CA2325489A1 - 2-[(2-arylthioethyl)amino]-4-amino-1,3,5-triazines used as herbicides - Google Patents

Abstract

The invention relates to novel substituted 2,4-diamino-1,3,5-triazines of formula (I) in which n represents 0, 1 or 2, R1 represents H or C1-C6-alkyl for example, R2 represents H, formyl, C1-C6-alkyl, C1-C6-alkyl carbonyl or C1C6-alkoxy carbonyl for example, R3 represents C1-C6-alkyl or C3-C6-cycloalkyl for example, R4 represents H or C1-C4-alkyl for example, Ar represents phenyl, naphthyl or heterocyclyl for example and Z represents H, C1-C6-alkyl, C1-C6-alkyl carbonyl, C1-C6 alkoxycarbonyl, C2-C6-alkenyl, C2-C6-alkinyl or C3-C6-cycloalkyl. The invention also relates to a method and to novel biguanide intermediate products, the production and use thereof.

Description

Le A 32 939-Foreign Countries Lu/by/NT

Substituted 2,4-diamino-1,3,5-triazines The invention relates to novel substituted 2,4-diamino-1,3,5-triazines, to processes and novel intermediates for their preparation and to their use as herbicides.
A number of substituted aryloxyalkylaminotriazines (cf. EP 273 328, EP 411 153 /
WO 90/09378) and arylthioalkylaminotriazines (cf. EP 273 328, DE 19 522 137) have already been disclosed in the (patent) literature. However, these compounds have hitherto not attained any particular importance.
This invention, accordingly, provides the novel substituted 2,4-diamino-1,3,5-triazines of the general formula (I) R~\N,RZ
N ~ N R3 Ar Z I _ N I I N S(i)n (I) in which n represents the numbers 0, 1 or 2, Rl represents hydrogen or represents optionally hydroxyl-, cyano-, halogen- or C1-C4-alkoxy-substituted alkyl having 1 to 6 carbon atoms, R2 represents hydrogen, represents formyl or represents in each case optionally cyano-, halogen- or C1-C4-alkoxy-substituted alkyl, alkylcarbonyl or alkoxy-carbonyl having in each case 1 to 6 carbon atoms in the alkyl groups, Le A 32 939-Foreign Countries R3 represents hydrogen or represents optionally hydroxyl-, cyano-, halogen- or C1-C4-alkoxy-substituted alkyl having 1 to 6 carbon atoms or represents optionally cyano-, halogen- or C1-C4-alkyl-substituted cycloalkyl having 3 to 6 carbon atoms, R4 represents hydrogen or represents alkyl having 1 to 4 carbon atoms, Ar represents in each case optionally substituted phenyl, naphthyl or hetero-cyclyl, where the possible heterocyclyl groupings are preferably selected from the group below:
furyl, benzofuryl, thienyl, benzothienyl, thiazolyl, benzothiazolyl, oxazolyl, benzoxazolyl, thiadiazolyl, oxadiazolyl, pyrazolyl, imidazolyl, tetrazolyl, pyridinyl, quinolinyl and pyrimidinyl, and where the possible substituents are in each case preferably selected from the group below:
hydroxyl, cyano, carbamoyl, thiocarbamoyl, nitro, halogen, in each case optionally hydroxyl-, cyano- or halogen-substituted alkyl or alkoxy having in each case 1 to 6 carbon atoms, in each case optionally halogen-substituted alkylcarbonyl, alkoxycarbonyl, alkylthio, alkylsulfinyl, alkylsulfonyl, dialkyl-,..
amino, alkylcarbonylamino, alkylsulfonylamino, bis-alkylcarbonyl-amino, bis-alkylsulfonyl-amino, N-alkyl-N-alkylcarbonyl-amino or N-alkyl-N-alkyl-sulfonyl-amino having in each case 1 to 6 carbon atoms in the alkyl groups, in each case optionally hydroxyl-, cyano-, nitro-, halogen-, C1-C4-alkyl-, C~-C4-halogenoalkyl-, C1-C4-alkoxy- or C1-Cq-halogenoalkoxy-substituted phenyl or phenoxy, and in each case optionally halogen-substituted methylenedioxy or ethylenedioxy, and Le A 32 939-Foreign Countries Z represents hydrogen, represents in each case optionally hydroxyl-, cyano-, halogen-, C1-C4-alkoxy-, C1-C4-alkyl-carbonyl-, Cl-C4-alkoxy-carbonyl-, C1-C4-alkylthio-, C1-C4-alkylsulfinyl- or Cl-C4-alkylsulfonyl-substituted alkyl, alkylcarbonyl or alkoxycarbonyl having in each case 1 to 6 carbon atoms in the alkyl groups, represents in each case optionally cyano-, halogen-or C1-C4-alkoxy-substituted alkenyl or alkinyl having in each case 2 to 6 carbon atoms, or represents optionally cyano-, halogen- or C 1-C4-alkyl-sub-stituted cycloalkyl having 3 to 6 carbon atoms.
The novel substituted 2,4-diamino-1,3,5-triazines of the general formula (I) are obtained when biguanides of the general formula (II) H~N H~N R3 Ar I i R~N~N~N S(~~n R' H H R4 in which n, R1, R2, R3, R4 and Ar are as defined above - and/or acid adducts of compounds of the general formula (II) -are reacted with alkoxycarbonyl compounds of the general formula (III) Z-CO-OR' (III) in which Z is as defined above and R' represents alkyl, Le A 32 939-Foreign Countries _ -4-if appropriate in the presence of a reaction auxiliary and if appropriate in the presence of a diluent, and, if appropriate, further conversions within the scope of the definition of substituents are carried out by customary methods on the resulting compounds of the general formula (I).
The compounds of the general formula (I) can be converted by customary methods into other compounds of the general formula (I) according to the above definition of substituents, for example by reacting compounds of the formula (I) in which R2 represents hydrogen with acylating agents, such as, for example, acetyl chloride, acetic anhydride, propionyl chloride or methyl chloroformate (R2 for example H
-~
COCH3), or with oxidizing agents, such as, for example, hydrogen peroxide or m-chloro-perbenzoic acid (n for example 0 -~ 1 or 2) - cf. the Preparation Examples.
The novel substituted 2,4-diamino-1,3,5-triazines of the general formula (I) have 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 thus be present in different enantiomeric (R- and S-configured forms) or diastereomeric forms. The invention relates both to the different 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 in alkyl, are in each case straight-chain or branched - including in combination 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.

