EP0932604A1

EP0932604A1 - Substituted 2,4-diamino-1,3,5-triazines as herbicides

Info

Publication number: EP0932604A1
Application number: EP97910377A
Authority: EP
Inventors: Hans-Jochem Riebel; Stefan Lehr; Uwe Stelzer; Yukiyoshi Watanabe; Markus Dollinger; Seishi Ito; Toshio Goto; Akihiko Yanagi
Original assignee: Bayer AG; Nihon Bayer Agrochem KK
Current assignee: Bayer CropScience AG; Bayer CropScience KK
Priority date: 1996-10-10
Filing date: 1997-09-29
Publication date: 1999-08-04
Also published as: CA2267931A1; WO1998015536A1; AU4778997A; JP2001501938A; KR20000048676A; CN1233242A; AU729054B2; CN1186331C; KR100503912B1; US6440903B1; BR9713255A; DE19641692A1

Abstract

The invention relates to novel substituted 2,4-diamino-1,3,5-triazines of formula (I), (in which R<1>, R<2>, R<3>, X and Z have the meaning cited in the description), methods and new intermediate products for their production and their use as herbicides.

Description

SUBSTITUTED 2,4-DIAMINO-l, 3,5-TRIAZINE AS HERBICIDES

The invention relates to new substituted 2,4-diamino-l, 3,5-triazines, processes and new intermediates for their preparation and their use as herbicides.

A number of substituted 2,4-diamino-triazines are already known from the (patent) literature (cf. US 3816419, US 3932167, EP 191496, EP 273328, EP 411153 / WO 90/09378, JP 62294669 - cited in Chem. Abstracts 109: 129062v). However, these connections have so far not gained any particular importance.

The new substituted 2,4-diamino-1,3,5-triazines of the general formula (I) have now been found

in which

R ^{1 represents} hydrogen or alkyl having 1 to 6 carbon atoms which is optionally substituted by hydroxy, cyano, halogen or C _] -C4-alkoxy,

R ² for hydrogen, for formyl, for alkyl, alkylcarbonyl, alkoxycarbonyl or alkylsulfonyl, each optionally substituted by cyano, halogen or C _] -C4-alkoxy, each having 1 to 6 carbon atoms in the alkyl groups, or for each optionally by cyano, halogen, C ] C4-alkyl, halo-C _j - C4-alkyl, Cι-C4-alkoxy, halo-Cι-C4-alkoxy or _C] -C4- alkoxycarbonyl-substituted phenylcarbonyl, naphthylcarbonyl, phenylsulfonyl or naphthylsulfonyl group, R ^{3 represents} alkyl with 1 to 6 carbon atoms optionally substituted by cyano, halogen or C 1 -C 4 alkoxy or cycloalkyl with 3 to 6 carbon atoms optionally substituted by cyano, halogen or C 1 -C 4 alkyl,

X represents a substituent from the following group:

Hydroxy, cyano, nitro, halogen, each optionally substituted by hydroxy, cyano or halogen-substituted alkyl or alkoxy each having 1 to 6 carbon atoms, each optionally substituted by halogen, alkylcarbonyl, alkoxycarbonyl, alkylthio, alkylsulfinyl or alkylsulfonyl each having 1 to 6 carbon atoms in the alkyl groups, each optionally substituted by hydroxyl, cyano, nitro, halogen, C] -C4-alkyl, C \ -C4-haloalkyl, C j -C4-alkoxy or C] -C4-haloalkoxy, and phenyl or phenoxy, and

Z for hydrogen, hydroxy, halogen, each optionally by hydroxy,

Cyano, nitro, halogen, C 1 -C4- alkoxy, C] -C4-alkyl-carbonyl, C1-C4-alkoxy-carbonyl, Cι-C4-alkylthio, C \ -C 4 alkylsulphinyl or C _j -C 4 alkyl sulfonyl-substituted alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylthio, alkylsulfinyl or alkylsulfonyl each having 1 to 6 carbon atoms in the alkyl groups, for each optionally substituted by halogen alkenyl or alkynyl each having 2 to 6 carbon atoms, or for optionally by cyano, halogen or C1 -C4- alkyl substituted cycloalkyl having 3 to 6 carbon atoms,

however, the compounds (known from JP 62294669)

2-amino-4-methox \ '- 6- [l- (3-chlorophenyl) ethylamino] -l, 3,5-triazine, 2-amino-4-methoxy-6- [l- (3- methyl-phenyl) -ethylamino] -l, 3,5-triazine, 2-amino-4-chloro-6- [l- (3-trifluoromethyl-phenyl) -ethylamino] -l, 3,5-triazine, 2- Amino-4-chloro-6- [l- (3-nitro-phenyl) -ethylamino-l, 3,5-triazine, 2-amino-4-chloro-6- [l- (3-chlorophenyl) - ethylamino] - 1, 3, 5 -triazine and 2-amino-4-chloro-6- [1 - (3-methylphenyl) ethylamino] - 1, 3, 5 -triazine excluded are.

The new substituted 2,4-diamino-1,3,5-triazines of the general formula (I) are obtained if

(a) substituted biguanides of the general formula (II)

in which

R ¹ , R ² , R ³ and X have the meaning given above,

and / or acid adducts of compounds of the general formula (II)

with alkoxycarbonyl compounds of the general formula (III)

Z-CO-OR '(III)

in which

Z has the meaning given above and

R 'represents alkyl,

if appropriate in the presence of a reaction auxiliary and if appropriate in the presence of a diluent, or if you

(b) substituted aminotriazines of the general formula (IV)

in which

R ³ , X and Z have the meaning given above and

Xl represents halogen or alkoxy,

with nitrogen compounds of the general formula (V)

. R ^

(V)

in which

R ¹ and R ^{2 have} the meaning given above,

if appropriate in the presence of a reaction auxiliary and if appropriate in the presence of a diluent,

or if you

(c) substituted aminotriazines of the general formula (VI) N

N N (VI)

^* N ^' ^' X ^*

in which

R ¹ , R ² and Z have the meaning given above and

X ^{2 represents} halogen or alkoxy,

with amino compounds of the general formula (VII)

in which

R ³ and X have the meaning given above,

or if you

(d) for the preparation of compounds of the formula (I), except those with R ² = H, 2,4-diamino-l, 3,5-triazines of the general formula (Ia)

in which

R ¹ , R ³ , X and Z have the meaning given above,

with alkylating, acylating or sulfonylating agents of the general formula (VIII)

YR ² (VIII)

in which

R ^{2 has} the meaning given above - except hydrogen - and

Y represents halogen, alkoxy, alkoxysulfonyloxy or acyloxy,

and optionally on the compounds of the general formula (I) obtained according to the processes described under (a), (b), (c) or (d), as part of the above definition of substituents, by further conversions by customary methods.

The new substituted 2,4-diamino-1,3,5-triazines of the general formula (I) are notable for their strong and selective herbicidal activity. The compounds of the general formula (I) according to the invention contain at least one asymmetrically substituted carbon atom and can therefore be present in various enantiomeric (R- and S-configured forms) or diastereomeric forms. The invention relates both to the various possible individual enantiomeric or stereoisomeric forms of the compounds of the general formula (I) and to the mixtures of these isomeric compounds.

In the definitions, the hydrocarbon chains, such as alkyl, are in each case straight-chain or branched, also in conjunction with heteroatoms, such as in alkoxy or alkylthio.

Halogen generally represents fluorine, chlorine, bromine or iodine, preferably fluorine, chlorine or bromine, in particular fluorine or chlorine.

