27 mmol, 2 eq) dissolved in dry THF (100 mL) cooled to 0 C. was added diisopropyethylamine (2.6 mL, 15 mmol, 1.1 eq) and the mixture was cooled to 10 C. After 15 min of stirring, a solution of 2-methylpyrrolidine (1.41 mL, 14 mmol, 1 eq) in dry THF (20 mL) was slowly added over a period of 1 hour at this temperature. After stirring for another one hour, a 25% w/w aqueous solution of ammonia (8.5 mL, 4 eq.) was added and the mixture was allowed to warm to room temperature and stirred for 16 h. The obtained mixture was washed with water (100 mL) and extracted with EtOAc (250 mL). The combined organic extracts were washed with brine (100 mL), dried (Na.sub.2SO.sub.4) and volatiles were removed by a rotary evapor. Chromatography (Silica gel, CH.sub.2Cl.sub.2:MeOH, 100:0 to 98:2 to 95:5) gave the desired chloro-triazine (590 mgs, 2.7 mmol, 19%) as a white solid.

[0884] LC/MS RT: 0.864. LC/MS (m/z): 214.4

1.2: 6-(2-methylpyrrolidin-1-yl)-N4-(2,3,4,5,6-pentafluorophenyl)-1,3,5-triazine-2,4-diamine

[0885] A mixture of the above chloro-triazine (500 mg, 2.34 mmol, 1 eq), 2,3,4,5,6-pentafluoroaniline (428 mg, 2.34 mmol, 1 eq), potassium tert-butoxide (788 mg, 7 mmol, 3 eq) and [1,1-bis(di-cyclohexylphosphino)ferrocene] dichloropalladium(II) (190 mg, 0.23 mmol, 0.1 eq) in dioxane (15 mL) was heated at 100 C. for 16 h. The obtained mixture was cooled to 22 C. and water (30 mL) was added and the mixture was extracted with EtOAc (330 mL). The combined organic extracts were washed with brine (100 mL), dried (Na.sub.2SO.sub.4) and volatiles were removed by a rotary evapor. Chromatography (Silica gel, CH: EtOAC, 100:0 gardient to 50:50) gave the desired product (262 mg, 0.73 mmol, 31%) as a pale brown solid.

[0886] LC/MS RT: 0.948, LC/MS (m/z): 361.5

[0887] The compounds 5 to 35 listed below in table C have been prepared by analogy to the example 1 mentioned above.

Example 2: 6-methoxy-N2-(2,3,4,5,6-pentafluorophenyl)-1,3,5-triazine-2,4-diamine

[0888] ##STR00019##

[0889] Potassium tert-butoxide (1.05 g, 9.34 mmol, 3 eq) and [1,1-Bis(di-cyclohexylphosphino)ferrocene] dichloropalladium(II) (250 mg, 0.31 mmol, 0.1 eq) were added to a mixture of 4-chloro-6-methoxy-1,3,5-triazin-2-amine (500 mg, 3.11 mmol, 1 eq) and 2,3,4,5,6pentafluoroaniline (630 mg, 3.43 mmol, 1.1 eq) in dioxane (10 mL). The resulting solution was stirred at 100 C. for 16 h. The obtained mixture was cooled to 22 C. and water (30 mL) was added and extracted with EtOAc (330 mL). The combined organic extracts were washed with brine (100 mL), dried (Na.sub.2SO.sub.4) and rotary evaporated. Chromatography

[0890] (CH: EtOAC, 100:0 gardient to 50:50) gave the desired product (290 mg, 0.94 mmol, 30%) as a pale brown solid.

[0891] LC/MS RT: 0.904, LC/MS (m/z): 307.18

[0892] The compounds 2 and 4 listed below in table C have been prepared by analogy to the example 2 mentioned above.