Le A 32 939-Foreign Countries The invention preferably provides compounds of the formula (I) in which n represents the numbers 0, 1 or 2, R1 represents hydrogen or represents in each case optionally hydroxyl-, cyano-, fluorine-, chlorine-, methoxy- or ethoxy-substituted methyl, ethyl, n- or i-propyl, R2 represents hydrogen, represents formyl or represents in each case optionally cyano-, fluorine-, chlorine-, methoxy- or ethoxy-substituted methyl, ethyl, n-or i-propyl, n-, i-, s- or t-butyl, acetyl, propionyl, n- or i-butyroyl, methoxy-carbonyl, ethoxycarbonyl, n- or i-propoxycarbonyl, 1 S R3 represents hydrogen or represents in each case optionally hydroxyl-, cyano-, fluorine-, chlorine-, methoxy- or ethoxy-substituted methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, or represents in each case optionally cyano-, fluorine-, chlorine-, methyl- or ethyl-substituted cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl, R4 represents hydrogen, methyl or ethyl, Ar represents in each case optionally substituted phenyl, naphthyl or hetero-cyclyl, where the possible heterocyclyl groupings are preferably selected from the group below:
furyl, benzofuryl, thienyl, benzothienyl, thiazolyl, benzothiazolyl, oxazolyl, benzoxazolyl, pyrazolyl, imidazolyl, tetrazolyl, pyridinyl, quinolinyl and pyrimidinyl, Le A 32 939-Foreign Countries and where the possible substituents are in each case preferably selected from the group below:
hydroxyl, cyano, carbamoyl, thiocarbamoyl, nitro, fluorine, chlorine, bromine, in each case optionally hydroxyl-, cyano-, fluorine-, chlorine- or bromine-sub-stituted methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, methoxy, ethoxy, n-or i-propoxy, in each case optionally fluorine- and/or chlorine-substituted acetyl, propionyl, n-or i-butyroyl, methoxycarbonyl, ethoxycarbonyl, n- or - 10 i-propoxycarbonyl, methylthio, ethylthio, n- or i-propylthio, methylsulfinyl, ethylsulfinyl, n- or i-propylsulfinyl, methylsulfonyl, ethylsulfonyl, n- or i-propylsulfonyl, dimethylamino, diethylamino, acetylamino, propionylamino, n- or i-butyroylamino, methylsulfonylamino, ethylsulfonylamino, n- or i-propylsulfonylamino, bis-acetyl-amino, bis-propionyl-amino, bis-methyl-sulfonyl-amino, bis-ethylsulfonyl-amino, N-methyl-N-acetyl-amino, N-ethyl-N-acetyl-amino, N-methyl-n-propionyl-amino, N-methyl-N-methylsulfonyl-amino, N-ethyl-N-methylsulfonyl-amino or N-methyl-N-ethylsulfonyl-amino, in each case optionally 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 in each case optionally fluorine- and/or chlorine-substituted methylenedioxy or ethylenedioxy, and Z represents hydrogen, represents in each case optionally hydroxyl-, cyano-, fluorine-, chlorine-, bromine-, methoxy-, ethoxy-, n- or i-propoxy-, acetyl-, propionyl-, n- or i-butyroyl-, methoxycarbonyl-, ethoxycarbonyl-, n- or i-propoxy-carbonyl-, methylthio-, ethylthio-, n- or i-propylthio-, methyl-sulfinyl-, ethylsulfinyl-, n- or i-propylsulfinyl-, methylsulfonyl-, ethyl-sulfonyl-, n- or i-propylsulfonyl-substituted methyl, ethyl, n- or i-propyl, n-, Le A 32 939-Foreign Countries _7_ i-, s- or t-butyl, acetyl, propionyl, n- or i-butyroyl, methoxycarbonyl, ethoxy-carbonyl, n- or i-propoxycarbonyl, represents in each case optionally cyano-, fluorine-, chlorine-, bromine-, methoxy- or ethoxy-substituted ethenyl, propenyl, butenyl, ethinyl, propinyl or butinyl, or represents in each case optionally cyano-, fluorine-, chlorine-, methyl- or ethyl-substituted cyclo-propyl, cyclobutyl, cyclopentyl or cyclohexyl.
The invention relates in particular to compounds of the formula (I) in which n represents the numbers 0, 1 or 2, Rl represents hydrogen, R2 represents hydrogen, represents formyl or represents in each case optionally cyano-, fluorine-, chlorine-, methoxy- or ethoxy-substituted acetyl, propionyl, n- or i-butyroyl, methoxycarbonyl, ethoxycarbonyl, n- or i-propoxycarbonyl, R3 represents methyl, ethyl, n- or i-propyl, R4 represents hydrogen, Ar represents in each case optionally substituted phenyl, naphthyl or hetero-cyclyl, where the possible heterocyclyl groupings are preferably selected from the following group below:
furyl, benzofuryl, thienyl, benzothienyl, thiazolyl, benzothiazolyl, oxazolyl, benzoxazolyl, tetrazolyl, pyridinyl, quinolinyl and pyrimidinyl, Le A 32 939-ForeiQrl Countries _g_ and where the possible substituents are in each case in particular selected from the group below:
cyano, carbamoyl, thiocarbamoyl, nitro, fluorine, chlorine, bromine, in each case optionally cyano-, fluorine- or chlorine-substituted methyl, ethyl, n- or i-propyl, methoxy, ethoxy, in each case optionally fluorine- and/or chlorine-substituted acetyl, propionyl, methoxycarbonyl, ethoxycarbonyl, methylthio, ethylthio, methylsulfinyl, ethylsulfinyl, methylsulfonyl, ethylsulfonyl, di-methylamino, acetylamino, propionylamino, methylsulfonylamino or ethyl-sulfonylamino, in each case optionally cyano-, nitro-, fluorine-, chlorine-, bromine-, methyl-, ethyl-, n- or i-propyl-, trifluoromethyl-, methoxy-, ethoxy-, difluoromethoxy- or trifluoromethoxy-substituted phenyl or phenoxy, and in each case optionally fluorine- and/or chlorine-substituted methylenedioxy or ethylenedioxy, and Z represents in each case optionally hydroxyl-, cyano-, fluorine-, chlorine-, bromine-, methoxy-, ethoxy-, acetyl-, propionyl-, methoxycarbonyl-, ethoxy-carbonyl-, methylthio-, ethylthio-, methylsulfinyl-, ethylsulfinyl-, methyl-sulfonyl- or ethylsulfonyl-substituted methyl, ethyl, n- or i-propyl.
The abovementioned general or preferred radical definitions apply both to the end products of the formula (I) and correspondingly to the starting materials or intermediates required in each case for the preparation. These radical definitions can be combined with one another as desired, i.e. including combinations between the given preferred ranges.
Examples of the compounds of the general formula (I) according to the invention are listed in the groups below.

Le A 32 939-Foreign Countries . _9-Group 1 N ~ N CH3 ~S
Z N N
H ( /
Here, Z has, for example, the meanings given below:
methyl, ethyl, n- or i-propyl, fluoromethyl, difluoromethyl, trifluoromethyl, chloro-methyl, dichloromethyl, chlorofluoromethyl, chlorobromomethyl, chlorodifluoro-methyl, fluorodichloromethyl, bromodifluoromethyl, trichloromethyl, 1-fluoro-ethyl, 2-fluoro-ethyl, 1-chloro-ethyl, 2-chloro-ethyl, 1-bromo-ethyl, 1-chloro-1-fluoro-ethyl, 1-fluoro-propyl, 2-fluoro-propyl, 3-fluoro-propyl, 1-chloro-propyl, 2-chloro-propyl, 3-chloro-propyl, 1-bromo-propyl, 1-fluoro-1-methyl-ethyl, 2-fluoro-1-methyl-ethyl, 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, perfluoro-ethyl, 1,1-difluoro-propyl, 1,1-dichloro-propyl, perfluoropropyl, 1-hydroxy-ethyl, 1-hydroxy-1-methyl-ethyl, 1-hydroxy-propyl, methoxymethyl, ethoxymethyl, dimethoxy-methyl, 1-methoxyethyl, 2-methoxy-ethyl, 1,1-dimethoxy-ethyl, 1-ethoxy ethyl, 2-ethoxy-ethyl, 2,2-dimethoxy-ethyl, 2,2-diethoxy-ethyl, 2-methoxy-1-methyl "' ethyl, 2-ethoxy-1-methyl-ethyl, 2,2-bis-methoxy-methyl, methylthiomethyl, ethyl thiomethyl, 1-methylthio-ethyl, 2-methylthioethyl, 1-ethylthio-ethyl, 2-ethylthioethyl, methylsulfinylmethyl, ethylsulfinylmethyl, methylsulfonylmethyl, ethylsulfonyl-methyl.

Le A 32 939-Foreign Countries Grou~2 HN ~O
N ~ N CH3 ~S
Z N N
H ~ /
Here, Z has, for example, the meanings given above in Group 1.
'" 5 Group,3 HN O
N~N CH3 ~S
Z N N
H ~ /
Here, Z has, for example, the meanings given above in Group 1.
Group 4 N ~ N CzHS
~S
Z N N
H ~ /
Here, Z has, for example, the meanings given above in Group 1.

Le A 32 939-Foreig~Countries Gr. ouQ 5 H N ~O
N ~ N C2H5 ~S
Z N N
H ( /
Here, Z has, for example, the meanings given above in Group 1.
S Group 6 HN O
N ~ N CZHS
~S
Z N N
H I /
Here, Z has, for example, the meanings given above in Group 1.
Group 7 H
,~.-.
HN ~O
N ~ N C2H5 ~S
Z N N
H I /
Here, Z has, for example, the meanings given above in Group 1.

Le A 32 939-Foreign Countries Group 8 H
H N ~O
N~N CH3 ~S
Z N N
H I /
Here, Z has, for example, the meanings given above in Group 1.
Group 9 NHZ
N ~ N C2H5 ~S
Z N N
H ~ / OCH

Here, Z has, for example, the meanings given above in Group 1.
Group 10 NHz N ~ N CH3 ~S
Z N N
H I / OCH
Here, Z has, for example, the meanings given above in Group 1.

Le A 32 939-Foreign Countries Groin 11 N ~ N CH3 S ~ CH3 Z N N
' H ~ /

Here, Z has, for example, the meanings given above in Group 1.
.. S Group 12 NHZ
N ~ N C2H5 S ~ CH3 Z N N
H ~ /

Here, Z has, for example, the meanings given above in Group 1.
Group 13 ....
N ~ N C2H5 S ~ CI
Z N N
H CI /
Here, Z has, for example, the meanings given above in Group 1.

Le A 32 939-Foreign Countries Group 14 N ~ N CH3 S ~ CI
Z N N
H CI /
Here, Z has, for example, the meanings given above in Group 1.
Group 15 N ~ N CH3 ~S
Z N N
H CI / CI
Here, Z has, for example, the meanings given above in Group 1.
Group 16 N ~ N C2H5 ~S
Z N N
"_ ' H CI / CI
Here, Z has, for example, the meanings given above in Group 1.
Group 17 N ~ N C2H5 S ~ CH3 Z N N

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

Le A 32 939-Fore: Countries Group 18 N ~ N CH3 Z~N~N~S ~ CH3 Here, Z has, for example, the meanings given above in Group 1.
Group 19 N ~ N CH3 S ~ CI
Z N N
H I /
Here, Z has, for example, the meanings given above in Group 1.
Group 20 N ~ N C2H5 S ~ CI
Z N N
H ( /
Here, Z has, for example, the meanings given above in Group 1.
Group 21 N ~ N C2H5 CI
~S
Z N N
H ~ /
1 S Here, Z has, for example, the meanings given above in Group 1.

Le A 32 939-Foreign Countries Group 22 N ~ N CH3 CI
~S
Z N N
H ~ /
Here, Z has, for example, the meanings given above in Group 1.
Group 23 ,~ NHZ
N ~ N CzH5 ~S
Z N N
H ~ /
CI
Here, Z has, for example, the meanings given above in Group 1.
Group 24 N ~ N CH3 ~S
Z N N
H ~ /
CI
Here, Z has, for example, the meanings given above in Group 1.
Group 25 N ~ N CH3 S ~ CI
Z N N
H ~ /
CI
Here, Z has, for example, the meanings given above in Group 1.

Le A 32 939-Forei~ Countries Group 26 N ~ N C2H5 S ~ CI
Z N N
H ~ /
CI
Here, Z has, for example, the meanings given above in Group 1.
Group 27 NHZ
N~N C H

S ~ CH3 Z N N
H ~ /
Here, Z has, for example, the meanings given above in Group 1.
Group 28 N ~ N CH3 S ~ CH3 Z N N
H I /
Here, Z has, for example, the meanings given above in Group 1.
Group 29 N~N CH3 S ~ OCH3 Z N N
H ~ /
Here, Z has, for example, the meanings given above in Group 1.