The invention preferably relates to compounds of the formula (I) in which

R ^{1 represents} hydrogen or alkyl having 1 to 4 carbon atoms which is optionally substituted by hydroxy, cyano, fluorine, chlorine, methoxy or ethoxy,

R ² for hydrogen, for formyl, for each optionally by cyano, fluorine,

Chlorine, methoxy or ethoxy substituted alkyl, alkylcarbonyl, alkoxycarbonyl or alkylsulfonyl each having 1 to 4 carbon atoms in the alkyl groups, or for each optionally by cyano, fluorine, chlorine, methyl, ethyl, n- or i-propyl, n-, i- , s- or t-butyl, trifluoromethyl, methoxy, ethoxy, n- or i-propoxy, n-, i-, s- or t-butoxy, difluoromethoxy,

Trifluoromethoxy, methoxycarbonyl or ethoxycarbonyl substituted phenylcarbonyl or phenylsulfonyl,

R ^{3 represents} alkyl having 1 to 4 carbon atoms which is optionally substituted by hydroxy, cyano, fluorine, chlorine, methoxy or ethoxy or represents cycloalkyl having 3 to 6 carbon atoms which is optionally substituted by cyano, fluorine, chlorine, methyl or ethyl, X represents a substituent from the following group:

Hydroxy, cyano, nitro, fluorine, chlorine, bromine, iodine, each optionally substituted by hydroxy, cyano, fluorine or chlorine, alkyl or alkoxy each having 1 to 4 carbon atoms, each optionally by fluorine or

Chlorine-substituted alkylcarbonyl, alkoxycarbonyl, alkylthio, alkylsulfinyl or alkylsulfonyl each having 1 to 4 carbon atoms in the alkyl groups, in each case optionally by hydroxy, cyano, nitro, fluorine, chlorine, bromine, iodine, methyl, ethyl, n- or i-propyl, n -, i-, s- or t-butyl, trifluoromethyl, methoxy, ethoxy, n- or i-propoxy, n-, i-, s- or t-butoxy, difluoromethoxy or trifluoromethoxy-substituted phenyl or phenoxy, and

Z for hydrogen, hydroxy, fluorine, chlorine, bromine, for each optionally by hydroxy, cyano, nitro, fluorine, chlorine, methoxy, ethoxy, acetyl, propionyl, methoxycarbonyl, ethoxycarbonyl, methylthio, ethylthio, methylsulfinyl, ethylsulfinyl, methylsulfonyl or Ethylsulfonyl-substituted alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylthio, alkylsulfinyl or alkylsulfonyl each having 1 to 4 carbon atoms in the alkyl groups, for each optionally substituted by fluorine, chlorine or bromine or alkenyl or alkynyl each having 2 to 4 carbon atoms, or for optionally by

Cyano, fluorine, chlorine, methyl or ethyl substituted cycloalkyl having 3 to 6 carbon atoms,

however, the compounds (known from JP 62294669)

2-amino-4-methoxy-6- [l- (3-chlorophenyl) ethylamino] -l, 3,5-triazine, 2-amino-4-methoxy-6- [1 - (3-methyl- phenyl) ethylamino] - 1, 3, 5-triazine, 2-amino-4-chloro-6- [1 - (3 - trifluoromethylphenyl) ethylamino] -l, 3,5-triazine, 2-amino- 4-chloro-6- [1- (3-nitro-phenyl) -ethylamino] - 1, 3,5-triazine, 2-amino-4-chloro-6- [1 - (3-chlorophenyl) -ethyl - amino] -l, 3,5-triazine and 2-amino-4-chloro-6- [l- (3-methylphenyl) ethylamino] - 1,3,5-triazine

excluded are. The invention relates in particular to compounds of the formula (I) in which

R ^{1 represents} hydrogen or methyl, ethyl, n- or i-propyl optionally substituted by hydroxy, cyano, fluorine, chlorine, methoxy or ethoxy,

R ² for hydrogen, for formyl, for each methyl, ethyl, acetyl, propionyl, methoxycarbonyl, ethoxycarbonyl, methylsulfonyl or ethylsulfonyl optionally substituted by cyano, fluorine, chlorine, methoxy or ethoxy, or for each optionally by cyano, fluorine, chlorine, methyl , Ethyl, trifluoromethyl, methoxy, ethoxy, difluoromethoxy, trifluoromethoxy, methoxycarbonyl or ethoxycarbonyl substituted phenylcarbonyl or phenylsulfonyl,

R ³ for each optionally by hydroxy, cyano, fluorine, chlorine, methoxy or

Ethoxy substituted methyl, ethyl, n- or i-propyl, or represents cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl which is optionally substituted by cyano, fluorine, chlorine, methyl or ethyl,

X represents a substituent from the following group:

Hydroxy, cyano, nitro, fluorine, chlorine, bromine, each optionally substituted by hydroxy, cyano, fluorine or chlorine, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, methoxy, ethoxy , n- or i-propoxy, in each case optionally substituted by fluorine or chlorine, acetyl, propionyl,

Methoxycarbonyl, ethoxycarbonyl, methylthio, ethylthio, methylsulfinyl, ethylsulfmyl, methylsulfonyl or ethylsulfonyl, each optionally by hydroxyl, cyano, nitro, fluorine, chlorine, bromine, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, trifluoromethyl, methoxy, ethoxy, n- or i-propoxy, difluoromethoxy or trifluoromethoxy-substituted phenyl or phenoxy, and

Z for hydrogen, hydroxyl, fluorine, chlorine, bromine, for each optionally by hydroxy, cyano, nitro, fluorine, chlorine, methoxy, ethoxy, acetyl, Propionyl, methoxycarbonyl, ethoxycarbonyl, methylthio, ethylthio, methylsulfinyl, ethylsulfinyl, methylsulfonyl or ethylsulfonyl substituted methyl, ethyl, n- or i-propyl, methoxy, ethoxy, n- or i-propoxy, acetyl, propionyl, methoxycarbonyl, ethoxycarbonyl, methylthio , Ethylthio, methylsulfinyl, ethylsulfinyl, methylsulfonyl or ethylsulfonyl, or represents in each case optionally substituted by fluorine, chlorine or bromine ethenyl, propenyl, butenyl, ethynyl, propynyl or butynyl,

however, the compounds (known from JP 62294669)

2-amino-4-methoxy-6- [1 - (3-chlorophenyl) ethylamino] - 1,3,5-triazine, 2-amino-4-methoxy-6- [l- (3-methyl- phenyl) -ethylamino] -l, 3,5-triazine, 2-amino-4-chloro-6- [l- (3-trifluoromethyl-phenyl) -ethylamino] -l, 3,5-triazine, 2-amino- 4-chloro-6- [l- (3-nitro-phenyl) ethylamino] -l, 3,5-triazine, 2-amino-4-chloro-6- [l- (3-chlorophenyl) ethyl - amino] - 1,3, 5-triazine and 2-amino-4-chloro-6- [l- (3-methylphenyl) ethylamino] -l, 3,5-triazine

excluded are.

The general or preferred radical definitions listed above apply both to the end products of the formula (I) and correspondingly to the starting or intermediate products required in each case for the preparation. These radical definitions can be combined with one another, that is to say also between the specified preferred ranges.

Examples of the compounds of formula (I) according to the invention are listed in the groups below. The general formulas stand for the R enantiomers, the S enantiomers and the racemates. Group 1

Z has, for example, the meanings given below:

Hydrogen, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, chlorofluoromethyl, chlorobromomethyl, chlorodifluoromethyl, fluorodichloromethyl, bromodifluoromethyl, trichloro- methyl, 1-fluoro-ethyl, 2-fluoro-ethyl, 1-chloro-ethyl, 2-chloro-ethyl, 1-chloro-1-fluoro-ethyl, 1-fluoropropyl, 2-fluoropropyl, 3- Fluoropropyl, 1-fluoro- 1-methyl-ethyl, 2-fluoro-1-methyl-ethyl, 1-chloro-1-methyl-ethyl, 1-fluoro- 1-methyl-propyl, 1-chloro-1- ethyl-propyl, 1-fluor-1-ethyl-propyl, 1-chloro-1-ethyl-propyl, l-fluoro-2-methyl-propyl, 1-chloro-2-methyl-propyl, 1-chloro-propyl, 2-chloropropyl, 3-chloropropyl, 1-chloro-1-methyl-ethyl, 2-chloro-1-methyl-ethyl, 1,1-difluoro-ethyl, 1,2-difluoro-ethyl,

1,1-dichloro-ethyl, 2,2,2-trifluoro-ethyl, 1,2,2,2-tetrafluoro-ethyl, perfluoroethyl, 1, 1-difluoropropyl, 1, 1-dichloropropyl, perfluoropropyl, 1-fluorobutyl, 1-chlorobutyl, perfluoro entyl, perfluorohexyl, 1-hydroxyethyl, acetyl, 1,1-bis-acetyl-methyl, 1-acetyl-1-methoxycarbonyl-methyl, 1-acetyl - 1-ethoxycarbonyl-methyl, methoxymethyl, 1,1-dimethoxy-methyl, 1-methoxyethyl, 2-methoxy-ethyl, 1,1-dimethoxy-ethyl, ethoxy-methyl, 1-ethoxyethyl, 2-ethoxy-ethyl, 2 -Methoxy- 1-methyl-ethyl, 2-methoxy-1-ethyl-ethyl, 2 -ethoxy-1-methyl-ethyl, 2-ethoxy-1-ethyl-ethyl, methylthiomethyl, ethylthiomethyl, 1-methylthio-ethyl, 2 -Methylthioethyl, 1-ethylthio-ethyl, 2-ethylthioethyl, methylsulfinylmethyl, ethylsulfinylmethyl, methylsulfonylmethyl, ethylsulfonylmethyl, methoxy, ethoxy, n- or i-propoxy, methylthio, ethylthio, n- or i-propylthio, methylsulfinyl, ethyl , Methylsulfonyl, ethylsulfonyl, fluoromethoxy, difluoromethoxy, trifluoromethoxy, fluoroethoxy, difluoroethoxy, trifluo r- ethoxy, difluoromethylthio, trifluoromethylthio, vinyl, 1-chloro-vinyl, 2-chloro-vinyl, 1-fluoro-vinyl, 2-fluoro-vinyl, 1-bromo-vinyl, 2-bromo-vinyl, 1,2- Dichlorovinyl, 1,2- Dibromo-vinyl, 1,2-difluoro-vinyl, 2,2-dichloro-vinyl, 2,2-difluoro-vinyl. 2,2-dibromo-vinyl, l-chloro-2-fluoro-vinyl, 2-bromo-2-chloro-vinyl, trichlorovinyl, allyl. 2-chloro-allyl, 3-chloro-allyl, 3,3-dichloro-allyl, 1-propenyl, isopropenyl, 1-chloro-2-propenyl, 1-fluoro-2-propenyl, l-bromo-2-propenyl, 1,2-dichloro-1-propenyl, 1,2-dibromo-1-propenyl, 1, 2-difluoro-1-propenyl, 1, 1-dichloro-2-propenyl, 1, 1 -dibromo-2-propenyl, l, l-difluoro-2-propenyl, l, l, 3,3,3-pentafluoro-2-propenyl _; 2-buten-1-yl, 2-buten-2-yl, 3-chloro-2-butenyl, 3-bromo-2-butenyl, 3,3,3-trifluoro-2-butenyl, ethynyl, 2-chloro ethynyl, 2-bromo-ethynyl, 1-propynyl, 2-propynyl, 3,3,3-trifluoro-l-propynyl.