TABLE-US-00008 TABLE C [00020] MS.sup.1) No. R.sup.a R.sup.b R.sup.c R.sup.d X [m/z] 2 F F F F OCH.sub.3 308.0 3 F F F F OCH.sub.2CF.sub.3 376.0 4 F F H F OCH.sub.3 290.0 5 F F F F 1-Piperidyl 361.1 6 F F F F Pyrrolidin-1-yl 347.1 7 F F F F Azepan-1-yl 375.1 8 F F F F 3,5-Dimethyl-1-piperidyl 389.2 9 F F F F Azocan-1-yl 389.2 10 F F F F Benzyl(methyl)amino 397.1 11 F F H F 1-Piperidyl 342.8 12 F F H F Pyrrolidin-1-yl 328.8 13 F H H F Pyrrolidin-1-yl 310.8 14 F F H H 1-Piperidyl 324.8 15 F H H H 1-Piperidyl 306.8 16 F H H H Pyrrolidin-1-yl 392.8 17 F F F F 2,5-Dimethyl-1-pyrrolidin-1-yl 374.8 18 F F H F 2,5-Dimethyl-1-pyrrolidin-1-yl 357.6 19 F F H F Morpholin-4-yl 344.8 20 F F F F 2-methyl-1-pyrrolidin-1-yl 361.5 21 F F H F 2-methyl-1-pyrrolidin-1-yl 343.7 22 F F H F Ethyl(methl)amino 317.5 23 F F F F Morpholin-4-yl 363.5 24 F F F F Ethyl(methl)amino 335.5 25 F F F F (2R)-2-(methoxy- 391.6 methyl)pyrrolidin-1-yl 26 F F H F (2R)-2-(methoxy- 373.6 methyl)pyrrolidin-1-yl 27 F F F F Methoxy(methyl)-amino 337.5 28 F F H F methoxy(methyl)-amino 319.5 29 F F F F (2S)-2-(methoxy- 391.6 methyl)pyrrolidin-1-yl 30 F F H F (2S)-2-(methoxy- 373.6 methyl)pyrrolidin-1-yl 31 F F F F 2-(methoxy-methyl)pyrrolidin-1-yl 391.6 32 F F H F 2-(methoxy-methyl)pyrrolidin-1-yl 373.6 33 F F F F azetidin-1-yl 333.5 34 F F H F azetidin-1-yl 315.5 35 F F F F diethylamino 349.6 36 F F H F diethylamino 331.5 37 F F H F (2S)-(2-methyl)-pyrrolidin-1-yl 342.8 38 F F F F (2S)-(2-methyl)-pyrrolidin-1-yl 360.7 .sup.1)Mass Spectrum M.sup.+ [m/z]

B Use Examples

[0893] The herbicidal activity of the azines of formula (I) was demonstrated by the following greenhouse experiments:

[0894] The culture containers used were plastic flowerpots containing loamy sand with approximately 3.0% of humus as the substrate. The seeds of the test plants were sown separately for each species.

[0895] For the pre-emergence treatment, the active ingredients, which had been suspended or emulsified in water, were applied directly after sowing by means of finely distributing nozzles. The containers were irrigated gently to promote germination and growth and subsequently covered with transparent plastic hoods until the plants had rooted. This cover caused uniform germination of the test plants, unless this had been impaired by the active ingredients.

[0896] For the post-emergence treatment, the test plants were first grown to a height of 3 to 15 cm, depending on the plant habit, and only then treated with the active ingredients which had been suspended or emulsified in water. For this purpose, the test plants were either sown directly and grown in the same containers, or they were first grown separately as seedlings and transplanted into the test containers a few days prior to treatment.

[0897] Depending on the species, the plants were kept at 10-25 C. or 20-35 C., respectively.

[0898] The test period extended over 2 to 4 weeks. During this time, the plants were tended, and their response to the individual treatments was evaluated.

[0899] Evaluation was carried out using a scale from 0 to 100. 100 means no emergence of the plants, or complete destruction of at least the aerial moieties, and 0 means no damage, or normal course of growth. A moderate herbicidal activity is given at values of at least 60, a good herbicidal activity is given at values of at least 70, and a very good herbicidal activity is given at values of at least 85.