Le A 32 939-Foreign Countries Group 30 N ~ N C2H5 Z~N~N~S \ OCH3 H ~ /
Here, Z has, for example, the meanings given above in Group 1.
S Group 31 "~, N H2 N ~ N C2H5 ~S
Z N N \ \
H ~ / /
Here, Z has, for example, the meanings given above in Group 1.
Group 32 N ~ N CH3 Z~N~N~S \ \
r..
H ~ / /
Here, Z has, for example, the meanings given above in Group 1.
Group 33 NH2 I \
N ~ N CH3 /
~SO
Z N N
H
Here, Z has, for example, the meanings given above in Group 1.

Le A 32 939-Foreign Countries Group 34 N ~ N CH3 /
~SOZ
Z N N
H
Here, Z has, for example, the meanings given above in Group 1.
Group 35 ,... NH2 N~N CH
~S ~ Br Z N N
H I /
Here, Z has, for example, the meanings given above in Group 1.
Group 36 N ~ N C2H5 ~S ~ Br Z N N
H I /
Here, Z has, for example, the meanings given above in Group 1.
Group 37 NHZ
N ~ N C2H5 Z~N~N~S ~ F
H I /
Here, Z has, for example, the meanings given above in Group 1.

Le A 32 939-Foreign Countries Group 3 8 N ~ N CH3 ~S ~ F
Z N N
H I /
Here, Z has, for example, the meanings given above in Group 1.
Group 39 ,..." N HZ
N~N CH3 F
~S
Z N N
H I/
Here, Z has, for example, the meanings given above in Group 1.
Group 40 N ~ N CZH5 F
~S
Z N N
~...
H I /
Here, Z has, for example, the meanings given above in Group 1.
Group 41 N ~ N C2Hs Br Z~N~N~S
H I /
Here, Z has, for example, the meanings given above in Group 1.

Le A 32 939-Foreign Countries Group 42 N ~ N CH3 Br ~S
Z N N
H ~ /
Here, Z has, for example, the meanings given above in Group 1.
Group 43 r. NH2 N ~ N CH3 ~S
Z N N
H ~ /
Br Here, Z has, for example, the meanings given above in Group 1.
Group 44 N ~ N CZH5 ~S
Z N N
H
Br Here, Z has, for example, the meanings given above in Group 1.
Group 45 N ~ N C2H5 ~S
Z N N
H ~ /
F
Here, Z has, for example, the meanings given above in Group 1.

Le A 32 939-Foreign Countries Group 46 N ~ N CH3 ~~~5 Z N N
H ~/
F
Here, Z has, for example, the meanings given above in Group 1.
Group 47 .- N Hz N ~ N CH3 C2H5 ~S
Z N N
H ~ /
Here, Z has, for example, the meanings given above in Group 1.
Group 48 N ~ N C2H5 C2H5 i~ ~S
Z N N
H (/
Here, Z has, for example, the meanings given above in Group 1.
Group 49 N ~ N C2H5 ~S ~ C2Hs Z N N
H ~ /
Here, Z has, for example, the meanings given above in Group 1.

Le A 32 939-Foreign Countries Group 50 N ~ N CH3 ~/S ~ C2Hs Z N N
H I/
Here, Z has, for example, the meanings given above in Group 1.
Group 51 ~. NH2 N ~ N CH3 ~S ~ CN
Z N N
H I/
Here, Z has, for example, the meanings given above in Group 1.
Group 52 N ~ N C2H5 ~S ~ CN
Z N N
H I /
Here, Z has, for example, the meanings given above in Group 1.
Group 53 NHZ
N ~ N C2H5 CN
~S
Z N N
H I/
Here, Z has, for example, the meanings given above in Group 1.

Le A 32 939-Foreign Countries GrouQ54 NHZ
N ~ N CH3 CN
i~ ~S
Z N N
H /
Here, Z has, for example, the meanings given above in Group 1.
Group 55 NHz N ~ N CH COOCH

S
Z N N
H ~/
Here, Z has, for example, the meanings given above in Group 1.
Group 56 NHZ
N ~ N C2H5 COOCH3 ~ I ~ ' Z~N~N~S
a H ~ /
Here, Z has, for example, the meanings given above in Group 1.
Using, for example, 1-(1-phenylthiomethyl-propyl)-biguanide and methyl trifluoroacetate as starting materials, the course of the reaction in the process according to the invention can be illustrated by the formula scheme below:
NH
O\'OCH H~N H~N C H
H. ~ ~ ~g --~ N~N CZHS
CF N N N ~ I
H H H \ ~ FsC~N~N~s \
H

Le A 32 939-Foreign Countries The formula (II) provides a general definition of the biguanides to be used as starting materials in the process according to the invention for preparing compounds of the formula (I). In the formula (II), n, Ar, R1, R2, R3 and R4 preferably or in particular have those meanings which have already been mentioned above in connection with the description of the compounds of the formula (IJ according to the invention as being preferred or as being particularly preferred for n, Ar, R1, R2, R3 and R4.
Suitable acid adducts of compounds of the formula (II) are their adducts with protic acids, such as, for example, with hydrogen chloride, hydrogen bromide, sulfuric acid, methanesulfonic acid, benzenesulfonic acid and p-toluenesulfonic acid.
The starting materials of the general formula (II) have hitherto not been disclosed in the literature; as novel substances, they also form part of the subject-matter of the present invention.
The novel biguanides of the general formula (II) are obtained when substituted alkylamines of the general formula (N) R3 Ar i S(O)n (N) ~..

Ra in which n, Ar, R3 and R4 are as defined above - and/or acid adducts of compounds of the general formula (N), such as, for example, the hydrochlorides -are reacted with cyanoguanidine ("dicyandiamide") of the formula (V}

Le A 32 939-Foreign Countries H~N
H.N~N~N (V) H H
if appropriate in the presence of a reaction auxiliary, such as, for example, hydrogen chloride, and if appropriate in the presence of a diluent, such as, for example, n-decane or 1,2-dichloro-benzene, at temperatures between 100°C and 200°C (cf. the Preparation Examples).
After their preparation, the biguanides of the general formula (II) can also be employed without intermediate isolation directly for preparing compounds of the general formula (I) by the process according to the invention (cf. the Preparation Examples).
The substituted alkylamines of the general formula (IV) required as precursors are known and/or can be prepared by processes known per se (cf. J. Med. Chem.
1991, 34, 1082-1085; Synlett 1994, 145-147; J. Org. Chem. 1996, 61, 3375-3387; loc.
cit.
1997, 62, 3424-3425; Tetrahedron 1997, 53, 16883-16890; WO 9323418; WO
9414832; Preparation Examples).
The formula (III) provides a general definition of the alkoxycarbonyl compounds further to be used as starting materials in the process according to the invention for preparing compounds of the formula (I). In the formula (III), Z preferably or in particular has that meaning which has already been mentioned above in connection with the description of the compounds of the formula (I) according to the invention as being preferred or as being particularly preferred for Z; R' preferably represents alkyl having 1 to 4 carbon atoms, in particular methyl or ethyl.
The starting materials of the general formula (III) are known organic chemicals for synthesis.

Le A 32 939-Foreign Countries The process according to the invention for preparing compounds of the general formula ()] is preferably carried out using a reaction auxiliary. Here, suitable reaction auxiliaries are, in general, the customary inorganic or organic bases or acid acceptors.
These preferably include alkali metal or alkaline earth metal acetates, amides, carbonates, bicarbonates, hydrides, hydroxides or alkoxides, such as, for example, sodium acetate, potassium acetate or calcium acetate, lithium amide, sodium amide, potassium amide or calcium amide, sodium carbonate, potassium carbonate or calcium carbonate, sodium bicarbonate, potassium bicarbonate or calcium bicarbonate, lithium hydride, sodium hydride, potassium hydride or calcium hydride, lithium hydroxide, sodium hydroxide, potassium hydroxide or calcium hydroxide, sodium methoxide, ethoxide, n- or i-propoxide, n-, i-, s- or t-butoxide or potassium methoxide, ethoxide, n- or i-propoxide, n-, i-, s- or t-butoxide; furthermore also basic organic nitrogen compounds, such as, for example, trimethylamine, triethylamine, tripropylamine, tributylamine, ethyl-diisopropylamine, N,N-dimethyl-cyclohexyl-amine, dicyclohexylamine, ethyl-dicyclohexylamine, N,N-dimethyl-aniline, N,N-di-methyl-benzylamine, 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-di-methylamino-pyridine, N-methyl-piperidine, 1,4-diazabicyclo[2,2,2]-octane (DABCO), 1,5-diazabicyclo[4,3,0]-non-S-ene (DBN), or 1,8-diazabicyclo[5,4,0]-undec-7-ene (DBU).
Suitable diluents for carrying out the process according to the invention are especially inert organic solvents. These include, in particular, aliphatic, alicyclic or aromatic, optionally halogenated hydrocarbons, such as, for example, benzine, 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 ether or ethylene glycol diethyl ether; ketones, such as acetone, butanone or methyl isobutyl ketone; nitrites, such as acetonitrile, propionitrile or butyronitrile; amides, such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-formanilide, N-Le A 32 939-Foreign Countries methyl-pyrrolidone or hexamethylphosphoric triamide; esters such as methyl acetate or ethyl acetate, sulfoxides, such as dimethyl sulfoxide, alcohols, such as methanol, ethanol, n- or i-propanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, mixtures thereof with water or pure water.
When carrying out the process according to the invention, the reaction temperatures can be varied within a relatively wide range. In general, the process is carried out at temperatures between -20°C and +150°C, preferably between -10°C and +100°C.
The process according to the invention is generally carried out under atmospheric pressure. However, it is also possible to carry out the process according to the invention under elevated or reduced pressure - in general between 0.1 bar and 10 bar.
For carrying out the process according to the invention, the starting materials are generally employed in approximately equimolar amounts. However, it is also possible to use a relatively large excess of one of the components. The reaction is generally carried out in a suitable diluent in the presence of a reaction auxiliary and the reaction mixture is generally heated for several hours at the required temperature.
Work-up is carried out by customary methods (cf. the Preparation Examples).
The active compounds according to the invention can be used as defoliants, desiccants, haulm killers and, especially, as weed killers. By weeds in the broadest sense there are to be understood all plants which grow in locations where they are undesired. 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 connection with the following plants:

Le A 32 939-Foreign Countries Dicotyledonous weeds of the genera: Sinapis, Lepidium, Galium, Stellaria, Matricaria, Anthemis, Galinsoga, Chenopodium, Urtica, Senecio, Amaranthus, Portulaca, Xanthium, Convolvulus, Ipomoea, Polygonum, Sesbania, Ambrosia, Cirsium, Carduus, Sonchus, Solanum, Rorippa, Rotala, Lindernia, Lamium, Veronica, Abutilon, Emex, Datura, Viola, Galeopsis, Papaver, Centaurea, Trifolium, Ranunculus, Taraxacum.
Dicotyledonous crops of the genera: Gossypium, Glycine, Beta, Daucus, Phaseolus, Pisum, Solanum, Linum, Ipomoea, Vicia, Nicotiana, Lycopersicon, Arachis, Brassica, Lactuca, Cucumis, Cucurbita.
Monocotyledonous weeds of the Qenera: Echinochloa, Setaria, Panicum, Digitaria, Phleum, Poa, Festuca, Eleusine, Brachiaria, Lolium, Bromus, Avena, Cyperus, Sorghum, Agropyron, Cynodon, Monochoria, Fimbristylis, Sagittaria, Eleocharis, Scirpus, Paspalum, Ischaemum, Sphenoclea, Dactyloctenium, Agrostis, Alopecurus, Apera.
Monocotyledonous crops of the genera: Oryza, Zea, Triticum, Hordeum, Avena, Secale, Sorghum, Panicum, Saccharum, Ananas, Asparagus, Allium.
However, the use of the active compounds according to the invention is in no way restricted to these genera, but also extends in the same manner to other plants.
Depending on the concentration, the compounds are suitable for total weed control, for example on industrial terrain and rail tracks and on paths and areas with or without tree growth. Equally, the compounds can be employed for controlling weeds in perennial crops, for example forests, ornamental tree plantings, orchards, vineyards, citrus groves, nut orchards, banana plantations, coffee plantations, tea plantations, rubber plantations, oil palm plantations, cocoa plantations, soft fruit plantings and hop fields, on lawns and turf and pastures and for selective weed control in annual crops.

Le A 32 939-Foreign Countries The compounds of the formula (17 according to the invention are particularly suitable for selective control of monocotyledonous and dicotyledonous weeds in monocotyledonous and dicotyledonous crops, both by the pre-emergence and by the post-emergence method.
The active compounds can be converted into the customary formulations, such as solutions, emulsions, wettable powders, suspensions, powders, dusts, pastes, soluble powders, granules, suspo-emulsion concentrates, natural and synthetic substances ""' 10 impregnated with active compound, and microencapsulations in polymeric substances.
These formulations are produced in a known manner, for example by mixing the active compounds with extenders, that is to say liquid solvents and/or solid carriers, optionally with the use of surfactants, that is to say emulsifiers and/or dispersants andlor foam formers.
If the extender used is water, it is also possible to use, for example, organic solvents as auxiliary solvents. Liquid solvents which are mainly suitable are:
aromatics, such as xylene, toluene or alkylnaphthalenes, chlorinated aromatics and chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, for example petroleum fractions, mineral and vegetable oils, alcohols, such as butanol or glycol, and also 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.
Suitable solid carriers are: for example ammonium salts and ground natural minerals, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and ground synthetic minerals, such as finely divided silica, alumina and silicates; suitable solid carriers for granules are: for example crushed Le A 32 939-Foreign Countries and fractionated natural rocks, such as calcite, marble, pumice, sepiolite, dolomite and synthetic granules of inorganic and organic meals, and granules of organic material, such as sawdust, coconut shells, maize cobs and tobacco stalks;
suitable emulsifiers and/or foam formers are: for example nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkylsulfonates, alkyl sulfates, arylsulfonates and protein hydrolysates; suitable dispersants are: for example lignosulfite waste liquors and methylcellulose.
Tackifiers, such as carboxymethylcellulose, natural and synthetic polymers in the form of powders, granules or latices, such as gum arabic, polyvinyl alcohol and polyvinyl acetate, and also natural phospholipids, such as cephalins and lecithins, and synthetic phospholipids can be used in the formulations. Other possible additives are mineral and vegetable oils.
It is possible to use colorants, such as inorganic pigments, for example iron oxide, titanium oxide, Prussian blue, and organic dyestuffs, such as alizarin dyestuffs, azo dyestuffs and metal phthalocyanine dyestuffs, and trace nutrients, such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.
The formulations generally comprise between 0.1 and 95 per cent by weight of active compound, preferably between 0.5 and 90%.
For controlling weeds, the active compounds according to the invention, as such or in the form of their formulations, can also be used as mixtures with known herbicides, finished formulations or tank mixes being possible.
Possible components for the mixtures are known herbicides, for example acetochlor, acifluorfen(-sodium), aclonifen, alachlor, alloxydim(-sodium), ametryne, amidochlor, amidosulfuron, anilofos, asulam, atrazine, azafenidin, azimsulfizron, benazolin(-ethyl), benfuresate, bensulfuron(-methyl), bentazon, benzofenap, Le A 32 939-Foreign Countries benzoylprop(-ethyl), bialaphos, bifenox, bispyribac(-sodium), bromobutide, bromofenoxim, bromoxynil, butachlor, butroxydim, butylate, cafenstrole, caloxydim, carbetamide, carfentrazone(-ethyl), chlomethoxyfen, chloramben, chloridazon, chlorimuron(-ethyl), chlornitrofen, chlorsulfuron, chlortoluron, cinmethylin, cinosulfuron, clethodim, clodinafop(-propargyl), clomazone, clomeprop, clopyralid, clopyrasulfuron(-methyl), cloransulam(-methyl), cumyluron, cyanazine, cycloate, cyclosulfamuron, cycloxydim, cyhalofop(-butyl), 2,4-D, 2,4-DB, 2,4-DP, desmedipham, diallate, dicamba, diclofop(-methyl), diclosulam, diethatyl(-ethyl), difenzoquat, diflufenican, diflufenzopyr, dimefuron, dimepiperate, dimethachlor, '"" 10 dimethametryn, dimethenamid, dimexyflam, dinitramine, diphenamid, diquat, dithiopyr, diuron, dymron, epoprodan, EPTC, esprocarb, ethalfluralin, ethametsulfuron(-methyl), ethofumesate, ethoxyfen, ethoxysulfuron,etobenzanid, fenoxaprop(-P-ethyl), flamprop(-isopropyl), flamprop(-isopropyl-L), flam-prop(-methyl), flazasulfuron, fluazifop(-P-butyl), flufenacet,flumetsulam, flumiclorac(-pentyl), flumioxazin, flumipropyn, flumetsulam,fluometuron, fluoroglycofen(-ethyl), flupoxam, flupropacil, fluorochloridone, flurpyrsulfuron(-methyl, -sodium), flurenol(-butyl), fluridone, fluroxypyr(-meptyl), flurprimidol, flurtamone, fluthiacet(-methyl), fluthiamide, fomesafen, 1 hosate -iso ro lammonium , halosafen, glufosinate(-ammonium), g yp ( p py ) haloxyfop(-ethoxyethyl), haloxyfop(-P-methyl), hexazinone, imazamethabenz-(-methyl), imazamethapyr, imazamox, imazapyr, imazaquin, imazethapyr, imazosulfuron, ioxynil, isopropalin, isoproturon, isouron, isoxaflutole, isoxaben, isoxapyrifop, lactofen, lenacil, linuron, MCPA, MCPP, mefenacet,metamitron, metazachlor, methabenzthiazuron, metobenzuron, m etobromuron, (alpha-)metolachlor, metosulam, metoxuron, metribuzin, metsulfuron(-methyl), molinate, monolinuron, naproanilide, napropamide, neburon, nicosulfuron, norflurazon, orbencarb, oryzalin, oxadiargyl, oxadiazon, oxasulfuron, oxaziclomefone, oxyfluorfen, paraquat, pelargonic acid, pendimethalin, pentoxazone, phenmedipham, piperophos, pretilachlor, primisulfuron(-methyl), prometryn, propachlor, propanil, propaquizafop, propisochlor, propyzamide, prosulfocarb, prosulfuron, pyraflufen(-ethyl), pyrazolate, pyrazosulfuron(-ethyl), pyrazoxyfen, Le A 32 939-Foreign Countries pyribenzoxim, pyributicarb, pyridate, pyriminobac(-methyl), pyrithiobac(-sodium), quinchlorac, quinmerac, quinoclamine, quizalofop(-P-ethyl), quizalofop(-P-tefuryl), rimsulfuron, sethoxydim, simazine, simetryn, sulcotrione, sulfentrazone, sulfometuron(-methyl), sulfosate, sulfosulfuron, tebutam, tebuthiuron, terbuthylazine, terbutryn, thenylchlor, thiafluamide, thiazopyr, thidiazimin, thifensulfuron(-methyl), thiobencarb, tiocarbazil, tralkoxydim, triallate, triasulfuron, tribenuron(-methyl), triclopyr, tridiphane, trifluralin and triflusulfuron.
A mixture with other known active compounds, such as fungicides, insecticides, acaricides, nematicides, bird repellents, 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. They are used in the customary manner, for example by watering, spraying, atomizing, scattering.
The active compounds according to the invention can be applied both before and after emergence of the plants. They can also be incorporated into the soil before sowing.
The amount of active compound used can vary within a relatively wide range. It depends essentially on the nature of the desired effect. In general, the amounts used are between 1 g and 10 kg of active compound per hectare of soil surface, preferably between 5 g and S kg per ha.
The preparation and the use of the active compounds according to the invention can be seen from the examples below.

