AU717425B2 - Substituted thienylsulphonyl (thio) ureas as herbicides - Google Patents

Description

WO 97/32875 PCT/EP97/00877 SUBSTITUTED THIENYLSULPHONYL (THIO) UREAS AS HERBICIDES The invention relates to novel substituted thienylsulphonyl(thio)ureas, to processes for their preparation and to their use as herbicides.

It is already known that certain substituted thienylsulphonylureas, such as, for example, the compound N-(4-cyclopropyl-6-methoxy-1,3,5-triazin-2-yl)-N'-(2-methoxycarbonyl-4methyl-thien-3-yl-sulphonyl)-urea, have herbicidal properties (cf. EP 207609, cf. also EP 30142). However, the herbicidal activity of these known compounds is not satisfactory in all aspects.

This invention, accordingly, provides the novel substituted thienylsulphonyl(thio)ureas of the general formula (I)

R'

A N Q

R

4

R

3 H

S

0 S 0-R in which A represents nitrogen or a CH grouping, Q represents oxygen or sulphur, R' represents hydrogen, halogen or respectively optionally substituted alkyl, alkoxy, alkylthio, alkylamino, dialkylamino, cycloalkyl, cycloalkyloxy, aryloxy or heterocyclyloxy,

R

2 represents hydrogen, halogen or respectively optionally substituted alkyl, alkoxy, alkylthio, alkylamino, dialkylamino, cycloalkyl, cycloalkyloxy, aryloxy or heterocyclyloxy, 2- R 3 represents hydrogen or optionally substituted alkyl, R 4 represents optionally substituted alkyl and

R

5 represents hydrogen or respectively optionally substituted alkyl, alkenyl, alkinyl, cycloalkyl, cycloalkylalkyl or heterocyclyl, and salts of compounds of the formula except for the prior-art compounds N-(4-methoxy-6-methyl-pyrimidin-2-yl)-N'-[2-(2chloro-ethoxycarbonyl)-4-methyl-thien-3-yl-sulphonyl] -urea, N-(4-methoxy-6-methylpyrimidin-2-yl)-N'-(4-ethyl-2-i-propoxycarbonyl-thien-3-yl-sulphonyl)-urea, N-(4methoxy-6-methyl-pyrimidin-2-yl)-N'-(2-allyloxycarbonyl-4-n-butyl-thien-3-ylsulphonyl)-urea, N-(4-methoxy-6-methyl-pyrimidin-2-yl)-N'(2-methoxycarbonyl-4-ipropyl-thien-3-yl-sulphonyl)-urea and N-(4-methoxy-6-methyl-pyrimidin-2-yl)-N t methoxycarbonyl-4-trifluoromethyl-thien-3-yI-sulphonyl)-urea (cf. EP 30142), and also the likewise prior-art compounds N-(4-cyclopropyl-6-methoxy-pyrimidin-2-yl)-N'-(4methyl-2-n-propoxycarbonyl-thien-3-yl-sulphonyl)-urea, N-(4-cyclopropyl-6-methylpyrimidin-2-yl)-N'-(2-methoxycarbonyl-4-methyl-thien-3-yl-sulphonyl)-urea, N-(4cyclopropyl-6-methoxy-pyrimidin-2-yl)-N'-(2-methoxycarbonyl-4-methyl-thien-3-ysulphonyl)-urea, N-(4-cyclopropyl-6-methoxy- 1,3,5-triazin-2-yI)-N'-(2-methoxycarbonyl- 4-methyl-thien-3-yl-sulphonyl)-urea, N-(4-cyclopropyl-6-methyl- 1,3 ,5-triazin-2-yl)-N'- (2-methoxycarbonyl-4-methyl-thien-3-yl-sulphonyl)-urea and N-(4-cyclopropyl-6methoxy- 1 ,3,5-triazin-2-yl)-N'-(2-i-propoxycarbonyl-4-methyl-thien-3-yl-sulphonyl)-urea (cf. EP 207609), which are excluded by disclaimer.

The novel substituted thienylsulphonyl(thio)ureas of the general formnula are obtained when aminoazines of the general formula (11) -3-

R

I

A' N (I) in which

R

2 N NMH A, R' and R 2 are each as defined above, are reacted with thienylsulphonyl iso(thio)cyanates of the general formula (III)

R

4 Q=C=N-SO, (11)

S

0 s

O

O-R

s in which Q, R 4 and R 5 are each as defined above, if appropriate in the presence of a reaction auxiliary and if appropriate in the presence of a diluent, or substituted aminoazines of the general formula (IV)

R

1 A N

Q

R

in which -4- A, Q, R' and R 2 are each as defined above, Z represents halogen, alkoxy or aryloxy and R has the meaning given above for R 3 or represents grouping -C(Q)-Z are reacted with thiophenesulphonamides of the general formula (V)

R

4 NH

R

so 2 Mv)

S

0 !P

O-R

in which

R

4 and R 5 are each as defined above, if appropriate in the presence of a reaction auxiliary and if appropriate in the presence of a diluent, or aminoazines of the general formula (II)

R

A N

R

2 AN ONH in which A, R' and R 2 are each as defined above, are reacted with substituted thiophenesulphonamides of the general formula (VI) 4 Q R 4 .A so, (v) in which Q, R 4 and R 5 are each as defined above and Z represents halogen, alkoxy or aryloxy, if appropriate in the presence of a reaction auxiliary and if appropriate in the presence of a diluent, and the compounds of the formula obtained by processes and are optionally converted into salts by customary methods.

The novel substituted thienylsulphonyl(thio)ureas of the general formula have strong herbicidal activity.