[0900] The plants used in the greenhouse experiments were of the following species:

TABLE-US-00009 Bayer code Scientific name ABUTH Abutilon theophrasti ALOMY Alopecurus myosuroides AMARE Amaranthus retroflexus APESV Apera spica-venti ECHCG Echinocloa crus-galli LAMPU Lamium purpureum POLCO Polygonum convolvulus SETFA Setaria faberi SETVI Setaria viridis STEME Stellaria media VIOAR Viola arvensis

[0901] Example 2 applied by post-emergence method at an application rate of

[0902] 0.500 kg/ha, showed very good herbicidal activity against ECHCG, POLCO and SETVI.

[0903] Example 2 applied by pre-emergence method at an application rate of 0.125 kg/ha, showed good to very good herbicidal activity against APESV, AMARE and ALOMY.

[0904] Example 3 applied by post-emergence method at an application rate of 0.500 kg/ha, showed very good herbicidal activity against STEME, SETVI and VIOAR.

[0905] Example 3 applied by pre-emergence method at an application rate of 1.000 kg/ha, showed very good herbicidal activity against ECHCG, SETFA and AMARE.

[0906] Example 4 applied by pre-emergence method at an application rate of 0.500 kg/ha, showed very good herbicidal activity against LAMPU, STEME and VIOAR.

[0907] Example 5 applied by post-emergence method at an application rate of 1.000 kg/ha, showed very good herbicidal activity against ECHCG, SETFA and AMARE.

[0908] Example 5 applied by pre-emergence method at an application rate of 1.000 kg/ha, showed very good herbicidal activity against ALOMY, APESV and AMARE.

[0909] Example 6 applied by post-emergence method at an application rate of 1.000 kg/ha, showed very good herbicidal activity against ABUTH, SETFA and AMARE.

[0910] Example 6 applied by pre-emergence method at an application rate of 0.500 kg/ha, showed very good herbicidal activity against ALOMY, SETFA and APESV.

[0911] Example 7 applied by post-emergence method at an application rate of 1.000 kg/ha, showed very good herbicidal activity against ABUTH and AMARE.

[0912] Example 7 applied by pre-emergence method at an application rate of 0.500 kg/ha, showed good to very good herbicidal activity against ALOMY, SETFA and APESV.

[0913] Example 10 applied by post-emergence method at an application rate of 1.000 kg/ha, showed very good herbicidal activity against ABUTH and AMARE.

[0914] Example 12 applied by post-emergence method at an application rate of 0.500 kg/ha, showed very good herbicidal activity against ABUTH, SETFA and AMARE.

[0915] Example 12 applied by pre-emergence method at an application rate of 0.500 kg/ha, showed very good herbicidal activity against ALOMY, SETFA and AMARE.

[0916] Example 13 applied by post-emergence method at an application rate of 0.500 kg/ha, showed very good herbicidal activity against APESV and AMARE.

[0917] Example 13 applied by pre-emergence method at an application rate of 0.500 kg/ha, showed very good herbicidal activity against APESV and AMARE.

[0918] Example 14 applied by post-emergence method at an application rate of 0.500 kg/ha, showed very good herbicidal activity against APESV and AMARE.

[0919] Example 14 applied by pre-emergence method at an application rate of 0.500 kg/ha, showed very good herbicidal activity against APESV and AMARE.

[0920] Example 15 applied by pre-emergence method at an application rate of 0.500 kg/ha, showed very good herbicidal activity against APESV and AMARE.

[0921] Example 17 applied by pre-emergence method at an application rate of 0.500 kg/ha, showed very good herbicidal activity against SETFA, APESV and AMARE.

[0922] Example 18 applied by pre-emergence method at an application rate of 0.500 kg/ha, showed very good herbicidal activity against ECHCG, APESV and AMARE.

[0923] Example 19 applied by pre-emergence method at an application rate of 0.500 kg/ha, showed good to very good herbicidal activity against APESV and AMARE.

[0924] Example 20 applied by pre-emergence method at an application rate of 0.500 kg/ha, showed very good herbicidal activity against SETFA, APESV and AMARE.

[0925] Example 21 applied by pre-emergence method at an application rate of 0.500 kg/ha, showed very good herbicidal activity against SETFA, ALOMY and AMARE.