Le A 32 939-Foreign Countries Preparation Examples:
Example 1 N ~ N C2H5 H C~~'C~N~N~S \ CH3 3 2 i H H I /
1.3 g (4.0 mmol) of 1-[1-(3-methyl-phenylthiomethyl)-propyl]-biguanide hydrochloride (racemic) are dissolved in 30 ml of methanol and admixed with 1.2 g of zeolite molecular sieve. The mixture is cooled to -10°C, admixed with 0.43 g (8.0 mmol) of sodium methoxide and then admixed dropwise with stirring with 0.46 g (4.4 mmol) of methyl methoxy acetate. After warming to room temperature (approximately 20°C), the reaction mixture is stirred for another 15 hours. The solid components are separated off by filtration with suction, the filtrate is concentrated under waterpump vacuum and the residue is worked up by column chromatography (silica gel, ethyl acetate / hexane, vol.: 1:1 ).
This gives 0.9 g (70% of theory) of 2-amino-4-methoxymethyl-6-[1-(3-methyl-phenylthiomethyl)-propylamino]-1,3,5-triazine (racemate) as a viscous oil.
Examine 2 NHZ
N ~ N CZHS
i~ ~ S CI
H3C' H N N I \
H CI
(with synthesis of the starting material) Le A 32 939-Foreign Countries A mixture of 2.9 g (10 mmol) of 1-(2,5-dichloro-phenylthiomethyl)-propylamine hydrochloride (racemic) and 0.8 g (10 mmol) of dicyandiamide is heated at 160°C for 30 minutes. The mixture is then allowed to cool to about 80°C, and 30 ml of methanol are added. The resulting solution is cooled to -10°C and admixed successively with 2 g of zeolite molecular sieve, 1.1 g (20 mmol) of sodium methoxide and 1.0 g (11 mmol) of methyl propionate. The reaction mixture is stirred at room temperature (approximately 20°C) for 15 hours and then filtered. The filtrate is concentrated under waterpump vacuum and the residue is worked up by column chromatography (silica gel, ethyl acetate / hexane, vol.: 1:2).
"" 10 This gives 1.9 g (51 % of theory) of 2-amino-4-ethyl-6-[ 1-(2,5-dichloro-phenylthio-methyl)-propylamino]-1,3,5-triazine (racemate) of melting point 96°C.
Example 3 N ~ N CZH5 H3C~C~N~N~S02 i CI H
(subsequent reaction) 1.7 g (S.0 mmol) of 2-amino-4-(1-chloro-ethyl)-6-(1-phenylthiomethyl-propyl-amino)-1,3,5-triazine (racemic) and 3.5 g (20 mmol) of 3-chloro-perbenzoic acid in 100 ml of dichloromethane are stirred at room temperature (approximately 20°C) for two days. The mixture is then washed with 50 ml of 5% strength aqueous sodium bicarbonate solution and the organic phase is dried with sodium sulfate and filtered.
The filtrate is concentrated under waterpump vacuum, the residue is crystallized by digestion with diethyl ether and the crystalline product is isolated by filtration with suction.

Le A 32 939-Forei~ Countries This gives 0.5 g (27% of theory) of 2-amino-4-(1-chloro-ethyl)-6-(1-phenylsulfonyl-methyl-propylamino)-1,3,5-triazine (racemate) of melting point 134°C.
Example 4 HN O
N ~ N CZHS
H3C.C~N~N~S
i F H
(subsequentreaction) A mixture of 1.2 g (3.7 mmol) of 2-amino-4-(1-fluoro-ethyl)-6-(1-phenylthio-methyl-propylamino)-1,3,5-triazine (racemic) and 30 ml of propionic anhydride is stirred at 80°C for 60 minutes. After cooling to room temperature (approximately 20°C), the reaction mixture is stirred with about the same amount by volume of water, and the resulting crystalline product is isolated by filtration with suction.
This gives 1.3 g (92% of theory) of 2-propionylamino-4-(1-fluoro-ethyl)-6-(1-phenyl-thiomethyl-propylamino)-1,3,5-triazine (racemate) of melting point 58°C.
Example 5 H
H N ~O
N ~ N C2H5 ~ CI
H3C ~N ~ N ~S

(subsequent reaction) Le A 32 939-Foreign Countries 1.85 g (S.0 mmol) of 2-amino-4-(1-fluoro-1-methyl-ethyl)-6-[1-(2-chloro-phenylthio-methyl)-propylamino]-1,3,5-triazine (racemic) and 0.8 g (6.0 mmol) of N,N-dimethyl-formamide dimethyl acetal in 50 ml of dioxane are stirred at room temperature (approximately 20°C) for 15 hours. The mixture is then concentrated under waterpump vacuum, the residue is admixed with 30 ml of water and 25 ml of 1 N hydrochloric acid and the resulting crystalline product is isolated by filtration with suction.
This gives 1.2 g (60% of theory) of 2-formylamino-4-(1-fluoro-1-methyl-ethyl)-6-[1-(2-chloro-phenylthiomethyl)-propylamino]-1,3,5-triazine (racemate) of melting point 150°C.
Analogously to Preparation Examples 1 to 5 and in accordance with the general description of the preparation process according to the invention, it is also possible to prepare, for example, the compounds of the formula (I) listed in Table 1 below.
Table 1: Examples of the compounds of the formula (I) R'wN.R2 N ~ N R3 Ar I
i () Z~N~N S~O)n Le A 32 939-Foreign Countries Table 1 (continued) Ex. Physical data No. R1 R2 R3 R4 Ar Z n and stereochem.

specifications 6 H H C2H5 H ~ CF(CH3)2 0 (oil) (racemate) 7 H H CH3 H CH3 CF(CH3)2 0 (oil) (racemate) /

8 H H CH3 H HsC ~ CHa CF(CH3)2 0 (oil) (racemate) 9 H H CH3 H HsC ~ CHa C2H5 0 (oil) (racemate) ...., H H C2H5 H ~ CI CF(CH3)2 0 (oil) (racemate) CI

11 H H C2H5 H CI CF(CH3)2 0 (oil) (racemate) /

~CI

Le A 32 939-Foreign Countries Table 1 (continued) Ex. Physical data No. R1 R2 R3 R4 Ar Z n and stereochem.

specifications 12 H H C2H5 H CI C2H5 0 (oil) (racemate) /

,...
~CI

13 H H CH3 H ~ CI C2H5 0 (oil) (racemate) CI

14 H H C2H5 H ~ CHC12 0 (oil) (racemate) 15 H H C2H5 H ~ C3H7-i 0 (oil) (racemate) 16 H ~ C2H5 H ~ H 0 m.p.:143C
(racemate) O

17 H CH3 H CI CF(CH3)2 0 m.p.:131C

~ ~ (racemate) o CI

Le A 32 939-Forei~,n Countries Table 1 (continued) Ex. Physical data No. R1 R2 R3 R4 Ar Z n and stereochem.
specifications 18 H H C2H5 H ~ CHFCH3 0 (amorphous) (racemate) 19 H ~ C2H5 H ~ CHFCH3 0 m.p.:125°C
o (racemate) 20 H ~ C2H5 H ~ CHFCH3 0 m.p.:124°C
o (racemate) 21 H ~ C2H5 H ~ C2H5 0 m.p.:126°C
O (racemate) 22 H ~ C2H5 H ~ C2H5 0 m.p.:113°C
o (racemate) 23 H ~ CH3 CH3 ~ CF(CH3)2 0 m.p.:122°C
o (racemate) Le A 32 939-Foreign Countries Table 1 (continued) Ex. Physical data No. Rl R2 R3 R4 Ar Z n and stereochem.
specifications 24 H ~ C2H5 H ~ CF(CH3)2 0 m.p.:99°C
o (racemate) 25 H H CH3 CH3 ~ CHC12 0 (amorphous) (racemate) 26 H H CH3 CH3 ~ CHFCH3 0 (oil) (racemate) 27 H H C2H5 H ~ off/ 0 (oil) c"3 (racemate) 28 H H C2H5 H ~ 0 (oil) (racemate) 29 H H C2H5 H ~ CHC1CH3 0 (oil) (racemate) Le A 32 939-Foreign Countries Table 1 (continued) Ex. Physical data No. R1 R2 R3 R4 Ar Z n and stereochem.
specifications 30 H H C2H5 H ~ CHC1CH3 1 (racemate) 31 H H CH3 H ~ CH3 CF(CH3)2 0 (oil) (racemate) 32 H H C2H5 H H3C ~ CHs CF(CH3)2 0 (oil) ( / (racemate) 33 H H CH3 H ~ CI CF(CH3)2 0 m.p.:74°C
(racemate) CI
"'~' 34 H H C2H5 H ~ CH3 CF(CH3)2 0 (oil) (racemate) 35 H H CH3 H ~ ~ CF(CH3)2 0 m.p.:62°C
/ / (racemate) 36 H H CH3 H CI CF(CH3)2 0 m.p.:53°C
CI (racemate) Le A 32 939-Foreign Countries Table 1 (continued) Ex. Physical data No. R1 R2 R3 R4 Ar Z n and stereochem.