The invention preferably provides compounds of the formula in which A represents nitrogen or a CH grouping, Q represents oxygen or sulphur, R' represents hydrogen, halogen, represents respectively optionally cyano-, halogen- or C-C 4 -alkoxy-substituted alkyl, alkoxy, alkylthio, alkylamino or dialkylamino having in each case 1 to 4 carbon atoms in the alkyl groups, represents respectively optionally cyano-, halogen-, Ci-C 4 -alkyl- or C,-C4 -6alkoxy-substituted cycloalkyl or cycloalkyloxy having in each case 3 to 6 carbon atoms, or represents respectively optionally cyano-, halogen-, C,-C 4 alkyl- or C-C 4 -alkoxy-substituted phenoxy, oxetanyloxy, furyloxy or tetrahydrofuryloxy,

R

2 represents hydrogen or halogen, represents respectively optionally cyano-, halogen- or Cl-C 4 -alkoxy-substituted alkyl, alkoxy, alkylthio, alkylamino or dialkylamino having in each case I to 4 carbon atoms in the alkyl groups, represents respectively optionally cyano-, halogen-, Cl-C 4 -alkyl- or C,-C4 alkoxy-substituted cycloalkyl or cycloalkyloxy having in each case 3 to 6 carbon atoms, or represents respectively optionally cyano-, halogen-, C 1

-C

4 alkyl- or Cl-C 4 -alkoxy-substituted phenoxy, oxetanyloxy, furyloxy or tetrahydrofuryloxy,

R

3 represents hydrogen or optionally C 1

-C

4 -alkoxy-, Cl-C 4 -alkyl-carbonyl- or CI-C4 alkoxy-carbonyl-substituted alkyl having 1 to 4 carbon atoms,

R

4 represents optionally cyano-, halogen- or C-C 4 -alkoxy-substituted alkyl having 1 to 6 carbon atoms and

R

5 represents hydrogen, represents optionally cyano-, halogen- or CI-C 4 -alkoxysubstituted alkyl having I to 6 carbon atoms, represents respectively optionally halogen-substituted alkenyl or alkinyl having in each case 2 to 6 carbon atoms, represents respectively optionally cyano-, halogen- or C 1

-C

4 -alkyl-substituted cycloalkyl or cycloalkylalkyl having in each case 3 to 6 carbon atoms in the cycloalkyl groups and optionally 1 to 4 carbon atoms in the alkyl moiety, or represents respectively optionally cyano-, halogen-, Cl-C 4 -alkyl- or C,-C 4 alkoxy-substituted oxetanyl, furyl or tetrahydrofuryl, except for the prior-art compounds N-(4-methoxy-6-methyl-pyrimidin-2-yl)-N'-[ 2 2 chloro-ethoxycarbonyl)-4-methyl-thien-3-yl-sulphonyl]-urea, N-(4-methoxy-6-methylpyrimidin-2-yl)-N'-(4-ethyl-2-i-propoxycarbonyl-thien-3-yl-sulphonyl)-urea, N-(4- 7methoxy-6- methylI-pyrimi din -2-y allIyl oxycarbon ylI-4-n -butylI-th ien- 3-yl sulphonyl)-urea, N-(4-methoxy-6-methyl-pyrimidin-2-yl)-N'(2-methoxycarbonyl-4-ipropyl-thien-3-yl-sulphonyl)-urea and N-(4-methoxy-6-methyl-pyrimidin-2-yl)-N'-(2methoxycarbonyl-4-trifluoromethyl-thien-3-yl-sulphonyl)-urea (cf. EP 30142), and also the likewise prior-art compounds N-(4-cyclopropyl-6-methoxy-pyrimidin-2-yl)-N'-(4methyl-2-n-propoxycarbonyl-thien-3-yl-sulphonyl)-urea, N-(4-cyclopropyl-6-methylpyrimidin-2-yl)-N'-(2-methoxycarbonyl-4-methyl-thien-3-yl-sulphonyl)-urea, N-(4cyclopropyl-6-methoxy-pyrimidin-2-yl)-N'-(2-methoxycarbonyl-4-methyl- thien-3-ylsulphonyl)-urea, N-(4-cyclopropyl-6-methoxy- 1,3,5-triazin-2-yl)-N'-(2-methoxycarbonyl- 4-methyl-thien-3-yl-sulphonyl)-urea, N-(4-cyclopropyl-6-methyl- 1,3,5-triazin-2-yl)-N'- (2-methoxycarbonyl-4-methyl-thien-3-yl-sulphonyl)-urea and N-(4-cyclopropyl-6methoxy- I ,3,5-triazin-2-yl)-N'-(2-i-propoxycarbonyl-4-methyl-thien-3-yl-sulphonyl)-urea (cf. EP 207609), which are excluded by disclaimer.

The invention furthermore preferably provides sodium, potassium, magnesium, calcium, ammonium, C -C 4 -alkyl-ammonium, di-(CF 1

C

4 -alkyl)-ammonium, tri-(C 1

-C

4 -alkyl)ammonium, tetra-(C 1

-C

4 -alkyl)-ammonium, tri-(C 1

-C

4 -alkyl)-sulphonium, C 5 or C 6 cycloalkyl-ammonium and di-(C -C 2 -alkyl)-benzyl -ammonium salts of compounds of the formula in which A, Q, R 2

R

4 and R 5 are each preferably as defined above.