Group 2

Z has, for example, the meanings given above in Group 1.

Group 3

Z has, for example, the meanings given above in Group 1.

Group 4

Z has, for example, the meanings given above in Group 1. Group 5

Z has, for example, the meanings given above in Group 1.

Group 6

Z has, for example, the meanings given above in Group 1.

Group 7

Z has, for example, the meanings given above in Group 1.

Group 8

Z has, for example, the meanings given above in Group 1. Group 9

Z has, for example, the meanings given above in Group 1.

Group 10

Z has, for example, the meanings given above in Group 1.

Group 11

Z has, for example, the meanings given above in Group 1.

Group 12

Z has, for example, the meanings given above in Group 1. Group 13

Z has, for example, the meanings given above in Group 1.

Group 14

Z has, for example, the meanings given above in Group 1.

Group 15

Z has, for example, the meanings given above in Group 1.

Group 16

Z has, for example, the meanings given above in Group 1. Group 17

Z has, for example, the meanings given above in Group 1.

Group 18

Z has, for example, the meanings given above in Group 1.

Group 19

Z has, for example, the meanings given above in Group 1.

Group 20

Z has, for example, the meanings given above in Group 1. Group 21

Z has, for example, the meanings given above in Group 1.

Group 22

Z has, for example, the meanings given above in Group 1.

Group 23

Z has, for example, the meanings given above in Group 1.

Group 24

Z has, for example, the meanings given above in Group 1. Group 25

Z has, for example, the meanings given above in Group 1.

Group 26

Z has, for example, the meanings given above in Group 1.

Group 27

Z has, for example, the meanings given above in Group 1.

Group 28

Z has, for example, the meanings given above in Group 1. Group 29

Z has, for example, the meanings given above in Group 1.

Group 30

Z has, for example, the meanings given above in Group 1.

Group 31

Z has, for example, the meanings given above in Group 1.

Group 32

Z has, for example, the meanings given above in Group 1. Group 33

Z has, for example, the meanings given above in Group 1.

Group 34

Z has, for example, the meanings given above in Group 1.

Group 35

Z has, for example, the meanings given above in Group 1.

Group 36

Z has, for example, the meanings given above in Group 1. Group 37

Z has, for example, the meanings given above in Group 1.

Group 38

Z has, for example, the meanings given above in Group 1.

Group 39

Z has, for example, the meanings given above in Group 1.

Group 40

Z has, for example, the meanings given above in Group 1. Group 41

Z has, for example, the meanings given above in Group 1.

Group 42

Z has, for example, the meanings given above in Group 1.

Group 43

Z has, for example, the meanings given above in Group 1.

Group 44

Z has, for example, the meanings given above in Group 1. Group 45

Z has, for example, the meanings given above in Group 1.

Group 46

Z has, for example, the meanings given above in Group 1.

Group 47

Z has, for example, the meanings given above in Group 1. Group 48

Z has, for example, the meanings given above in Group 1.

Group 49

CH ₃

0 N _* H

Z has, for example, the meanings given above in Group 1.

Group 50

Z has, for example, the meanings given above in Group 1. Group 51

Z has, for example, the meanings given above in Group 1.

Group 52

Z has, for example, the meanings given above in Group 1.

Group 53

Z has, for example, the meanings given above in Group 1. Group 54

Z has, for example, the meanings given above in Group 1.

Group 55

Z has, for example, the meanings given above in Group 1.

Group 56

Z has, for example, the meanings given above in Group 1. Group 57

Z has, for example, the meanings given above in Group 1.

Group 58

Z has, for example, the meanings given above in Group 1.

Group 59

Z has, for example, the meanings given above in Group 1. Group 60

Z has, for example, the meanings given above in Group 1.

Group 61

Z has, for example, the meanings given above in Group 1.

Group 62

Z has, for example, the meanings given above in Group 1.

Group 63

Z has, for example, the meanings given above in Group 1. Group 64

Z has, for example, the meanings given above in Group 1.

Group 65

Z has, for example, the meanings given above in Group 1.

Group 66

Z has, for example, the meanings given above in Group 1.

If, for example, l- [1- (4-chlorophenyl) ethyl] biguanide and methyl trifluoroacetate are used as starting materials, the course of the reaction in process (a) according to the invention can be outlined using the following formula:

If, for example, 2-chloro-4- [l- (3-fluorophenyl) propylamino] -6- (l-chloro-ethyl) - 1,3, 5-triazine and ammonia are used as starting materials, the course of the reaction can be as follows Process (b) according to the invention are outlined by the following formula scheme '

If, for example, 2-amino-4-methoxy-6-trifluoromethyl-l, 3,5-triazine and l- (4-ethylphenyl) propylamine are used as starting materials, the course of the reaction in process (c) according to the invention can be carried out by the following Formula scheme to be outlined '

If, for example, 2-amino-4- (l-fluoro-l-methyl-ethyl) -6- [l- (2-methylphenyl) ethylamino] -l, 3,5-triazine and acetyl chloride are used as starting materials, then the course of the reaction in process (d) according to the invention can be outlined using the following formula:

Formula (II) provides a general definition of the substituted biguanides to be used as starting materials in process (a) according to the invention for the preparation of compounds of the formula (I). In the formula (II), R ¹ , R ² , R ³ and X preferably or in particular have those meanings which have already been described above in connection with the description of the compounds of the formula (I) according to the invention, preferably or as particularly preferred for R ¹ , R ² , R ³ and X were specified.

As examples of the substituted biguanides of the formula (II) - each of which

Racemates, the R-enantiomers and the S-enantiomers are preferred - may be mentioned:

1 - (1 - (2-fluorophenyl) ethyl) -, 1 - (1 - (3-fluorophenyl) ethyl) -, 1 - (1 - (4-fluorophenyl) ethyl) - , l- (l- (2-chlorophenyl) ethyl) -, l- (l- (3-chlorophenyl) ethyl) -, l- (l- (4-chlorophenyl) ethyl) -, l- (l- (2-Bromo-phenyl) -ethyl) -, l- (l- (3-bromo-phenyl) -ethyl) -, l- (l- (4-bromo-phenyl) -ethyl ) -, 1 - (1 - (2-nitro-phenyl) -ethyl) -, 1 - (1 - (3-nitro-phenyl) -ethyl) -, 1 - (1 - (4-nitro-phenyl) - ethyl) -, 1 - (1 - (2-methyl-phenyl) -ethyl) -, 1 - (1 - (3-methyl-phenyl) -ethyl) -, l- (l- (4-methyl- phenyl) -ethyl) -, l- (l- (2-trifluoromethyl-phenyl) -ethyl) -, 1- (l- (3-trifluoromethyl-phenyl) -ethyl) -, l- (l- (4-trifluoromethyl -phenyl) -ethyl) -, l- (l- (2-

Methoxy-phenyl) -ethyl) -, 1 - (1 - (3-methoxy-phenyl) -ethyl) -, 1 - (1 - (4-methoxy-phenyl) -ethyl) -, 1 - (1 - (2nd -Difluoromethoxy-phenyl) -ethyl) -, 1 - (1 - (2-difluoromethoxy-phenyl) -ethyl) -, 1 - (1 - (2-difluoromethoxy-phenyl) -ethyl) -, 1 - (1 - ( 2-trifluoromethoxy-phenyl) - ethyl) -, 1 - (1 - (3-trifluoromethoxy-phenyl) -ethyl) -, 1 - (1 - (4-trifluoromethoxy-phenyl) - ethyl) -, l- (l- (2-Methoxycarbonyl-phenyl) -ethyl) -, l- (l- (2-Ethoxycarbonyl-phenyl) -ethyl) -, 1 - (1 - (4-methoxycarbonyl-phenyl) -ethyl) -, 1 - (1 - (4-Ethoxycarbonyl-phenyl) - ethyl) -, l- (l- (2-Methylthio-phenyl) -ethyl) -, l- (l- (4-Methylthio-phenyl) -ethyl) -, 1- ( 1- (2-Methylsulfinyl-phenyl) -ethyl) -, 1 - (1 - (4-Methylsulfinyl-phenyl) -ethyl) -, 1 - (1 - (2- Methylsulfonylphenyl) ethyl) and 1 - (1 - (4-methylsulfonylphenyl) ethyl) biguanide.