specifications 37 H H CH3 H ~ ~ C2H5 0 (oil) / (racemate) 38 H H CH3 H ~ ~H3 C2H5 0 (oil) (racemate) HsC

39 H H C2H5 H ~ CHs C2H5 0 (oil) (racemate) 40 H H CH3 H CI CF(CH3)2 0 m.p.:124C

(racemate) -CI

-- 41 H H CH3 H CI C2H5 0 (oil) (racemate) -CI

42 H H CH3 H CI C2H5 0 (oil) CI (racemate) Le A 32 939-Foreign Countries Table 1 (continued) Ex. Physical data No. R1 R2 R3 R4 Ar Z n and stereochem.

specifications 43 H H C2H5 H ~ CI C2H5 0 (oil) (racemate) 44 H H C2H5 H ~ CHs CH3 0 (oil) (racemate) 45 H H CH3 H ~ CF(CH3)2 0 m.p.:115C

(racemate) / CI

46 H H C2H5 H ~ CI CF(CH3)2 0 (oil) (racemate) ,.." 47 H H C2H5 H ~ CF(CH3)2 0 (oil) (racemate) CI

48 H H C2H5 H ~ CI CH3 0 (oil) (racemate) 49 H H C2H5 H CI CF(CH3)2 0 (oil) (racemate) (/

Le A 32 939-Forei~ Countries Table 1 (continued) Ex. Physical data No. R1 R2 R3 R4 Ar Z n and stereochem.

specifications 50 H H CH3 H CI CF(CH3)2 0 (oil) (racemate) 51 H H C2H5 H ~ OCH3 CF(CH3)2 0 (oil) (racemate) 52 H H C2H5 H ~ OCH3 C2H5 0 (oil) (racemate) 53 H H C2H5 H OCH3 CF(CH3)2 0 (oil) (racemate) 54 H H CH3 H ~ OCH3 CF(CH3)2 0 (oil) (racemate) SS H H C2H5 H ~ C2H5 0 (oil) (racemate) Le A 32 939-Foreign Countries Table 1 (continued) Ex. Physical data No. R1 R2 R3 R4 Ar Z n and stereochem.

specifications 56 H H C2H5 H ~ C2H5 0 (oil) (racemate) -CI

57 H H C2H5 H CI C2H5 0 (oil) (racemate) 58 H H CH3 H CI C2H5 0 (oil) (racemate) 59 H H CH3 H ~ ~ CHCI2 0 (oil) ( / / (racemate) 60 H H CH3 H ~ CHs CHCI2 0 (oil) (racemate) 61 H H C2H5 H ~ CHs CHC12 0 (oil) (racemate) 62 H H CH3 H CI CHC12 0 (oil) CI (racemate) Le A 32 939-Foreign Countries Table 1 (continued) Ex. Physical data No. R RZ R3 R4 Ar Z n and stereochem.

specifications 63 H H C2H5 H ~ CI CHCl2 0 (oil) (racemate) CI

64 H H C2H5 H ~ CI CHC12 0 (oil) (racemate) 65 H H CH3 H ~ CHC12 0 (oil) (racemate) CI

66 H H C2H5 H ~ CHC12 0 (oil) (racemate) ~CI

67 H H C2H5 H ~ CH3 CHC12 0 (oil) (racemate) 68 H H C2H5 H ~ CH3 CF(CH3)2 0 (oil) (racemate) 69 H H C2H5 H ~ CH3 CHFCH3 0 (oil) (racemate) Le A 32 939-Foreign Countries Table 1 (continued) Ex. Physical data No. R1 R2 R3 R4 Ar Z n and stereochem.
specifications 70 H H C2H5 H ~ CH3 q~/ 0 (oil) c"3 (racemate) 71 H H C2H5 H ~ CH3 C3H7-i 0 (oil) (racemate) 72 H H C2H5 H ~ CH3 CHFCH3 0 m.p.:128°C
(racemate) 73 H ~H3 C2H5 H ~ CH3 CHFCH3 0 m.p.:116°C
(racemate) 74 H H C2H5 H ~ CH3 CHC1CH3 0 (oil) (racemate) 75 H ~"3 C2H5 H ~ CHC1CH3 0 m.p.:124°C
(racemate) 76 H H C2H5 H ~ CI CHFCH3 0 (oil) (racemate) Le A 32 939-Foreign Countries Table 1 (continued) Ex. Physical data No. R R2 R3 R4 Ar Z n and stereochem.

specifications 77 H H C2H5 H ~ CI off/ 0 (oil) c"3 (racemate) 78 H H C2H5 H ~ CI C3H7-i 0 (oil) (racemate) 79 H CZ"s C2H5 H ~ CF(CH3)2 0 m.p.:lllC
(racemate) -CI

80 H CZHS CH3 H ~ ~ CF(CH3)2 0 m.p.:138C
(racemate) /
-CI

81 H ~H3 C2H5 H ~ CI CF(CH3)2 0 m.p.:117C
(racemate) 82 H H C2H5 H ~ CI CHC1CH3 0 (oil) (racemate) 83 H H C2H5 H ~ OCH3 CHFCH3 0 (oil) (racemate) Le A 32 939-Foreign Countries Table 1 (continued) Ex. - Physical data No. R1 R2 R3 R4 Ar Z n and stereochem.

specifications 84 H H CH3 H ~ CF(CH3)2 0 m.p.:120C

(racemate) 85 H H CH3 H ~ CF(CH3)2 2 m.p.:202C

(racemate) 86 H H CH3 H ~~ -N CF(CH3)2 0 (oil) N ~ ~ (racemate) N

n p :

CH .

Le A 32 939-Foreign Countries Table 1 (continued) Ex. Physical data No. R1 R2 R3 R4 '°'r Z n and stereochem.
specifications 87 H H C2H5 H ~ CF(CH3)2 0 m.p.:150°C
O I (racemate) ~CI
88 H H CZHs H ~ B~ CF(CH3)2 0 (oil) (racemate) 89 H CzHs C2Hs H ~ CI CH20CH3 0 m.p.: 84°C
O I (racemate) 90 H CH3 CZHs H ~ OCH3 CHFCH3 0 m.p.:109°C
O I (racemate) 91 H CH3 C2Hs H ~ OCH3 CF(CH3)2 0 m.p.:135°C
O (racemate) 92 H CzHS CzHs H ~ OCH3 CF(CH3)2 0 m.p.: 91 °C
O I (racemate) Le A 32 939-Foreign Countries Table 1 (continued) Ex. Physical data No. R1 R2 R3 R4 ~. Z n and stereochem.

specifications 93 H H CH3 H ~ CI CF(CH3)2 0 (oil) (racemate) 94 H H CH3 H ~ CI CHFCH3 0 (oil) (racemate) 95 H H CH3 H ~ CI CHC1CH3 0 (oil) (racemate) 96 H CH3 CH3 H CI CF(CH3)2 0 m.p.:119C

~ (racemate) 97 H CZHS CH3 H CI CHC1CH3 0 m.p.: 100C

~ (racemate) 98 H H C2H5 H ~ CI CF(CH3)2 0 (amorphous) (racemate) ~CI

99 H H C2H5 H ~ CI CHFCH3 0 (amorphous) (racemate) -CI

Le A 32 939-Foreign Countries Table 1 (continued) Ex. Physical data R1 R2 R3 R4 ''r Z n and No.

stereochem.

specifications 100 H H C2H5 H ~ CI CHC1CH3 0 (amorphous) (racemate) ~CI

...,. 101 H CH3 C2H5 H CI CF(CH3)20 m.p.:169C

/~ ~ (racemate) C I

~CI

102 H CZHS C2H5 H CI CF(CH3)20 m.p.: 161 C

o ~ (racemate) I

~CI

103 H CH3 C2H5 H CI CHFCH3 0 m.p.:146C

C ~ (racemate) ~

-CI

104 H CZHS C2H5 H CI CHFCH3 0 m.p.: 154C

0 ~ (racemate) I

105 H CH3 CZHS H CI CHC1CH3 0 m.p.:147C

0 ~ (racemate) -CI

106 H CZHS C2H5 H CI CHC1CH3 0 m.p.: 141 C

C ~ (racemate) I

-CI

Le A 32 939-Foreign Countries Table 1 (continued) Ex. Physical data R1 R2 R3 R4 p,i- Z n and No. stereochem.

specifications 107 H H C2Hs H ~ CF3 CF(CH3)20 (oil) (racemate) 108 H H CzHs H ~ CFa CHFCH3 0 (oil) (racemate) 109 H H CZHs H ~ CF3 CHC1CH~ 0 (oil) (racemate) 110 H CHs CzHs H CFs CF(CH3)20 m.p.:117C

0 ~ (racemate) I

111 H CzHs CzHs H CFa CF(CH3)20 m.p.:95C

~ (racemate) 112 H CHs C2Hs H CFs CHFCH3 0 m.p.:102C

~ (racemate) 113 H CzHs C2Hs H CFs CHFCH3 0 m.p.:68C

~ (racemate) Le A 32 939-Foreign Countries Table 1 (continued) Ex. Physical data R1 R2 R3 R4 ~ Z n and No.

stereochem.

specifications 114 H CH3 C2H5 H CF3 CHC1CH3 0 m.p.:79C

~ (racemate) .._. 115 H CZHS C2H5 H CF3 CHC1CH3 0 m.p.:61C

0 ~ (racemate) I

116 H H C2H5 H ~ CHFCH3 0 (oil) (racemate) -CI

Le A 32 939-Fore~n Countries Starting materials of the formula (II):
Example (II-11 H.N H.N C2Hs H~N~N~N S ~ CH3 x HCI