The invention in particular provides compounds of the formula in which A represents nitrogen or a CH grouping, Q represents oxygen or sulphur, R' represents hydrogen, fluorine, chlorine, bromine or respectively optionally cyano-, fluorine-, chlorine-, methoxy- or ethoxy-substituted methyl, ethyl, n- or i-propyl, methoxy, ethoxy, n- or i-propoxy, methylthio, ethylthio, n- or ipropylthio, methylamino, ethylamino, n- or i-propylamino, dimethylamino or diethylamino, -8 R 2 represents fluorine, chlorine, bromine or respectively optionally cyano-, fluorine-, chlorine-, methoxy- or ethoxy-substituted methyl, ethyl, n- or i-propyl, methoxy, ethoxy, n- or 1-propoxy, methylthio, ethylthio, n- or i-propylthio, methylamino, ethylamino, n- or i-propylamino, dimethylamino or diethylamino, R' represents hydrogen or optionally methoxy-, ethoxy-, n- or i-propoxy-, acetyl-, propionyl, n- or i-butyroyl-, methoxycarbonyl-, ethoxycarbonyl-, n- or ipropoxycarbonyl-substituted methyl or ethyl, R' represents respectively optionally cyano-, fluorine-, chlorine-, methoxy- or ethoxy-substituted methyl, ethyl, n- or i-propyl, s- or t-butyl, and R 5 represents hydrogen, represents respectively optionally cyano-, fluorine-, chlorine-, methoxy-, ethoxy-, n- or i-propoxy-substituted methyl, ethyl, n- or i propyl, s- or t-butyl, represents respectively optionally fluorine-, chlorineor bromine-substituted propenyl, butenyl, propinyl or butinyl, or represents respectively optionally cyano-, fluorine-, chlorine-, bromine-, methyl-, ethyl-, nor i-propyl-substituted cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl or cyclohexylmethyl, except for the prior-art compounds N-(4-methoxy-6-methyl-pyrimidin-2-yl)-N'-[2-(2chiloro-ethoxycarbonyl)-4-methyl-thien-3 -yl-sulphonyl] -urea, N-(4-methoxy-6-methylpyrimi din- 2-yl)-N'-(4-ethyl -2 -i -propoxycarbonylI-thien- 3-yl -sulphonyl)-urea, N-(4methoxy-6-methyl-pyrimidin-2-yI)-N'-(2-allyloxycarbonyl-4-n-butyl-thien-3-ylsulphonyl)-urea, N-(4-methoxy-6-methyl-pyrimidin-2-yl)-N'(2-methoxycarbonyl-4-ipropyl-thien-3-yl-sulphonyl)-urea and N-(4-methoxy-6-methyl-pyrimidin-2-yl)-N'-(2methoxycarbonyl-4-trifluoromethyl-thien-3-yl-sulphonyl)-urea (cf. EP 30142), and also the likewise prior-art compounds N-(4-cyclopropyl-6-methoxy-pyrimidin-2-yl)-N'-(4methyl-2-n-propoxycarbonyl-thien-3-yl-sulphonyl)-urea, N-(4-cyclopropyl-6-methylpyrimidi n- (2 -methoxycarbon yl-4-methyl -th ien-3 -yl -sul phonyI)-urea, N-(4cyclopropyl-6-methoxy-pyrimidin-2-yl)-N'-(2-methoxycarbonyl-4-methyl-thien-3-ylsulphonyl)-urea, N-(4-cyclopropyl-6-methoxy-1I,3,5-triazin-2-yI)-N'-(2-methoxycarbonyl- WO 9lh23SAc IMfl99 -9- 4-methyl-thien-3-yI-sulphonyl)-urea, N-(4-cyclopropyl-6-methyl-1I,3,5-triazin-2-yl)- N'-(2-methoxycarbonyl-4-methyl-thein-3-yl-sulphonyl)-urea and N-(4-cycloproy- 6-methoxy- 1,3,5-triazin-2-yl)-N'-(2-i-propoxycarbonyl-4-methyl-thein-3-ylsuiphonyl)_urea (cf. EP 207609), which are excluded by disclaimer.

The invention further provides, substituted thienylsulphonyl(thio)ureas of the general formula (I) in which *A represents nitrogen, S 20 Q represents oxygen or sulphur, represents hydrogen, fluorine, chlorine, bromine or respectively optionally 25cyano-, fluorine-, chlorine-, methoxy- or ethoxy-substituted methyl, ethyl, noi-propyl, methoxy, ethoxy, n- or i-propoxy, methylthio, ethylthio, n- or i- 21- propylthio, methylamino, ethylamino, n- or i-propylamino, dimethylamnino, or diethylamino, R represents fluorine, chlorine, bromine or respectively optionally cyano-, fluorine-, chlorine-, methoxy- or ethoxy-substituted methyl, ethyl, n- or i-propyl, methoxy, ethoxy, n- or i-propoxy, methylthio, ethylthio, n- or i-propylthio, methylamino, ethylamino, n- or i-propylamnino, dimethylamino or diethylamino, WO 97 32175 i .IIVi 9a

R

3 represents hydrogen or optionally metlioxy-, ethoxy-, n- or i-propoxy-, acetyl-, propionyl, n- or i-butyroyl-, nithoxycarbonyl-, ethoxycarbonyl:, d- or i-propoxycarbonyl-substituted methyl or ethyl,

R

4 represents .methyl, ethyl, n- or i-propyi, nisort-butyl, and

R

5 r epresents respectively optionally cymno-, fluorine-, chlorine-, methoxy-, ID) ethoxy-, n- or i-propoxy-substituted ethyl, or i-propyl, and salts of compounds of the formula 15 The abovementioned general or preferred radical definiftions: apply both to the end products of the formula and, correspondingly, to the starting materials or a...intermediates required in each case for. the preparation. These radical definitions can be combined with each other as desired, that is to say combinations between the stated-ranges of preferred compounds are also possible.