Suitable acid adducts of compounds of formula (II) are their addition products with protonic acids, such as e.g. with hydrogen chloride (hydrogen chloride),

Hydrogen bromide (hydrogen bromide), sulfuric acid, methanesulfonic acid, benzenesulfonic acid and p-toluenesulfonic acid.

With the exception of 1- [1- (4-trifluoromethyl-phenyl) -ethyl] -biguanide (see US Pat. No. 3,860,648), the starting materials of the general formula (II) are not yet known from the literature; With the exception of 1- [1- (4-trifluoromethyl-phenyl) -ethyl] -biguanide, they are also the subject of the present application as new substances.

The substituted biguanides of the general formula (II) are obtained if substituted phenylalkylamines of the general formula (VII)

in which

R ³ and X have the meaning given above,

and / or acid adducts of compounds of the general formula (VII), such as e.g. the hydrochloride -

with cyanoguanidines of the general formula (IX)

in which

R ¹ and R ^{2 have} the meaning given above,

optionally in the presence of a reaction auxiliary, e.g. Hydrogen chloride, and optionally in the presence of a diluent, e.g. n-Decane or 1,2-dichlorobenzene, at temperatures between 100 ° C and 200 ° C (see US 3860648, manufacturing examples).

The substituted phenylalkylamines of the formula (VII) required as precursors are known and / or can be prepared by processes known per se (cf. DE 2442845; DE 4038356; EP 490175; US 5300437; J. Am. Chem. Soc. 105 ( 1983), 1578-1584; Tetrahedron: Asymmetry 4 (1993), 2095-2100; Bio-technol. Tech. 10 (1996), 335-338 - cited in Chem. Abstracts 125: 58008).

The cyanoguanidines of the formula (IX) are known synthetic chemicals.

The process (a) according to the invention for the preparation of compounds of

Formula (I) further alkoxycarbonyl compounds to be used as starting materials are generally defined by the formula (III). In formula (III), Z preferably or in particular has the meaning which has already been mentioned above in connection with the description of the compounds of the formula (I) according to the invention preferably or as particularly preferred for Z; R 'is preferably

Alkyl with 1 to 4 carbon atoms, especially for methyl or ethyl.

The starting materials of the formula (III) are known synthetic chemicals. Formula (IV) provides a general definition of the substituted aminotriazines to be used as starting materials in process (b) according to the invention for the preparation of compounds of the formula (I). In the formula (IV), R ³ , X and Z preferably or in particular have those meanings which, in connection with the description of the compounds of the formula (I) according to the invention, are preferred or particularly preferred for R ³ , X and Z were specified; X ¹ preferably represents fluorine, chlorine, bromine or -CC ₄ alkoxy, in particular fluorine, chlorine, methoxy or ethoxy.

The starting materials of the general formula (IV) are known and / or can be prepared by processes known per se (cf. EP 300313).

Formula (V) provides a general definition of the nitrogen compounds to be used further as starting materials in process (b) according to the invention for the preparation of compounds of the formula (I). In the formula (V), R ¹ and R ² preferably or in particular have those meanings which have already been mentioned above in connection with the description of the compounds of the formula (I) according to the invention preferably or as particularly preferred for R ¹ and R ² .

The starting materials of the general formula (V) are known synthetic chemicals.

Formula (VI) provides a general definition of the substituted aminotriazines to be used as starting materials in process (c) according to the invention for the preparation of compounds of the formula (I). In the formula (VI), R ¹ , R ² and Z preferably or in particular have those meanings which have already been described above in connection with the description of the compounds of the formula (I) as preferred or as particularly preferred for R ¹ , R ² and Z were specified; X ² preferably represents fluorine, chlorine, bromine or C _r C ₄ alkoxy, in particular fluorine, chlorine, methoxy or ethoxy.

The starting materials of the general formula (VI) are known and / or can be prepared by processes known per se (cf. WO 95/11237). Formula (VII) provides a general definition of the amino compounds to be used further as starting materials in process (c) according to the invention. In formula (VII), R ³ and X preferably or in particular have those meanings which have already been mentioned above in connection with the description of the compounds of the formula (I) according to the invention preferably or as particularly preferred for R ³ and X.

The starting materials of the formula (VTI) are known and / or can be prepared by processes known per se (cf. DE 2442845; DE 4038356; EP 490175; US 5300437; J. Am. Chem. Soc. 105 (1983), 1578- 1584; Tetrahedron: Asymmetry 4

(1993), 2095-2100; Biotechnol. Tech. 1996, 10: 335-338 - cit. in Chem. Abstracts 125: 58008).

Formula (Ia) provides a general definition of the 2,4-diamino-1,3,5-triazines to be used as starting materials in process (d) according to the invention for the preparation of compounds of the formula (I). In the formula (Ia), R ¹ , R ³ , X and Z preferably or in particular have those meanings which, in connection with the description of the compounds of the formula (I) according to the invention, are preferred or particularly preferred for R ¹ , R ³ , X and Z were specified.

The starting materials of the general formula (Ia) are also the subject of the present application as new compounds; they can be prepared according to processes (a), (b) or (c) according to the invention.

The process (d) according to the invention for the preparation of compounds of

Formula (I), alkylating, acylating or sulfonylating agents to be used as starting materials are generally defined by formula (VIII). In the formula (VHI), R ² preferably or in particular has the meaning which has already been mentioned above in connection with the description of the compounds of the formula (I) according to the invention preferably or as particularly preferred for R ² ; Y preferably represents fluorine, chlorine, bromine, iodine, methoxy, ethoxy, methoxysulfonyloxy, ethoxysulfonyloxy, acetyloxy or propionyloxy. The starting materials of the general formula (VIII) are known synthetic chemicals.

The processes according to the invention for the preparation of the compounds of the formula (I) are optionally carried out using a reaction auxiliary.

The usual inorganic or organic bases or acid acceptors are suitable as reaction aids for processes (a), (b), (c) and (d). These preferably include alkali metal or alkaline earth metal acetates, amides, carbonates, hydrogen carbonates, hydrides, hydroxides or alkanolates, such as, for example, sodium, potassium or calcium acetate, lithium, sodium, potassium or Calcium amide, sodium, potassium or calcium carbonate, sodium, potassium or calcium hydrogen carbonate, lithium, sodium, potassium or calcium hydride, lithium, sodium, potassium or calcium hydroxide, Sodium or potassium methoxide, ethanolate, n or i propanolate, n, i, s or t butanolate; also basic organic nitrogen compounds, such as trimethylamine, triethylamine, tripropylamine, tributylamine, ethyl diisopropylamine, N, N-dimethylcyclohexylamine, dicyclohexylamine, ethyl dicyclohexylamine, N, N-dimethylaniline, N, N- Dimethylbenzylamine, pyridine, 2-methyl, 3-methyl, 4-methyl, 2,4-dimethyl, 2,6-dimethyl, 3,4-dimethyl and 3,5- Dimethyl-pyridine, 5-ethyl-2-methyl-pyridine, 4-dimethylamino-pyridine, N-methyl-piperidine, 1,4-diazabicyclo [2,2,2] octane (DABCO), 1,5- Diazabicyclo [4,3,0] non-5-ene (DBN), or 1,8-diazabicyclo [5,4,0] -undec-7-ene (DBU).

Suitable diluents for carrying out processes (a), (b), (c) and (d) are, if appropriate, inert organic solvents.