A mixture of 1.9 g (8.0 mmol) of 1-(3-methyl-phenylthio)-2-amino-butane hydrochloride (racemic) and 0.69 g (8.0 mmol) of cyanoguanidine (dicyandiamide) is stirred at 160°C for 30 minutes. After the resulting melt has cooled, 2.5 g (99% of theory) of 1-[1-(3-methyl-phenylthiomethyl)-propyl]-biguanide hydrochloride are obtained as a hygroscopic solid of melting point 110°C.
Analogously to Example (II-1}, it is also possible to prepare, for example, the compounds of the formula (II) listed in Table 2 below.
Table 2: Examples of the compounds of the formula (II) H~N H~N R3 Ar i RvN~N~N S(O)n R' H H R4 In all cases, the compounds are the corresponding hydrochlorides Le A 32 939-Foreign Countries Table 2 (continued) Ex. Physical data No. R1 R2 R3 R4 Ar n and stereochem.
specifications II-2 H H CH3 H ~ 0 (racemate) -CI
II-3 H H CH3 CH3 ~ 0 (racemate) (racemate) /
~CI
II-5 H H CH3 H ~ CH3 0 (racemate) (racemate) II-7 H H CH3 H H3C ~ CHs 0 (racemate) Le A 32 939-Foreign Countries Table 2 (continued) Ex. Physical data No. R1 R2 R3 R4 Ar n and stereochem.
specifications II-8 H H CH3 H ~ CI 0 (racemate) II-9 H H C2H5 H ~ 0 ( / (racemate) -CI
II-10 H H C2H5 H CI ~ 0 CI (racemate) II-11 H H CH3 H ~ OCH3 0 (racemate) II-12 H H C2H5 H ~ CI 0 (racemate) CI
II-13 H H C2H5 H ~ CI 0 (racemate) Le A 32 939-Forei~ Countries Table 2 (continued) Ex. Physical data No. R1 R2 R3 R4 Ar n and stereochem.
specifications (racemate) /

(racemate) /
~CI

(racemate) /
II-17 H H C2H5 H ~ CHs 0 (racemate) ~CH3 II-18 H H CH3 H ~ CHs 0 (racemate) ~CH3 II-19 H H C2H5 H H3C ~ CHs 0 (racemate) Le A 32 939-Foreign Countries Table 2 (continued) Ex. Physical data No. R1 R2 R3 R4 Ar n and stereochem.
specifications II-20 H H CH3 H ~ CH3 0 (racemate) (racemate) II-22 H H CH3 H C~ 0 (racemate) (racemate) ~

Le A 32 939-Foreign Countries Startins materials of the formula (IV):
Examule (IV-1) C2Hs H2N~S ~ CH3 x HCI
( Step 1 %\3 C2H5 ~S ~ CH3 H

A mixture of 9.0 g (65 mmol) of 2,5-dimethyl-thiophenol and 7.3 g (65 mmol) of methyl-4-ethyl-2-oxazoline is stirred at 140°C for 15 hours.
Subsequently - after cooling to room temperature - the mixture is stirred with diethyl ether and the resulting crystalline product is isolated by filtration with suction.
This gives 14.7 g (90% of theory) of N-acetyl-1-(2,5-dimethyl-phenylthio)-2-amino-butane of melting point 132°C.
.._ 15 Steu 2 C2Hs H2N~S ~ CH3 x HCI
I~

12.2 g (52 mmol) of N-acetyl-1-(2,5-dimethy-phenylthio)-2-amino-butane in 30 ml of conc. hydrochloric acid are heated under reflux for 15 hours. After cooling to room temperature, the reaction mixture is admixed with 100 ml of water and shaken with diethyl ether. The aqueous phase is separated off and concentrated under waterpump vacuum. The residue is digested with diethyl ether and the resulting crystalline product is isolated by filtration with suction.

Le A 32 939-Foreign Countries This gives 8.3 g (69% of theory) of 1-(2,5-dimethyl-phenylthio)-2-amino-butane hydrochloride of melting point 119°C.
S Analogously to Example (N-1), it is also possible to prepare, for example, the compounds of the formula (N) listed in Table 3 below.
Table 3: Examples of the compounds of the formula (N) R3 Ar i S(O)~ (N) HzN
Ra In all cases, the compounds are the corresponding hydrochlorides.
Ex. Physical data and No. R3 R4 Ar n stereochem.

specifications N-2 CH3 H OCH3 0 (oil) ~ (racemate) N-3 C2H5 H ~ 0 (oil) (racemate) N-4 CH3 H H3C ~ CHs 0 (oil) (racemate) Le A 32 939-Foreien Countries Table 3 (continued) Ex. Physical data and No. R3 R4 Ar n stereochem.

specifications IV-S C2H5 H H3C ~ CH3 0 m.p.:57C

(racemate) IV-6 CH3 H ~ ~ 0 m.p.:102C

(racemate) / /

1V-7 CH3 H ~ CH3 0 m.p.:119C

(racemate) IV-8 CH3 H ~ CI 0 m.p.:148C

( (racemate) CI

IV-9 CH3 H CI 0 m.p.:160C

CI (racemate) /

IV-10 C2H5 H ~ CI 0 m.p.:102C

( (racemate) CI

Le A 32 939-Foreign Countries Table 3 (continued) Ex. Physical data and No. R3 R4 Ar n stereochem.

specifications IV-11C2H5 H CI 0 m.p.:126C

(racemate) /

-CI

IV-12C2H5 H ~ CI 0 m.p.:87C

(racemate) IV-13C2H5 H ~ 0 m.p.:100C

/ (racemate) I

IV-14CH3 H ~ 0 m.p.:145C

/ (racemate) I

IV-15CH3 CH3 ~ 0 m.p.:106C

/ (racemate) IV-16C2H5 H CI 0 m.p.:113C

(racemate) /

Le A 32 939-Foreign Countries Table 3 (continued) Ex. Physical data and No. R3 R4 Ar n stereochem.

specifications 1V-17 CH3 H C~ 0 m.p.:135C

(racemate) IV-18 C2H5 H ~ OCH3 0 (oil) (racemate) IV-19 C2H5 H OCH3 0 (oil) (racemate) IV-20 CH3 H ~ OCH3 0 m.p.:133C

(racemate) IV-21 C2H5 H ~ 0 m.p.:180C

( , N (racemate) N-22 C2H5 H ~ \ 0 m.p.:163C

(racemate) N

Le A 32 939-Foreign Countries Table 3 (continued) Ex. Physical data No. R3 R4 Ar n and stereochem.
specifications IV-23C2H5 H ~ CI 0 m.p.:133C

(racemate) ~CI

IV-24C2H5 H ~ CF3 0 (oil) (racemate) Le A 32 939-Foreign Countries _67_ Use Examples:
Example A
Pre-emergence test Solvent: 5 parts by weight of acetone Emulsifier: 1 part by weight of alkylaryl polyglycol ether w 10 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.
Seeds of the test plants are sown in normal soil. After about 24 hours, the soil is sprayed with the preparation of active compound such that the particular amounts of active compound desired are applied per unit area. The concentration of the spray liquor is chosen so that the particular amounts of active compound desired are applied in 10001 of water/ha.
After three weeks, the degree of damage to the plants is rated in % damage in comparison to the development of the untreated control.
The figures denote:
0 % - no effect (like untreated control) 100 % - total destruction In this test, for example, the compounds of Preparation Example 4, 10, 17, 18, 19, 20, 21, 23, 24, 29, 31, 32, 33, 45, 46, 47, 54, 56, 60, 65, 67 and 84 exhibit strong activity against weeds, and some of them are tolerated well by crop plants, such as, for example, maize, wheat and barley.

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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 S-15 cm are sprayed with the preparation of active compound such that the particular amounts of active compound desired are applied per unit area. The concentration of the spray liquor is chosen so that the particular amounts of active compound desired are applied in 10001 of water/ha.
After three weeks, the degree of damage to the plants is rated in % damage in comparison to the development of the untreated control.
The figures denote:
0 % = no effect (like untreated control) 100 % = total destruction In this test, for example, the compounds of Preparation Example 2, 4, 6, 8, 9, 10, 11, 12, 13, 24, 31, 32, 33, 34, 36, 38, 39, 40, 41, 42, 45, 46, 47, 51, 56, 67 and 84 exhibit strong activity against weeds, and some are tolerated well by crop plants, such as, for example, maize, wheat, barley, oilseed rape and sugar beet.