Examples of compounds of the formula according to the invention are listed in the groups below.

10 Group 1 AZ 'N Q H 31

R

3

H

O-C43 A, Q, R 2 and R' have, for example, the meaning listed below: A Q R 2R Cli 0 OCH 3 OCH3 H Cli 0 CH 3

OCH

3

H

Cli 0 CH 3

CH

3

H

CHi 0 CI OCH 3

H

CH 0 H CH 3

H

N 0 CH 3 0CH 3

CH

3 N 0 0CM 3 0CM 3

CM

3 N 0 CH 3 0CM 3

H

N 0 OCH 3 0CH 3

H

N 0 CH 3

CM

3

H

N 0 CH2 N(CH3)2 H N 0 CUi 3

SCM

3

H

N 0 CAM 0CM 3

H

N 0 CM 3 0CAH H N 0 H OCM3 H N 0 0CM 3

H

0

CH

3 N(M)

H

N(CH3)2 H 11

OCH

3 0 Cl 0

H

0 ml

H

0 ml

H

0 ml 0 ml 0 ml 0 0mf 0 0mf

C[H

3

H

CH

3 N(CHi)

N(CH

3 2 OCH3

OCH

2

CF

3

OCAH

12 Group 2 A'N a CH 3 R2~N~ V~N2([A-2) 13 I R H s 0 A, Q, R 2 and R' have, for example, the meaning given above in Group 1.

Group 3 A ~N a CH 3 N N' -k.-S2 N([A-3) I3 I R0 H S 0 A, Q, R 2 and R' have, for example, the meaning given above in Group 1.

Group 4 A'N Q CH 3

R

2 .ZW N NAN N (A-4) 4 3 H S 0 A, Q, R 2 and R' have, for example, the meaning given above in Group 1.

13 Group A N a OH, RH S 0: 0\D A, Q, R 2 and R' have, for example, the meaning given above in Group 1.

Group 6 R 2 N IL N N (I.8 I3 1 R' H S 0 0-CM, A, Q, R 2 and R 3 have, for example, the meaning given above in Group 1.

Group 7

R

2

N

13 1 R3 H A, Q, R 2 and R 3 have, for example, the meaning given above in Group 1.

14 Group 8 A N a cps R-kN-j %NS2 N (A-8) 1 3 1 R H 08\ A, Q, R 2 and R' have, for example, the meaning given above in Group 1.

Group 9 A N CA R2'4N-!-N)N9o (LA-9) R0 H

S

0 A, Q, R 2 and R' have, for example, the meaning given above in Group 1.

Group A N 0 C

I

2

N

Oe H 0:A\ O\0 A, Q, R' and R 3 have, for example, the meaning given above in Group 1.

15 Group I11 A" N a CF 3 I I RH

S

0 0

-CH

3 A, Q, R 2 and R 3 have, for example, the meaning given above in Group 1.

Group 12 N Q C 3 R2"ZN- WSO2(IA-12) I3 I R: H S

C-

A, Q, R 2 and R 3 have, for example, the meaning given above in Group 1.

Group 13 31 A" N Q CF 3 -2 iS. l 2 IS02 1 (IA- 13) A, Q, R' and R 3 have, for example, the meaning given above in Group 1.

16- Group 14 (IA-14) A, Q, R 2 and R 3 have, for example, the meaning given above in Group 1.

Group At'kN a R2 -kNA 2-> .4X,13 0 A, Q, R 2 and R 3 have, for example, the meaning given above in Group 1.

Using, for example, 2-amino-4-methoxy-6-methyl-pyrimidine and 2-ethoxycarbonyl-4trifluoromethyl-thien-3-yl-sulphonyl isocyanate as starting materials, the course of the reaction in the process according to the invention can be illustrated by the following equation: 17-

OCH

3

CF

3

O=CNSO

2

H

2 C No% NH 2 0-

CH

OCHS

V N 0 CF 3

H

3 C N N N" H H S O-C 2

HS

Using, for example, 2-methoxycarbonylamino-4-methoxy-6-trifluoromethyl-1,3,5triazine and 4-ethyl-2-i-propoxycarbonyl-thiophene-3-sulphonamide as starting materials, the course of the reaction in the process according to the invention can be illustrated by the following equation:

OCX,

Nk N 0+ FC N N OCM

H

OCH

3 Nl% N 0

-MOCH

3

F

3 C N N N I I H H Using, for example, 2-amino-4-chloro-6-methoxy-pyrimidine and N-(2-ethoxycarbonyl- 4-methyl-thien-3-yl-sulphonyl)-O-phenyl-urethane as starting materials, the course of the reaction in the process according to the invention can be illustrated by the following equation: ocKS

CM

3 I I H H

O-C

2

H

O-Ct The formula (II) provides a general definition of the aminoazines to be used as starting materials in the process and according to the invention for preparing the compounds of the general formula In the formula A, R' and R 2 each preferably or in particular have those meanings which have already been indicated above, in connection with the description of the compounds of the formula as being preferred or particularly preferred for A, R' and R 2 18 The aminoazines of the formula (II) are known chemicals for synthesis, some of which are commercially available.