These include in particular aliphatic, alicyclic or aromatic, if appropriate halogenated hydrocarbons, such as, for example, gasoline, benzene, toluene, xylene, chlorobenzene, dichlorobenzene, petroleum ether, hexane, cyclohexane, dichloromethane, chloroform, carbon tetrachloride; Ethers, such as diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran or ethylene glycol dimethyl or diethyl ether; Ketones like

Methyl isopropyl ketone or methyl isobutyl ketone; Nitriles, such as acetonitrile, propionitrile or butyronitrile; Amides such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methylformanilide, N-methylpyrrolidone or hexamethylphosphoric triamide; Esters such as methyl acetate, ethyl ester, n- or i-propyl ester, n-, i- or s-butyl ester; Sulfoxides such as dimethyl sulfoxide; Alcohols, such as methanol, ethanol, n- or i-propanol, n-, i-, s- or t-butanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, their mixtures with water or pure water .

The reaction temperatures can be varied within a substantial range when carrying out processes (a), (b), (c) and (d). In general, temperatures between 0 ° C and 300 ° C, preferably between 10 ° C and 250 ° C.

Processes (a), (b), (c) and (d) according to the invention are generally carried out under atmospheric pressure. However, it is also possible to carry out the processes according to the invention under elevated or reduced pressure - generally between 0.1 bar and 10 bar.

To carry out the processes according to the invention, the starting materials are generally used in approximately equimolar amounts. However, it is also possible to use one of the components in a larger excess. The reaction is generally carried out in a suitable diluent in the presence of a reaction auxiliary and the reaction mixture is generally stirred at the required temperature for several hours. Working up is carried out according to customary methods (cf. the production examples).

The active compounds according to the invention can be used as defoliants, desiccants, haulm killers and in particular as weed killers. Weeds in the broadest sense are all plants that grow in places where they are undesirable. Whether the substances according to the invention act as total or selective herbicides depends essentially on the amount used.

The active compounds according to the invention can be used, for example, in the following plants: Dicotyledon weeds of the genera: Sinapis, Lepidium, Galium, Stellaria, Matricaria, Anthemis, Galinsoga, Chenopodium, Urtica, Senecio, Amaranthus, Portulaca, Xanthium, Convolvulus, Ipomoea, Polygonum, Sesbania, Ambrosia, Cirsium, Carduippum, Sonuanum , Rotala, Lindernia, Lamium, Veronica, Abutilon, Emex, Datura, Viola, Galeopsis, Papaver, Centaurea, Trifolium,

Ranunculus, Taraxacum.

Dicotyledon cultures of the genera: Gossypium, Glycine, Beta, Daucus, Phaseolus, Pisum, Solanum, Linum, Ipomoea, Vicia, Nicotiana, Lycopersicon, Arachis, Brassica, Lactuca, Cucumis, Cucurbita.

Monocotyledon weeds of the genera: Echinochloa, Setaria, Panicum, Digitaria, Phleum, Poa, Festuca, Eleusine, Brachiaria, Lolium, Bromus, Avena, Cyperus, Sorghum, Agropyron, Cynodon, Monochoria, Fimbristylis, Sagittaria, Iochasumirumum, Scalumumum, Scalumumum , Sphenoclea, Dactyloctenium, Agrostis, Alopecurus,

Apera, phalaris.

Monocot cultures of the genera: Oryza, Zea, Triticum, Hordeum, Avena, Seeale, Sorghum, Panicum, Saccharum, Pineapple, Asparagus, Allium.

However, the use of the active compounds according to the invention is by no means restricted to these genera, but extends in the same way to other plants.

Depending on the concentration, the compounds are suitable for total weed control, for example on industrial and rail tracks and on paths and squares with and without tree cover. Likewise, the compounds for weed control in permanent crops, for example forest, ornamental trees, fruit, wine, citrus, nut, banana, coffee, tea, rubber, oil palm, cocoa, berry fruit and hop- plants, on ornamental and sports turf and pastures and for selective weed control in annual crops. The compounds of the formula (I) according to the invention are particularly suitable for the selective control of monocotyledon and dicotyledon weeds in monocotyledon and dicotyledon crops both in the pre-emergence and in the post-emergence process.

The active ingredients can be converted into the usual formulations, such as

Solutions, emulsions, wettable powders, suspensions, powders, dusts, pastes, soluble powders, granules, suspension emulsion concentrates, active ingredient-impregnated natural and synthetic substances as well as very fine encapsulations in polymeric substances.

These formulations are prepared in a known manner, e.g. B. by mixing the active ingredients with extenders, ie liquid solvents and / or solid carriers, optionally using surface-active agents, ie emulsifiers and / or dispersants and / or foam-generating agents.

If water is used as an extender, e.g. also organic

Solvents are used as auxiliary solvents. The following are essentially suitable as liquid solvents: aromatics, such as xylene, toluene, or alkylnaphthalenes, chlorinated aromatics and chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chlorethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, e.g. Petroleum fractions, mineral and vegetable

Oils, alcohols such as butanol or glycol and their ethers and esters, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents such as dimethylformamide and dimethyl sulfoxide, and water.

Possible solid carriers are: e.g. Ammonium salts and natural

Rock powders such as kaolins, alumina, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth and synthetic rock powders such as highly disperse silica, aluminum oxide and silicates are suitable as solid carriers for granules: eg broken and fractionated natural rocks such as calcite, Marble, pumice, sepiolite, dolomite and synthetic granules from inorganic and organic flours and granules from organic material such as sawdust, coconut shells, corn cobs and tobacco stalks; suitable emulsifiers and / or foam-generating agents are: for example nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for example alkyl aryl polyglycol ethers, alkyl sulfonates, alkyl sulfates, aryl sulfonates and protein hydrolyzates; Possible dispersing agents are, for example, lignin sulfite waste liquor and methyl cellulose.

Adhesives such as carboxymethyl cellulose, natural and synthetic polymers in the form of powders, granules or latices, such as gum arabic, polyvinyl alcohol, polyvinyl acetate, and natural phospholipids such as cephalins and lecithins and synthetic phospholipids can be used in the formulations. Other additives can be mineral and vegetable oils.

Dyes such as inorganic pigments, e.g. Iron oxide, titanium oxide, ferrocyan blue and organic dyes such as alizarin, azo and metal phthalocyanine dyes and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc can be used.

The formulations generally contain between 0.1 and 95 percent by weight of active compound, preferably between 0.5 and 90%.

The active compounds according to the invention, as such or in their formulations, can also be used for combating weeds, in a mixture with known herbicides, finished formulations or tank mixes being possible.

Known herbicides are suitable for the mixtures, for example

Acetochlor, Acifluorfen (-sodium), Aclonifen, Alachlor, Alloxydim (-sodium), Ametryne, Amidochlor, Amidosulfüron, Asulam, Atrazine, Azimsulfüron, Benazolin, Benfuresate, Bensulfuron (-methyl), Bentazon, Benzofenap, Benzoylprop Bialaphos, Bifenox, Bromobutide, Bromofenoxim, Bromoxynil, Butachlor, Butylate, Cafenstrole, Carbetamides, Chlomethoxyfen, Chloramben, Chloridazon, Chlorimuron (- ethyl), Chlornitrofen, Chlorsulfuron, Chlortoluron, Cinmethylin, Clomorphophenon, Clinosulfuronparonodin, Clinosulfuronparonodin, Cinosulfuronparonodin, Cinosulfuronparonodin, Cinosulfuronparonodin, Cinosulfuronparonodin, Cinosulfuronparonon Clomazone, clopyralid, clopyrasulfüron, chlorosulam (methyl), cumyluron, cyanazines, cycloates, cyclosulfamuron, cycloxydim, Cyhalofop (-butyl), 2,4-D, 2,4-DB, 2,4-DP, Desmedipham, Diallate, Dicamba, Diclofop (-methyl), Difenzoquat, Diflufenican, Dimefuron, Dimepiperate, Dimethachlor, Di- methametryn, dimethenamid, dinitramine, diphenamide, diquat, dithiopyr, diuron, dymron, EPTC, esprocarb, ethalfluralin, ethametsulfuron (-methyl), ethof mesate, ethoxyfen, etobenzanid, fenoxaprop (-ethyl), flamprop (-isopropyl), isopropyl-L), flamprop (-methyl), flazasulfuron, fluazifop (-butyl), flumetsulam, flumiclorac (-pentyl), flumioxazin, flumipropyn, fluometuron, fluorochloridone, fluoroglycofen (-ethyl), flupoxam, flupropacil , Flurenol, Fluridone, Fluroxypyr, Flurprimidol, Flurtamone, Fomesafen, Glufosinate (-ammonium), Glyphosate (-isopropyl-ammonium), Halosafen, Haloxyfop (-ethoxyethyl), Hexazinone, Imazamethabenz (- methyl), Imazamethazyr, Imazamoxaza, Imazamoxaza , Imazethapyr, Imazosulfüron, Ioxynil, Isopropalin, Isoproturon, Isoxaben, Isoxaflutole, Isoxapyrifop, Lactofen, Lenacil, Linuron, MCPA, MC PP, Mefenacet, Metamitron, Metazachlor, Methabenzthiazuron, Metobenzuron, Metobromuron, Metolachlor, Metosulam, Metoxuron, Metribuzin, Metsulfüron (-methyl), Molinate, Monolinuron, Naproanilide,

Napropamide, Neburon, Nicosulf ron, Norflurazon Orbencarb, Oryzalin, Oxadiazon, Oxyfluorfen, Paraquat, Pendimethalin, Phenmedipham, Piperophos, Pretilachlor, Primisulfüron (-methyl), Prometryn, Propachlor, Propanil, Propaquizafarbide, Prosulfuron Pyrazosulfüron (-ethyl), Pyrazoxyfen, Pyributicarb, Pyridate, Pyrithiobac (-sodium), Quinchlorac, Quinmerac, Quizalofop (- ethyl), Quizalofop (-p-tefüryl), Rimsulfüron, Sethoxydim, Simazine, Simetrynent, Sulrazone, Trione Sulfione Sulfometuron (-methyl), sulfosate, tebutam, tebuthiuron, terbuthylazine, terbutryn, thenylchlor, thiafluamides, thiazopyr, thidiazimin, thifene-sulfuron (-methyl), thiobencarb, tiocarbazil, tralkoxydim, triallate, triasuronuron (triasulfonon), Triclopyr, Tridiphane, Trifluralin and Triflusulfüron.