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a~ p v~ oo , cd ~.
O
_'~
v Q., O
O O
"-. Q ~ O O
r. ,..,., O
z z z se z z n ~ Z t~ U Z ~ U
m D
Z = / Z 2 =Z ~ =Z
4. Z
, o U
a.

o; ~' U cn t~
o U
Q

Claims (9)

Claims

1. Substituted 2,4-diamino-1,3,5-triazines of the general formula (I), in which n represents the numbers 0, 1 or 2, R1 represents hydrogen or represents optionally hydroxyl-, cyano-, halogen- or C1-C4-alkoxy-substituted alkyl having 1 to 6 carbon atoms, R2 represents hydrogen, represents formyl or represents in each case optionally cyano-, halogen- or C1-C4-alkoxy-substituted alkyl, alkyl-carbonyl or alkoxycarbonyl having in each case 1 to 6 carbon atoms in the alkyl groups, R3 represents hydrogen or represents optionally hydroxyl-, cyano-, halogen- or C1-C4-alkoxy-substituted alkyl having 1 to 6 carbon atoms or represents optionally cyano-, halogen- or C1-C4-alkyl-substituted cycloalkyl having 3 to 6 carbon atoms, R4 represents hydrogen or represents alkyl having 1 to 4 carbon atoms, Ar represents in each case optionally substituted phenyl, naphthyl or heterocyclyl, where the possible heterocyclyl groupings are preferably selected from the group below:
furyl, benzofuryl, thienyl, benzothienyl, thiazolyl, benzothiazolyl, oxazolyl, benzoxazolyl, thiadiazolyl, oxadiazolyl, pyrazolyl, imidazolyl, tetrazolyl, pyridinyl, quinolinyl and pyrimidinyl, and where the possible substituents are in each case preferably selected from the group below:
hydroxyl, cyano, carbamoyl, thiocarbamoyl, nitro, halogen, in each case optionally hydroxyl-, cyano- or halogen-substituted alkyl or alkoxy having in each case 1 to 6 carbon atoms, in each case optionally halogen-substituted alkylcarbonyl, alkoxycarbonyl, alkylthio, alkylsulphinyl, alkylsulphonyl, dialkylamino, alkylcarbonylamino, alkylsulphonylamino, bis-alkylcarbonyl-amino, bis-alkylsulphonyl-amino, N-alkyl-N-alkylcarbonyl-amino or N-alkyl-N-alkylsulphonyl-amino having in each case 1 to 6 carbon atoms in the alkyl groups, in each case optionally hydroxyl-, cyano-, nitro-, halogen-, C1-C4-alkyl-, C1-C4-halogenoalkyl-, C1-C4-alkoxy- or C1-C4-halogenoalkoxy-substituted phenyl or phenoxy, and in each case optionally halogen-substituted methylenedioxy or ethylenedioxy, and Z represents hydrogen, represents in each case optionally hydroxyl-, cyano-, halogen-, C1-C4-alkoxy-, C1-C4-alkyl-carbonyl-, C1-C4-alkoxy-carbonyl-, C1-C4-alkylthio-, C1-C4-alkylsulphinyl- or C1-C4-alkylsulphonyl-substituted alkyl, alkylcarbonyl or alkoxycarbonyl having in each case 1 to 6 carbon atoms in the alkyl groups, represents in each case optionally cyano-, halogen- or C1-C4-alkoxy-substituted alkenyl or alkinyl having in each case 2 to 6 carbon atoms, or represents optionally cyano-, halogen- or C1-C4-alkyl-substituted cycloalkyl having 3 to 6 carbon atoms.

2. Compounds of the formula (I) according to Claim 1, characterized in that n represents the numbers 0, 1 or 2, R1 represents hydrogen or represents in each case optionally hydroxyl-, cyano-, fluorine-, chlorine-, methoxy- or ethoxy-substituted methyl, ethyl, n- or i-propyl, R2 represents hydrogen, represents formyl or represents in each case optionally cyano-, fluorine-, chlorine-, methoxy- or ethoxy-substituted methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, acetyl, propionyl, n- or i-butyroyl, methoxycarbonyl, ethoxycarbonyl, n- or i-propoxycarbonyl, R3 represents hydrogen or represents in each case optionally hydroxyl-, cyano-, fluorine-, chlorine-, methoxy- or ethoxy-substituted methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, or represents in each case optionally cyano-, fluorine-, chlorine-, methyl- or ethyl-substituted cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl, R4 represents hydrogen, methyl or ethyl, Ar represents in each case optionally substituted phenyl, naphthyl or heterocyclyl, where the possible heterocyclyl groupings are selected from the group below:

furyl, benzofuryl, thienyl, benzothienyl, thiazolyl, benzothiazolyl, oxazolyl, benzoxazolyl, pyrazolyl, imidazolyl, tetrazolyl, pyridinyl, quinolinyl and pyrimidinyl, and where the possible substituents are in each case selected from the group below:
hydroxyl, cyano, carbamoyl, thiocarbamoyl, nitro, fluorine, chlorine, bromine, in each case optionally hydroxyl-, cyano-, fluorine-, chlorine- or bromine-substituted methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, methoxy, ethoxy, n- or i-propoxy, in each case optionally fluorine- and/or chlorine-substituted acetyl, propionyl, n-or i-butyroyl, methoxycarbonyl, ethoxycarbonyl, n- or i-propoxycarbonyl, methylthio, ethylthio, n- or i-propylthio, methylsulphinyl, ethylsulphinyl, n- or i-propylsulphinyl, methylsulphonyl, ethylsulphonyl, n-or i-propylsulphonyl, dimethylamino, diethylamino, acetylamino, propionyl-amino, n- or i-butyroylamino, methylsulphonylamino, ethylsulphonylamino, n- or i-propylsulphonylamino, bis-acetyl-amino, bis-propionyl-amino, bis-methylsulphonyl-amino, bis-ethylsulphonyl-amino, N-methyl-N-acetyl-amino, N-ethyl-N-acetyl-amino, N-methyl-n-propionyl-amino, N-methyl-N-ethylsulphonyl-amino, N-ethyl-N-methylsulphonyl-amino or N-methyl-N-ethylsulphonyl-amino, in each case optionally 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 in each case optionally fluorine- and/or chlorine-substituted methylenedioxy or ethylene-dioxy, and Z represents hydrogen, represents in each case optionally hydroxyl-, cyano-, fluorine-, chlorine-, bromine-, methoxy-, ethoxy-, n- or i-propoxy-, acetyl-, propionyl-, n- or i-butyroyl-, methoxycarbonyl-, ethoxycarbonyl-, n- or i-propoxy-carbonyl-, methylthio-, ethylthio-, n- or i-propylthio-, methylsulphinyl-, ethylsulphinyl-, n- or i-propyl-sulphinyl-, methylsulphonyl-, ethylsulphonyl-, n- or i-propyl-sulphonyl-substituted methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, acetyl, propionyl, n- or i-butyroyl, methoxycarbonyl, ethoxycarbonyl, n- or i-propoxycarbonyl, represents in each case optionally cyano-, fluorine-, chlorine-, bromine-, methoxy- or ethoxy-substituted ethenyl, propenyl, butenyl, ethinyl, propinyl or butinyl, or represents in each case optionally cyano-, fluorine-, chlorine-, methyl- or ethyl-substituted cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl.

3. Compounds of the formula (I) according to Claim 1, characterized in that n represents the numbers 0, 1 or 2, R1 represents hydrogen, R2 represents hydrogen, represents formyl or represents in each case optionally cyano-, fluorine-, chlorine-, methoxy- or ethoxy-substituted acetyl, propionyl, n- or i-butyroyl, methoxycarbonyl, ethoxycarbonyl, n- or i-propoxycarbonyl, R3 represents methyl, ethyl, n- or i-propyl, R4 represents hydrogen, Ar represents in each case optionally substituted phenyl, naphthyl or heterocyclyl, where the possible heterocyclyl groupings are selected from the groups below:
furyl, benzofuryl, thienyl, benzothienyl, thiazolyl, benzothiazolyl, oxazolyl, benzoxazolyl, tetrazolyl, pyridinyl, quinolinyl and pyrimidinyl, and where the possible substituents are in each case selected from the group below:
cyano, carbamoyl, thiocarbamoyl, nitro, fluorine, chlorine, bromine, in each case optionally cyano-, fluorine- or chlorine-substituted methyl, ethyl, n- or i-propyl, methoxy, ethoxy, in each case optionally fluorine- and/or chlorine-substituted acetyl, propionyl, methoxycarbonyl, ethoxycarbonyl, methylthio, ethylthio, methylsulphinyl, ethylsulphinyl, methylsulphonyl, ethylsulphonyl, dimethylamino, acetylamino, propionylamino, methylsulphonylamino or ethylsulphonylamino, in each case optionally cyano-, nitro-, fluorine-, chlorine-, bromine-, methyl-, ethyl-, n- or i-propyl-, trifluoromethyl-, methoxy-, ethoxy-, difluoromethoxy- or trifluoromethoxy-substituted phenyl or phenoxy, and in each case optionally fluorine- and/or chlorine-substituted methylenedioxy or ethylenedioxy, and Z represents in each case optionally hydroxyl-, cyano-, fluorine-, chlorine-, bromine-, methoxy-, ethoxy-, acetyl-, propionyl-, methoxycarbonyl-, ethoxycarbonyl-, methylthio-, ethylthio-, methylsulphinyl-, ethylsulphinyl-, methylsulphonyl- or ethylsulphonyl-substituted methyl, ethyl, n- or i-propyl.

4. Process for preparing compounds of the formula (I) according to Claim 1, characterized in that biguanides of the general formula (II) in which n, R1, R2, R3, R4 and Ar are as defined in Claim 1 - and/or acid adducts of compounds of the general formula (II)- are reacted with alkoxycarbonyl compounds of the general formula (III) Z-CO-OR' (III) in which Z is as defined in Claim 1 and R' represents alkyl, if appropriate in the presence of a reaction auxiliary and if appropriate in the presence of a diluent, and, if appropriate, further conversions within the scope of the definition of substituents are carried out by customary methods on the resulting compounds of the general formula (I).

5. Herbicidal compositions, characterized in that they comprise at least one compound of the formula (I) according to Claim 1.

6. Use of compounds of the formula (I) according to Claim 1 for controlling undesirable vegetation.

7. Method for controlling weeds, characterized in that compounds of the formula (I) according to Claim 1 are allowed to act on the weeds or their habitat.

8. Process for preparing herbicidal compositions, characterized in that compounds of the formula (I) according to Claim 1 are mixed with extenders and/or surfactants.

9. Biguanides of the general formula (II) in which n, R1, R2, R3, R4 and Ar are as defined in Claim 1, and acid adducts of compounds of the general formula (II).