The formula (III) provides a general definition of the thienylsulphonyl iso(thio)cyanates further to be used as starting materials in the process according to the invention. In the formula (III), Q, R 4 and R 5 each preferably or in particular have those meanings which have already been indicated above, in connection with the description of the compounds of the formula as being preferred or particularly preferred for Q, R 4 and

R

5 The starting materials of formula (III) are known and/or can be prepared by processes known per se (cf. EP 30142).

The thienylsulphonyl iso(thio)cyanates of the formula (III) are obtained when thiophenesulphonamides of the general formula above are reacted with phosgene or thiophosgene, if appropriate in the presence of an alkyl isocyanate, such as, for example, butyl isocyanate, if appropriate in the presence of a reaction auxiliary, such as, for example, diazabicyclo[2.2.2]octane, and in the presence of a diluent, such as, for example, toluene, xylene or chlorobenzene, at temperatures between 80°C and 150 0

C,

and the volatile components are distilled off under reduced pressure after the reaction has ended.

The formula (IV) provides a general definition of the substituted aminoazines to be used as starting materials in the process according to the invention for preparing compounds of the formula In the formula A, Q, R 2 and R each preferably or in particular have those meanings which have already been indicated above, in connection with the description of the compounds of the formula as being preferred or particularly preferred for A, Q, R 2 or R 3 where R may also represent Z preferably represents fluorine, chlorine, bromine, C,-C 4 -alkoxy or phenoxy, in particular chlorine, methoxy, ethoxy or phenoxy.

The starting materials of the formula (IV) are known and/or can be prepared by 19processes known per se (cf. US 4690707, DE 19501174, Preparation Examples).

The formula provides a general definition of the thiophenesulphonamides further to be used as starting materials in the process according to the invention. In the formula R 4 and R 5 each preferably or in particular have those meanings which have already been indicated above, in connection with the description of the compounds of the formula as being preferred or particularly preferred for R 4 and

R

5 The starting materials of the formula are known and/or can be prepared by processes known per se (cf. EP 30142).

The formula (VI) provides a general definition of the substituted thiophenesulphonamides to be used as starting materials in the process according to the invention for preparing the compounds of the formula In the formula Q,

R

4 and R 5 each preferably or in particular have those meanings which have already been indicated above, in connection with the description of the compounds of the formula as being preferred or particularly preferred for Q, R 4 and R 5 Z preferably represents fluorine, chlorine, bromine, C 1

-C

4 -alkoxy or phenoxy, in particular chlorine, methoxy, ethoxy or phenoxy.

The starting materials of formula (VI) are known and/or can be prepared by processes known per se.

Suitable diluents for carrying out the processes and according to the invention are 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; nitriles, such as acetonitrile, propionitrile or benzonitrile; amides, such as N,Ndimethylformamide, N,N-dimethylacetamide, N-methyl-formanilide, N-methylpyrrolidone or hexamethylphosphoric triamide; esters such as methyl acetate or ethyl acetate; sulphoxides, such as dimethyl sulphoxide; 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.

The processes and according to the invention are preferably carried out in the presence of a suitable reaction auxiliary. Suitable reaction auxiliaries are all customary inorganic or organic bases. These include, for example, alkaline earth metal or alkali metal hydrides, hydroxides, amides, alkoxides, acetates, carbonates or dicarbonates, such as, for example, sodium hydride, sodium amide, sodium methoxide, sodium ethoxide, potassium tert-butoxide, sodium hydroxide, potassium hydroxide, ammonium hydroxide, sodium acetate, potassium acetate, calcium acetate, ammonium acetate, sodium carbonate, potassium carbonate, potassium bicarbonate, sodium bicarbonate or ammonium carbonate and also tertiary amines, such as trimethylamine, triethylamine, tributylamine, N,N-dimethylaniline, pyridine, N-methylpiperidine, N,Ndimethylaminopyridine, diazabicyclooctane (DABCO), diazabicyclononene (DBN) or diazabicycloundecene (DBU).

When carrying out the processes and according to the invention, the reaction temperatures can be varied within a relatively wide range. In general, the reaction is carried out at temperatures between -20 0 C and +150 0 C, preferably between 0°C and +120 0

C.

The processes and 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 in general between 0.1 bar and bar.

In the practice of the processes and according to the invention, the starting materials are generally employed in approximately equimolar amounts. However, it is -21 also possible to employ one of the components in a relatively large excess. The reaction is generally carried out in a suitable solvent in the presence of a reaction auxiliary, and the reaction mixture is generally stirred for a number of hours at the temperature required. Work-up is carried out by customary methods (cf. the Preparation Examples).

If required, salts of the compounds of the general formula according to the invention can be prepared. Such salts are obtained in a simple manner by customary methods of forming salts, for example by dissolving or dispersing a compound of the formula in a suitable solvent, such as, for example, methylene chloride, acetone, tert-butyl methyl ether or toluene, and addition of a suitable base. The salts can then be isolated if required after prolonged stirring by concentration or filtration with suction.

The active compounds according to the invention can be used as defoliants, desiccants, haulm killers and, especially, as weedkillers. By weeds in the broadest sense, there are to be understood all plants which grow in locations 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 connection with the following plants: 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 and Taraxacum.

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

-22- Monocotyledonous weeds of the genera: 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 and Apera.

Monocotyledonous crops of the genera: Oryza, Zea, Triticum, Hordeum, Avena, Secale, Sorghum, Panicum, Saccharum, Ananas, Asparagus and 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.

The compounds are suitable, depending on the concentration, for the total control of weeds, for example on industrial terrain and railway tracks, and on paths and squares with or without tree plantings. Equally, the compounds can be employed for controlling weeds in perennial cultures, for example forests, decorative 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, sports fields and pasture-land. Furthermore, the compounds can also be used for the selective control of weeds in annual cultures.