A mixture with other known active compounds, such as fungicides, insecticides, acaricides, nematicides, bird repellants, plant nutrients and agents which improve soil structure, is also possible.

The active compounds can be used as such, in the form of their formulations or in the use forms prepared therefrom by further dilution, such as ready-to-use solutions, suspensions, emulsions, powders, pastes and granules become. They are used in the customary manner, for example by watering, spraying, spraying or scattering.

The active compounds according to the invention can be applied both before and after emergence of the plants. They can also be worked into the soil before sowing.

The amount of active ingredient used can vary over a wide range. It essentially depends on the type of effect desired. In general, the application rates are between 1 g and 10 kg of active ingredient per hectare of soil, preferably between 5 g and 5 kg per ha.

The preparation and use of the active compounds according to the invention can be seen from the examples below.

Preparation Examples:

example 1

(Method (a))

A solution of 4.6 g (85 mmol) of sodium methylate in 15 ml of methanol is added dropwise with stirring at 20 ° C. to 35 ° C. to a mixture of 20.4 g (80 mmol) of 1- [1-

(4-Methylthio-phenyl) ethyl] biguanide (racemic), 13 g (80 mmol) of trifluoroacetic acid and 100 ml of methanol were added and the reaction mixture was then stirred for a further 15 hours at room temperature (approx. 20 ° C). Then it is shaken with methylene chloride and water, the organic phase is separated off, washed with 1% sodium hydroxide solution, dried with sodium sulfate and filtered. The filtrate is in the

Water jet vacuum carefully concentrated, the residue crystallized by digesting with ligroin and the product isolated by suction.

12.4 g (47% of theory) of 2-amino-4-trifluoromethyl-6- [l- (4-methylthiophenyl) ethylamino] -l, 3,5-triazine (racemate) of melting point 111 ° are obtained C.

Example 2

(Method (d))

A mixture of 16.5 g (50 mmol) of 2-amino-4-trifluoromethyl-6- [l- (4-methylthiophenyl) ethylamino] -l, 3,5-triazine (racemic) and 60 ml of acetic anhydride Stirred at 130 ° C for 3 hours, mixed with 200 ml of water after cooling to room temperature (about 20 ° C) and stirred for a further hour at room temperature. Then the crystalline product is isolated by suction.

13.3 g (72% of theory) of 2-acetylamino-4-trifluoromethyl-6- [l- (4-methylthio-phenyl) -ethylamino] -l, 3,5-triazine (racemate) of melting point are obtained 132 ° C.

Example 3

(Follow-up implementation)

5 g of 3-chloroperbenzoic acid (approx. 60%) are stirred within 30 minutes to give a mixture of 6.6 g (20 mmol) of 2-amino-4-trifluoromethyl-6- [l- (4- methylthio-phenyl) -ethylamino] -l, 3,5-triazine (racemic) and 80 ml of dichloromethane and the reaction mixture is then stirred for another hour at room temperature (approx. 20 ° C.). It is then washed with water and then with a 5% strength aqueous ammonia solution, dried with sodium sulfate and filtered. The solvent is carefully distilled off from the filtrate in a water jet vacuum.

This gives 4.4 g (64% of theory) of 2-amino-4-trifluoromethyl-6- [1- (4-methylsulfonylphenyl) ethylamino] - 1,3,5-triazine (racemate) as a solid product of Melting point 220 ° C (decomposition).

Analogously to Preparation Examples 1 to 3 and in accordance with the general description of the preparation processes according to the invention, it is also possible, for example, to prepare the compounds of the formula (I) listed in Table 1 below.

Table 1: Examples of the compounds of the formula (I)

Table I (continued)

Table 1 (continued)

"Z." = decomposition

The compound listed in Table 1 as Example 99 can also be prepared, for example, as follows:

(Method (c))

A mixture of 2.0 g (12 mmol) of 1- (4-chlorophenyl) ethylamine (racemic) and 1.0 g (5.2 mmol) of 2-amino-4-methoxy-6-trifluoromethyl-1, 3,5-triazine is heated to 170 ° C. under argon for 3 hours. After cooling, it is taken up in methylene chloride and acidified with 1N hydrochloric acid. The organic phase is separated off, washed with water, dried with sodium sulfate and filtered. The filtrate is concentrated in a water jet vacuum and the residue is purified by column chromatography (silica gel, ethyl acetate). 1.29 g (79% of theory) of 2-amino-4- (1- (4-chlorophenyl) ethylamino) -6-trifluoromethyl-1,3,5-triazine (racemate) of melting point 99 ° are obtained C.

Starting materials of formula (II)

Example (II- 1)

A mixture of 17 g (84 mmol) of 1- (4-methylthiophenyl) ethylamine hydrochloride

(Racemic), 8 g (95 mmol) of dicyandiamide (cyanoguanidine) and 100 ml of 1,2-dichlorobenzene are stirred for 4 hours at 160 ° C. After cooling, the product obtained in crystalline form is isolated by suction

23 g (95% of theory) of l- [l- (4-methylthiophenyl) ethyl] biguanide are obtained.

Hydrochloride (racemate) with a melting point of 220 ° C (decomposition)

The reaction can also be carried out at about the same temperature (140 ° C to 160 ° C) without a solvent - i.e. in the melt

Analogously to Example (II-1), the compounds of the formula (II) or their hydrochlorides listed in Table 2 below can also be prepared, for example

Table 2: Examples of the compounds of the formula (II)

- in all cases it is the corresponding hydrochloride!

Application examples Example A

Pre-emergence test solvent 5 weight point acetone

Emulsifier 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amount of solvent, the stated amount of emulsifier is added and the concentrate is diluted with water to the desired level

concentration

Seeds of the test plants are sown in normal soil. After about 24 hours, the soil is watered with the active ingredient preparation. The amount of water per unit area is expediently kept constant. The active ingredient concentration in the preparation is irrelevant, the decisive factor is only the application rate of the active ingredient per unit area

After three weeks, the degree of damage to the plants is bombed in% damage compared to the development of the untreated control

Mean it

0% - no effect (like untreated control) 100% = total destruction

In this test, for example, the compounds according to Preparation Example 13, 14, 16, 22, 142, 149, 155, 156, 157, 159 and 160, with good tolerance to crop plants such as, for example, maize, wheat and cotton, show a strong action against weeds (see table A)

"Ai" = active ingredient Example B

Post emergence test solvent 5 parts by weight of acetone emulsifier 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amount of solvent, the stated amount of emulsifier is added and the concentrate is diluted with water to the desired concentration

Test plants which have a height of 5-15 cm are sprayed with the active compound preparation in such a way that the desired amounts of active compound are applied per unit area. The concentration of the spray mixture is chosen so that the desired amounts of active compound are applied in 1000 l of water / ha

After three weeks, the degree of damage to the plants is rated in% damage compared to the development of the untreated control

Mean it

0% = no effect (like untreated control) 100% = total destruction

In this test, for example, the compounds according to Preparation Example 4, 5, 8, 13, 14, 15, 16, 21, 22, 79, 82, 84, 85, 86, 87, 90, 91, 93, 94, 96, 97 show , 98, 103,

104, 108, 112, 121, 126, 138, 145, 146, 153, 155, 157, 159, 166, 167, 168, 170, 171, 173, 175, 177, 178, 190 and 191 with partially good contractual relationships Cultivated plants, such as wheat and corn, have a strong action against weeds (see Table B) Table A: Pre-emergence test / greenhouse

Active ingredient according to effort- corn alope- digi- echino- abu- Datura MatriHerfertigungb sp. -No. quantity (g ai./ha) curus taria chloa tilon caria