[0926] Example 22 applied by pre-emergence method at an application rate of 0.500 kg/ha, showed very good herbicidal activity against APESV, ALOMY and AMARE.

[0927] Example 23 applied by pre-emergence method at an application rate of 0.500 kg/ha, showed very good herbicidal activity against APESV, ABUTH and AMARE.

[0928] Example 25 applied by post-emergence method at an application rate of 0.500 kg/ha, showed very good herbicidal activity against APESV, AMARE and SETFA.

[0929] Example 25 applied by pre-emergence method at an application rate of 0.500 kg/ha, showed good to very good herbicidal activity against SETFA, APESV, AMARE and LOMY.

[0930] Example 26 applied by post-emergence method at an application rate of 0.500 kg/ha, showed very good herbicidal activity against APESV, AMARE and SETFA.

[0931] Example 26 applied by pre-emergence method at an application rate of 0.500 kg/ha, showed very good herbicidal activity against SETFA, APESV, AMARE and ALOMY.

[0932] Example 27 applied by post-emergence method at an application rate of 0.500 kg/ha, showed very good herbicidal activity against ABUTH, AMARE and SETFA.

[0933] Example 27 applied by pre-emergence method at an application rate of 0.500 kg/ha, showed very good herbicidal activity against SETFA, ABUTH, APESV, AMARE and ALOMY.

[0934] Example 28 applied by post-emergence method at an application rate of 0.500 kg/ha, showed very good herbicidal activity against ABUTH, AMARE and SETFA.

[0935] Example 28 applied by pre-emergence method at an application rate of 0.500 kg/ha, showed very good herbicidal activity against SETFA, ABUTH, APESV, AMARE and ALOMY.

[0936] Example 29 applied by post-emergence method at an application rate of 0.500 kg/ha, showed very good herbicidal activity against APESV and AMARE.

[0937] Example 29 applied by pre-emergence method at an application rate of 0.500 kg/ha, showed very good herbicidal activity against APESV and AMARE.

[0938] Example 30 applied by post-emergence method at an application rate of 0.500 kg/ha, showed very good herbicidal activity against APESV and AMARE.

[0939] Example 30 applied by pre-emergence method at an application rate of 0.500 kg/ha, showed very good herbicidal activity against APESV and AMARE.

[0940] Example 31 applied by post-emergence method at an application rate of 0.500 kg/ha, showed very good herbicidal activity against APESV.

[0941] Example 31 applied by pre-emergence method at an application rate of 0.500 kg/ha, showed good to very good herbicidal activity against AMARE and APESV.

[0942] Example 32 applied by post-emergence method at an application rate of 0.500 kg/ha, showed very good herbicidal activity against APESV, AMARE and SETFA.

[0943] Example 32 applied by pre-emergence method at an application rate of 0.500 kg/ha, showed good to very good herbicidal activity against SETFA, APESV, AMARE and ALOMY.

[0944] Example 33 applied by post-emergence method at an application rate of 0.500 kg/ha, showed very good herbicidal activity against ABUTH, AMARE and ECHCG.

[0945] Example 33 applied by pre-emergence method at an application rate of 0.500 kg/ha, showed very good herbicidal activity against ABUTH, SETFA, AMARE and ECHCG.

[0946] Example 34 applied by post-emergence method at an application rate of 0.500 kg/ha, showed very good herbicidal activity against ABUTH, AMARE and ECHCG.

[0947] Example 34 applied by pre-emergence method at an application rate of 0.500 kg/ha, showed very good herbicidal activity against SETFA, ABUTH, AMARE and ECHCG.

[0948] Example 35 applied by post-emergence method at an application rate of 0.500 kg/ha, showed very good herbicidal activity against APESV and AMARE.

[0949] Example 35 applied by pre-emergence method at an application rate of 0.500 kg/ha, showed good to very good herbicidal activity against APESV and AMARE.

[0950] Example 36 applied by post-emergence method at an application rate of 0.500 kg/ha, showed very good herbicidal activity against APESV and AMARE.

[0951] Example 36 applied by pre-emergence method at an application rate of 0.500 kg/ha, showed good to very good herbicidal activity against APESV and AMARE.