The compounds of the formula according to the invention are suitable for controlling monocotyledonous and dicotyledonous weeds, both pre-emergence and postemergence. They have strong herbicidal activity and a broad activity spectrum when applied to the soil and to above-ground parts of plants.

The active compounds can be converted into the customary formulations, such as solutions, emulsions, wettable powders, suspensions, powders, dusting agents, pastes, soluble powders, granules, suspo-emulsion concentrates, natural and synthetic materials impregnated with active compound, and very fine capsules in polymeric substances.

These formulations are produced in a known manner, for example by mixing the active 23compounds with extenders, that is liquid solvents and/or solid carriers, optionally with the use of surfactants, that is emulsifiers and/or dispersing agents and/or foam-forming agents.

If the extender used is water, it is also possible to use for example organic solvents as auxiliary solvents. Essentially, suitable liquid solvents 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 their ethers and esters, ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents, such as dimethylformamide and dimethyl sulphoxide, and also 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 and fractionated natural rocks such as calcite, marble, pumice, sepiolite and dolomite, and also 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-forming agents are: for example nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkylsulphonates, alkyl sulphates, arylsulphonates as well as protein hydrolysates; suitable dispersing agents are: for example lignin-sulphite waste liquors and methylcellulose.

Tackifiers such as carboxymethylcellulose and natural and synthetic polymers in the form of powders, granules or latexes, such as gum arabic, polyvinyl alcohol and polyvinyl acetate, and natural phospholipids, such as cephalins and lecithins, and -24synthetic phospholipids, can be used in the formulations. Possible further additives are mineral and vegetable oils.

It is possible to use colorants such as inorganic pigments, for example iron oxide, titanium oxide and Prussian Blue, and organic dyes, such as alizarin dyes, azo dyes and metal phthalocyanine dyes, and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.

The formulations in general contain between 0.1 and 95 per cent by weight of active compound, preferably between 0.5 and 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 anilides, such as diflufenican and propanil; arylcarboxylic acids, such as dichloropicolinic acid, dicamba and picloram; aryloxyalkanoic acids, such as 2,4-D, 2,4-DB, 2,4-DP, fluroxypyr, MCPA, MCPP and triclopyr; aryloxy-phenoxy-alkanoic esters, such as diclofop-methyl, fenoxaprop-ethyl, fluazifop-butyl, haloxyfop-methyl and quizalofopethyl; azinones, such as chloridazon and norflurazon; carbamates, such as chlorpropham, desmedipham, phenmedipham and propham; chloroacetanilides, such as alachlor, acetochlor, butachlor, metazachlor, metolachlor, pretilachlor and propachlor; dinitroanilines, such as oryzalin, pendimethalin and trifluralin; diphenyl ethers, such as acifluorfen, bifenox, fluoroglycofen, fomesafen, halosafen, lactofen and oxyfluorfen; ureas, such as chlorotoluron, diuron, fluometuron, isoproturon, linuron and methabenzthiazuron; hydroxylamines, such as alloxydim, clethodim, cycloxydim, sethoxydim and tralkoxydim; imidazolinones, such as imazethapyr, imazamethabenz, imazapyr and imazaquin; nitriles, such as bromoxynil, dichlobenil and ioxynil; oxyacetamides, such as mefenacet; sulphonylureas, such as amidosulfuron, bensulfuronmethyl, chlorimuron-ethyl, chlorsulfuron, cinosulfuron, metsulfuron-methyl, nicosulfuron, primisulfuron, pyrazosulfuron-ethyl, thifensulfuron-methyl, triasulfuron and tribenuron-methyl; thiocarbamates, such as butylate, cycloate, diallate, EPTC, esprocarb, molinate, prosulfocarb, thiobencarb and triallate; triazines, such as atrazine, cyanazine, simazine, simetryne, terbutryne and terbutylazine; triazinones, such as hexazinone, metamitron and metribuzin; and others, such as aminotriazole, benfuresate, bentazone, cinmethylin, clomazone, clopyralid, difenzoquat, dithiopyr, ethofumesate, fluorochloridone, glufosinate, glyphosate, isoxaben, pyridate, quinchlorac, quinmerac, sulphosate and tridiphane.

Mixtures with other known active compounds, such as fungicides, insecticides, acaricides, nematicides, bird repellents, plant nutrients and agents which improve soil structure, are 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 or scattering.

The active compounds according to the invention can be applied either before or 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 substantial 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 5 kg per ha.

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

26 Preparationl Examples: CH-3 1 1 H4 H S 0 O-C4 3 (Process 1.24 g (10 mmol) of 2-amino-4,6-dimethyl-1,3,5-triazine are initially charged in 40 ml of acetonitrile, and 2.61 g (10 mmol) of 2-methoxycarbonyl-4-methyl-thien-3-ylsuiphonyl isocyanate are added at room temperature (about 20'C). The mixture is heated under reflux for 12 hours and the resulting crystalline product is then isolated by filtration with suction.

This gives 2.6 g (68% of theory) of N-(4,6-dimethyl-1,3,5-triazin-2-yl)-N'-(2methoxycarbonyl-4-methyl-thien-3-yl-sulphonyl)-urea of melting point 21 0 0

C.

27 Example 2

OCN

N"'N 0 CH3 I I H H S O-C^-4 (Process 1.30 g (3.9 mmol) of N,N-bis-phenoxycarbonyl-2-amino-4-methoxy-6-methyl-1,3,5triazine are initially charged in 50 ml of acetonitrile. 1.13 g (4.3 mmol) of 4-methyl-2i-propoxycarbonyl-thiophene-3-sulphonamide and 0.65g (4.3 mmol) of diazabicycloundecene (DBU) are then added at room temperature (about 20 0 and the mixture is stirred at this temperature for about 12 hours. The mixture is then concentrated using water pump vacuum, the residue is acidified using 2N hydrochloric acid and extracted using methylene chloride. The organic phase is washed with water, dried with magnesium sulphate and filtered. The filtrate is concentrated using water pump vacuum, the residue is digested with diethyl ether and the resulting crystalline product is isolated by filtration with suction.