CD

(14) 500 100 100 100 100 100 100

Table A: (continued)

Active ingredient according to effort - maize Abutilon Amaran- Sinapis Herstellungsspsp. -No. quantity (g ai./ha) thus

(13) 1000 100 100 100 o

(16) 1000 80 90 100

Table A: (continued)

Active ingredient according to expenditure - corn Alope- Setaria Abutilon Amaran- Galium Sinapis Herstel lungsbsp. -No. quantity (g ai./ha) curus thus

(22) 1000 20 100 100 100 100 100 100

Table A: (continued)

Active ingredient according to expenditure- wheat tree- digi- echino- amaran- poly- vero manufacturing ex. -No. amount (g ai./ha) wool taria chloa thus gonum nica

(142) 500 0 80 95 100 100 100

Table A: (continued)

Active ingredient according to expenditure- wheat tree- digi- echino- poly- sola- vero manufacturing ex. -No. tight (g ai./ha) wool taria chloa gonum num nica

>

(149) 500 95 100 100 100 100

Table A: (continued)

Active ingredient according to expenditure- wheat tree- digi- echino- amaran- sola- vero-production sp. -No. amount (g ai./ha) wool taria chloa thus num nica

(159) 1000 100 95 100 100 100

Table A: (continued)

Active ingredient according to expenditure- Wheat tree- Echino- Setaria poly- Sola- Vero- manufacturing ex. -No. amount (g ai./ha) wool chloa gonum num nica

Uz

(157) 500 100 95 100 100 100

Table A: (continued)

Active ingredient according to effort- Wei- Digi- Echino- Se- Amaran- Poly- Sola- Vero- manufacturing example -No. quantity (g ai./ha) zen taria chloa taria thus gonum num nica

(155) 1000 0 100 100 100 100 100 100 100

Table A: (continued)

(156) 1000 0 100 100 100 100 100 100 100

Table A: (continued)

(160) 1000 0 100 100 95 100 300 100 100

Table B: Post emergence test / greenhouse

Active ingredient according to expenditure- Wheat Maize Digitaria Setaria Cheno- Datura Poly- Viola Manufacturing Ex. -No. quantity (g ai./ha) podium gonum

(13) 125 10 80 90 100 100 100 100 vo

(14) 125 20 80 100 100 100 100

Table B: (continued)

Active ingredient according to effort- corn Alope- Setaria Ama- manufacturing example -No. quantity (g ai./ha) curus ranthus

(4) 1000 20 80 90 100 00 o

Table B: (continued)

Active ingredient according to effort - Alo-Avena Setaria Abutilon Ama- Sinapis manufacturing example -No. quantity (g ai./ha) pecurus fatua ranthus

(5) 1000 100 100 100 100 100 100

(8) 1000 70 80 100 100 100 100

Table B: (continued)

(15) 1000 100 100 100 100 100 100

(16) 1000 90 95 100 100 100 100

Table B: (continued)

Active ingredient according to expenditure - Avena Setaria Abutilon Ama- Galium Sinapis Xanthium Manufacturing Ex. -No. quantity (g ai./ha) fatua ranthus

(23) 1000 70 100 100 100 100 100 100

Table B: (continued)

Active ingredient according to effort- Wei- Setaria Ama- Cheno- Poly- Viola manufacturing ex. -No. quantity (g ai./ha) zen ranthus podium gonum

00

(108) 1000 90 100 100 80 100

(126) 500 80 100 100 100 100

Table B: (continued)

(138) 250 10 100 100 100 100 100

(91) 250 100 100 100 100 100

Table B: (continued)

(93) 250 10 95 100 100 100 100

(98) 250 80 100 100 100 100

Table B: (continued)

(94) 250 90 100 100 100 100 00

(96) 250 80 100 100 100 100

Table B: (continued)

(97) 250 10 80 100 100 100 100 00 00

(146) 250 10 80 100 100 100 95

Table B: (continued)

(153) 500 95 100 100 100 100 00

(155) 250 10 90 100 100 95 95

Table B: (continued)

vO o

(157) 250 10 80 100 95 95 95

(159) 500 10 90 100 100 100 100

Table B: (continued)

(166) 500 100 100 100 100 100 O

(167) 250 10 90 100 100 100 100

Table B: (continued)

(168) 500 10 100 100 100 100 100% of N3

(170) 250 10 100 100 100 100

Table B: (continued)

(171) 250 10 90 100 100 100 100)

(173) 500 80 100 100 100 100

Table B: (continued)

vO

500 10 ^

80 100 100 100 4

(175) 100

H

(177) 500 10 100 100 100 100 100

Table B: (continued)

Active ingredient according to effort- Wei- Setaria Ama- Cheno- Poly- Viola

Manufacturing example -No. quantity (g ai./ha) zen ranthus podium gonum

VO Ui

(178) 500 10 70 100 100 100 100

(190) 250 10-100 100 100 95

Table B: (continued)

Active ingredient according to effort - Wei- Setaria Ama- Cheno- Poly- Viola Manufacturing Ex. -No. quantity (g ai./ha) zen ranthus podium gonum

(85) 250 95 100 100 100 100

(79) 500 100 100 100 100 100

Table B: (continued)

(86) 1000 10 100 100 100 100% -4

(191) 500 10 95 100 100 100 100

Table B: (continued)

(82) 500 10 95 100 100 100 100

Table B (continued)

Active ingredient according to expenditure- Wheat Setaria Amaran- Cheno- Stellaria Viola Manufacturing Ex. -No. quantity (g ai./ha) thus podium

(87) 250 10 100 100 100 100 100% before

Table B: (continued)

Active ingredient according to effort- Corn Setaria Ama- Sinapis manufacturing example -No. quantity (g ai./ha) ranthus

© o

(103) 1000 100 100 100

Table B: (continued)

Active ingredient according to expenditure- Corn Setaria Abutilon Ama- Xanthium ex. -No. quantity (g ai./ha) ranthus

(90) 1000 10 100 100 100 90

Table B: (continued)

Active ingredient according to expenditure- Setaria Amaran- Sinapis manufacturing example -No. quantity (g ai./ha) thus

O

(104) 1000 100 100 100

(121) 1000 100 100 100

Table B: (continued)

Active ingredient according to expenditure - Avena Setaria Amaran-Galium -No. quantity (g ai./ha) fatua thus

O

(112) 500 90 100 100

(145) 1000 70 100 100 70

Table B: (continued)

Active ingredient according to effort - Alope- Setaria Abutilon Amaran- Galium Xanthium -No. quantity (g ai./ha) curus thus

(84) 1000 100 100 100 100 100 100

Claims

claims

1. Substituted 2,4-diamino-l, 3,5-triazines of the general formula (I),

in which

R ^{1 represents} hydrogen or alkyl having 1 to 6 carbon atoms which is optionally substituted by hydroxy, cyano, halogen or C] -C4-alkoxy,

R ² for hydrogen, for formyl, for alkyl, alkylcarbonyl, alkoxycarbonyl or alkylsulfonyl, each optionally substituted by cyano, halogen or C1-C4alkoxy, each having 1 to 6 carbon atoms in the alkyl groups, or for each optionally by cyano, halogen, Cι- C4-alkyl, halogen -CC-C4-alkyl, C \ -C4-alkoxy, halogen-Cj-C4-alkoxy or Cj-C4-alkoxy-carbonyl substituted phenylcarbonyl, naphthylcarbonyl, phenylsulfonyl or naphthylsulfonyl,

R ^{3 represents} alkyl with 1 to 6 carbon atoms which is optionally substituted by cyano, halogen or C 1 -C 4 -alkoxy or cycloalkyl with 3 to 6 carbon atoms which is optionally substituted by cyano, halogen or C 1 -C 4 -alkyl,

X represents a substituent from the following group: Hydroxy, cyano, nitro, halogen, each optionally substituted by hydroxy, cyano or halogen-substituted alkyl or alkoxy each having 1 to 6 carbon atoms, each optionally substituted by halogen alkylcarbonyl, alkoxycarbonyl, alkylthio, alkylsulfinyl or alkylsulfonyl each having 1 to 6 carbon atoms in the alkyl groups each substiuiertes optionally substituted by hydroxyl, cyano, nitro, halogen, Cj ^ alkyl, _Cj-C4 haloalkyl, Cι-C4-alkoxy, or C \ -C4 haloalkoxy phenyl or phenoxy, and

Z for hydrogen, hydroxy, halogen, each optionally by

Hydroxy, cyano, nitro, halogen, C1 -C4 alkoxy, C1-4 alkylcarbonyl, C1 -C4 alkoxycarbonyl, C1 -C4 alkylthio, C1 -C4 alkyl sulfinyl or C1 -C4 - Alkylsulfonyl substituted alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylthio, alkylsulfinyl or alkylsulfonyl each having 1 to 6 carbon atoms in the alkyl groups, for each optionally substituted by halogen alkenyl or alkynyl each having 2 to 6 carbon atoms, or for optionally by cyano, halogen or CJ-C4-alkyl substituted cycloalkyl having 3 to 6 carbon atoms,

however, the connections

2-amino-4-methoxy-6- [l- (3-chlorophenyl) ethylamino] -l, 3,5-triazine, 2-amino-4-methoxy-6- [1 - (3 - methyl-phenyl) -ethylamino] - 1, 3, 5-triazine, 2-amino-4-chloro-6- [l- (3-trifluoromethyl-phenyl) -ethylamino] -l, 3,5-triazine, 2- Amino-4-chloro-6- [l - (3-nitro-phenyl) -ethylamino-1, 3,5-triazine, 2-amino-4-chloro-6- [1 - (3-chlorophenyl) - ethylamino] - 1,3,5-triazine and 2-amino-4-chloro-6- [1 - (3-methyl-phenyl) -ethylamino] -l, 3,5-triazine

excluded are.