This gives 0.87 g (52% of theory) of N-(4-methoxy-6-methyl-l,3,5-triazin-2-yl)-N'-(4methyl-2-i-propoxycarbonyl-thien-3-yl-sulphonyl)-urea of melting point 185°C.

28- Example 3 CH3 0 CH 3 HC N N N o I I H H S 0== O-C3,H? (Process 1.24 g (5.1 mmol) of N-phenoxycarbonyl-2-amino-4,6-dimethyl-pyrimidine are initially charged in 50 ml of acetonitrile. 1.47 g (5.6 mmol) of 4-methyl-2-i-propoxycarbonylthiophene-3-sulphonamide and 0.85 g (5.6 mmol) of diazabicycloundecene (DBU) are then added at room temperature (about 20 0 and the mixture is stirred at this temperature for about 12 hours. The mixture is then concentrated using water pump vacuum, the residue is acidified with 2N hydrochloric acid and extracted with methylene chloride. The organic phase is washed with water, dried with magnesium sulphate and filtered. The filtrate is concentrated using water pump vacuum, the residue is digested with diethyl ether and the resulting crystalline product is isolated by filtration with suction.

This gives 1.29 g (56% of theory) of N-(4,6-dimethyl-pyrimidine-2-yl)-N'-(4-methyl-2i-propoxycarbonyl-thien-3-yl-sulphonyl)-urea of melting point 223°C.

Similarly 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 to prepare, for example, the compounds of the formula listed in Table 1 below.

-29- R

I

131 R H S 0 0-R' Table 1: Examples of compounds of the formula (1) Ex. A Q R' R 3 R RS Melting No. point

(OC)

4 N 0 CH 3 OCH3 H CH3 CH 3 211 N 0 OCH3 OCH3 H CH 3

CR

3 166 6 N 0 N(CH 3 2 OCH2C3 H CH3 CR3 212 7 N 0 N(CH 3 2

OC

6

H

5 H CH3 CR3 207 8 N O H OCR 3 H CR 3 CH3 195 9 N 0 CR 3

SCH

3 H CR 3

CR

3 209 N 0 CH 3

N(CH

3 2 H CR3 CR 3 217 11 N 0 CH3 OCH3 H CR 3 CH3 205 12 N 0 C 2

H

5 OCH3 H CH3 CH3 206 13 CH 0 CH3 CH3 H CR 3 CH3 236 14 CH 0 CR3 OCH3 H CH3 CR 3 226 CH 0 OC3 O03 H CH3 CR 3 217 16 CH 0 CI O013 H CR3 CH 3 218 17 CH 0 H CH 3 H CR3 CR 3 238 18 N 0 013 013 H CH3 C 2 HS 224 19 N 0 01, OCH3 H CH3 CAR 5 190 N 0 OCH, OCH3H CH3 CH 5 176 21 N 0 N(CHh OCH 2 CF H CR, CAR, 188 22 N 0 OC H CH3 CH 5 218 30 Table 1 (continued) Ex. A No.

Q R 1 Ri R R 5 23 N 0 CH 3 24' N 0 CH 3 N 0 CH 3 26 N 0 CAH 27 CH 0 CH 3 28 CH 0 OCH 3 29 CH 0 CI CHO0 H 31 N 0 CH 3 32 CHi 0 OCH 3 33 N 0 OCH 3 34 N 0 N(CH 3 2 N 0 OCH,

SCH

3

N(CH

3 2

OCAH

OH

3

CH

3

CH

3

OCH

3

OCH

3 0013 OCH2CF 3

CH

3 CH3

CH

3 CH3

CH

3

CH

3

CH

3

CH

3

CH

3

CH

3

CH

3

CAH

C

2

H

5 s

CAH

C

2

HS

CAH

CAl

C

3 Hrn

C

3 Hrn Melting point

(CC)

215 208 155 203 234 109 183 220 206 160 184 171 207 36 N 0 Ca 3 37 N 0 0CAH 38 N 0 CAH 39 Ca 0 013 CHI 0 OCH 3 41 Ca 0 CI 42 N 0 N(CH 3 2

SCH

3

H

CH

3

H

OCH

3

H

OCH

3

H

OCH

3

H

0013 H

OCH

2

CF

2

CHF

2

H

CH3 013

CH

3 013 013 013

C

3 H7-' C3Hri

C

3

H

7 013 31 Use Examples: In the use examples, the following compound is used as comparative substance: 0CH3 N J NNI0

(A)

H M S 0- N-(4-cyclopropyl-6-methoxy- 1,3 ,5-triazin-2-yl)-N'-(2-methoxycarbonyl-4-methyl-thien- 3-yl-sulphonyl)-urea (known from EP 207609).

32- Example A Pre-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.

Seeds of the test plants are sown in normal soil. After about 24 hours, the soil is watered with the preparation of the active compound. Advantageously, the amount of water per unit area is kept constant. The active compound concentration in the preparation is not important, only the active compound application rate per unit area is critical.

After three weeks, the degree of damage to the plants is rated in damage in comparison with 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 1, 2, 3, 4, 5, 11, 14, 16, 18, 20, 25, 26, 27, 28, 33, 37, 38, 39 and 41 exhibit, at application rates between 30 g and 125 g of a.i. per hectare, considerably stronger activity against weeds than the known compound cf. Tables A-I to A-6.

"active ingredient" 33 Tables for Example A: Pre-emergence test/greenhouse Table A-l: Active Applicacompound tion rate of (g of Preparation ai./ha) Ex. No.

Alope- Avena Cype- Setaria Abuti- Amaran- Galium curus fatua rus Ion thus

(A)

(13) (1) (4) (14) (33) (3) (39) (37) (18) 30 90 90 95 90 95 90 95 90 95 95 100 90 100 95 100 90 70 100 100 100 100 80 90 95 95 95 100 100 100 100 100 90 100 100 80 95 100 34- Table A-2: Active compound of Preparation Ex. No.

Application rate (g of ai./ha) Alope- Avena Cyperus Setaria Abutilon Amarancurus fatua thus 125 80 30 90 80 80 (16) 60 90 70 95 80 90 (11) 60 95 50 95 100 60 100 95 95 90 100 (19) 30 100 90 100 100 100 100 Table A-3: Active compound of Preparation Ex. No.

Application Alopecurus Avena Cyperus Amaranthus Galium rate fatua (g of ai./ha) 125 80 30 90 80 (27) 30 100 90 100 95 Table A-4: Active compound of Preparation Ex. No.

Application Alopecurus Cyperus Abutilon Amaranthus Galium rate (g of ai./ha) 125 80 90 80 80 125 100 95 95 95 (28) 60 100 100 100 100 (26) 30 100 100 100 100 100 35 Table Active compound of Preparation Ex. No.

Application rate (g of ai./ha) Alopecurus Cyperus Galium

(A)

(41) 90 100 100 Table A-6: Active compound of Preparation Ex. No.

Application Alopecurus Abutilon Amaranthus rate (g of ai./ha) Galium (38) 15 (38)60 100 95 9 0 90 100 36- Example B Post-emergence test Solvent: Emulsifier: 5 parts by weight of acetone 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 preparation of the active compound in such a way as to apply the particular amounts of active compound desired per unit area. The concentration of the sprayed liquor is chosen so that the amounts of active compound desired in each case are applied in 1000 1 of water/ha.

After three weeks, the degree of damage to the plants is rated in damage in comparison with the development of the untreated control.

The figures denote: 0% 100% no effect (like untreated control) total destruction In this test, for example the compounds of Preparation Example 11, 13, 14, 19, 20, 27 and 39 exhibit, at application rates between 8 g and 60 g per hectare, considerably stronger activity against weeds than the known compound cf. Tables B-l and B-2.

37 Tables for Example B: Post-emergence test/greenhouse Table B-1: Active Applica- Bromus Cype- Digi- Echino- Loli- Sor- Cheno- Verocompound of tion rate rus taria chloa um ghum podium nica (g of Preparation ai./ha) Ex. No.

(A)

(11) 60 10 0 0 60 30 60 60 70 80 90 90 60 60 70 70 90 90 Table B-2: Active Applica- Bro- Cype- Digi- Echino- Loli- Sor- Cheno- Gali- Poly- Verocompound tion rate mus rus taria chloa um ghum podium um gonum nica of (g of Preparation ai./ha) Ex. No.

(A)

(13) (14) (27) 30 0 0 0 20 20 10 30 90 60 80 95 95 80 15 80 70 60 70 60 70 40 70 80 90 80 30 60 90 60 95 90 90 100 95

Claims (3)

1. 2. Process for preparing compounds of formula according to Claim 1, characterized in that arninoazines of the general formula (11) S S S S S *5 S *5 S S S S S.. *5 *5 S in which fad4%N1 A, R' and R 2 are each as defined in Claim 1, are reacted with thienylsulphonyl iso(tbio)cyanates of the general formula (111) in which Q, R'and R 5 are each as defined in Claim 1, if appropriate in the presence of a reaction auxiliary and if appropriate in the presence of a diluent, or substituted aminoazines of the general formula (IV) A N QM R in which A, Q, R'and W 2 are, each as defined in Claim 1, Z represents' halogen, alkoxy 'or aiyloxy and R has the meaning given above for" r represents grouping -C(Q)-Z S are reacted with thiophenesulphonamides; of the general formula (V) 4 .in which R RWand R' are each as defined above, if appropriate 1i i the! zesc :of a reaction auxiliary and if appropriate in the presence ofai;diltAi-- or
2. 41- aminoazines of the general formula (II) A N in which A, R' and R 2 are each as defined in Claim 1, Q o .,.4b are reacted with substituted thiophenesulphonamides of the general formula (VI) a ZANM O-R I I. I I I: I in which Q, R 4 and R are each as defined above and Z represents halogen, alkoxy or aryloxy, if appropriate in the presence of a reaction auxiliary and if appropriate in the presence of a diluent, and the compounds of the formula obtained by processes and are optionally converted into salts by customary methods. 3 1 Herbicidal compositions, characterized in that they comprise at least one compound of the formula according to Claim 1.
3. 42- 4. The use of compounds of the general formula according to Claim I for controlling undesirable plant growth. Method for controlling weeds, characterized in that compounds of the general formula according to Claim 1 are allowed to act on the weeds or their habitat. 6. Process for preparing herbicidal compositions, characterized in that compounds of the general formula according to Claim I are mixed with extenders and/or surfactants. DATED this 15th day of December, 1999 BAYER AKTIENGESELLSCHACT o By its Patent Attorneys Davies Collison Cave e t 0* 49 4 e4* .4