2. Compounds of formula (I) according to claim 1, characterized in that therein R ^{1 represents} hydrogen or alkyl having 1 to 4 carbon atoms which is optionally substituted by hydroxy, cyano, fluorine, chlorine, methoxy or ethoxy,

R ^{2 represents} hydrogen, for formyl, for alkyl, alkylcarbonyl, alkoxycarbonyl or alkylsulfonyl, each optionally substituted by cyano, fluorine, chlorine, methoxy or ethoxy, each having 1 to 4 carbon atoms in the alkyl groups, or for each optionally substituted by cyano, fluorine, chlorine, Methyl, ethyl, n- or i-propyl, n-, i-, s- or t-

Butyl, trifluoromethyl, methoxy, ethoxy, n- or i-propoxy, n-, i-, s- or t-butoxy, difluoromethoxy, trifluoromethoxy, methoxycarbonyl or ethoxycarbonyl substituted phenylcarbonyl or phenylsulfonyl,

R ^{3 represents} alkyl having 1 to 4 carbon atoms which is optionally substituted by hydroxy, cyano, fluorine, chlorine, methoxy or ethoxy or represents cycloalkyl having 3 to 6 carbon atoms which is optionally substituted by cyano, fluorine, chlorine, methyl or ethyl,

X represents a substituent from the following group

Hydroxy, cyano, nitro, fluorine, chlorine, bromine, iodine, each optionally substituted by hydroxy, cyano, fluorine or chlorine alkyl or alkoxy each having 1 to 4 carbon atoms, each optionally substituted by fluorine or chlorine alkylcarbonyl, alkoxycarbonyl, alkylthio, alkylsulfinyl or Alkylsulfonyl, each with 1 to 4 carbon atoms in the alkyl groups, each optionally with hydroxyl, cyano, nitro, fluorine, chlorine, bromine, iodine, methyl, ethyl, n- or i-propyl, n-, i-, s- or t- Butyl, trifluoromethyl, methoxy, ethoxy, n- or i-propoxy, n-, i-, s- or t-butoxy, difluoromethoxy or trifluoromethoxy-substituted phenyl or phenoxy, and Z for hydrogen, hydroxy, fluorine, chlorine, bromine, for each optionally by hydroxy, cyano, nitro, fluorine, chlorine, methoxy, ethoxy, acetyl, propionyl, methoxycarbonyl, ethoxycarbonyl, methylthio, ethylthio, methylsulfinyl, ethylsulfinyl, methylsulfonyl or ethyl sulfonyl substituted alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl,

Alkylthio, alkylsulfinyl or alkylsulfonyl, each having 1 to 4 carbon atoms in the alkyl groups, for alkenyl or alkynyl, each optionally substituted by fluorine, chlorine or bromine, or alkynyl each having 2 to 4 carbon atoms, or for cycloalkyl optionally substituted by cyano, fluorine, chlorine, methyl or ethyl with 3 to 6

Carbon atoms,

the six individual connections mentioned in claim 1 being excluded.

3. Compounds of formula (I) according to claim 1, characterized in that therein

R ^{1 represents} hydrogen or methyl, ethyl, n- or i- which is optionally substituted by hydroxy, cyano, fluorine, chlorine, methoxy or ethoxy

Propyl stands,

R ² for hydrogen, for formyl, for each optionally by cyano,

Fluorine, chlorine, methoxy or ethoxy substituted methyl, ethyl, acetyl, propionyl, methoxycarbonyl, ethoxycarbonyl, methylsulfonyl or ethylsulfonyl, or for each optionally by cyano, fluorine, chlorine, methyl, ethyl, trifluoromethyl, methoxy, ethoxy, difluoromethoxy, trifluoromethoxy, methoxycarbonyl or ethoxycarbonyl substituted phenylcarbonyl or phenylsulfonyl,

R ³ for each methyl, ethyl, n- or i-propyl optionally substituted by hydroxy, cyano, fluorine, chlorine, methoxy or ethoxy, or for each optionally substituted by cyano, fluorine, chlorine, methyl or Ethyl substituted cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl,

X represents a substituent from the following group:

Hydroxy, cyano, nitro, fluorine, chlorine, bromine, each optionally substituted by hydroxy, cyano, fluorine or chlorine, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, methoxy, ethoxy , n- or i-propoxy, each optionally substituted by fluorine or chlorine, acetyl, propionyl, methoxycarbonyl, ethoxycarbonyl, methylthio,

Ethylthio, methylsulfinyl, ethylsulfinyl, methylsulfonyl or ethylsulfonyl, each optionally by hydroxy, cyano, nitro, fluorine, chlorine, bromine, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, trifluoromethyl , Methoxy, ethoxy, n- or i-propoxy, difluoromethoxy or trifluoromethoxy substituted phenyl or phenoxy, and

Z for hydrogen, hydroxy, fluorine, chlorine, bromine, for each optionally substituted by hydroxy, cyano, nitro, fluorine, chlorine, methoxy, ethoxy, acetyl, propionyl, methoxycarbonyl, ethoxycarbonyl, methylthio, ethylthio, methylsulfinyl, ethylsulfinyl, methylsulfonyl or ethylsulfonyl Methyl, ethyl, n- or i-propyl, methoxy, ethoxy, n- or i-propoxy, acetyl, propionyl, methoxycarbonyl, ethoxycarbonyl, methylthio, ethylthio, methylsulfinyl, ethylsulfinyl, methylsulfonyl or ethylsulfonyl, or for each optionally by fluorine, chlorine or Bromine substituted ethenyl, propenyl,

Butenyl, ethynyl, propynyl or butynyl,

the six individual connections mentioned in claim 1 being excluded.

A process for the preparation of new compounds of formula (I) according to claim 1, characterized in that (a) substituted biguanides of the general formula (II)

in which

R ¹ , R ² , R ³ and X have the meaning given in claim 1,

and / or acid adducts of compounds of the general formula (II)

with alkoxycarbonyl compounds of the general formula (III)

Z-CO-OR '(III)

in which

Z has the meaning given in claim 1 and

R 'represents alkyl,

or that one

(b) substituted aminotriazines of the general formula (IV)

in which

R ³ , X and Z have the meaning given above and

X ^{1 represents} halogen or alkoxy,

with nitrogen compounds of the general formula (V)

in which

R ¹ and R ^{2 have} the meaning given above,

or that one

(c) substituted aminotriazines of the general formula (VI)

in which

R ¹ , R ² and Z have the meaning given above and

X ^{2 represents} halogen or alkoxy,

with amino compounds of the general formula (VII)

in which

R ³ and X have the meaning given above,

or that one

(d) for the preparation of compounds of the formula (I), except those with R ² = H, 2,

4-diamino-l, 3,

5-triazines of the general formula (Ia)

in which

Rl, R ³ , X and Z have the meaning given above,

YR ² (VIII)

in which

R ^{2 has} the meaning given above - with the exception of hydrogen - and

Y represents halogen, alkoxy, alkoxysulfonyloxy or acyloxy,

Herbicidal agents, characterized in that they contain at least one new compound of the formula (I) according to Claim 1.

6. Use of new compounds of the general formula (I) according to Claim 1 for combating undesirable plant growth.

7. A method of combating weeds, characterized in that new compounds of the general formula (I) according to claim 1 on the

Weeds or their habitat.

8. A process for the preparation of herbicidal compositions, characterized in that new compounds of the general formula (I) according to Claim 1 are mixed with extenders and / or surface-active agents.

9. Substituted biguanides of the general formula (II),

in which

R ¹ , R ² , R ³ and X have the meanings given in Claim 1,

and their acid adducts

except for the compound 1- [1- (4-trifluoromethyl-phenyl) -ethyl] -biguanide.