Substituted sulphonylamino(thio)carbonyl compounds

Abstract

The invention relates to novel substituted sulphonylamino(thio)carbonyl compounds of the formula (I) 1

Description

[0001] The invention relates to novel substituted sulphonylamino(thio)carbonyl compounds, to a plurality of-processes and novel intermediates for their preparation and to their use as herbicides.

[0002] It is already known that certain sulphonylaminocarbonyl compounds such as, for example, the compounds N-(2-chloro-6-methoxycarbonyl-phenylsulphonyl)-5-phenyl-1,2,4-oxadiazole-3-carboxamide (cf. EP 569810, Example 204), N-(2-chloro-6-methoxycarbonyl-phenylsulphonyl)-oxazole-2-carboxamide (cf. EP 569810, Example 239), N-(2-chloro-6-methoxycarbonyl-phenylsulphonyl)-4-methyl-oxazole-2-carboxamide (cf. EP 569810, Example 278), N-(2-chloro-6-methoxycarbonyl-phenylsulphonyl)-4-ethyl-5-methyl-oxazole-2-carboxamide (cf. EP 569810, Example 329), N-(2-chloro-6-methoxycarbonyl-phenylsulphonyl)-5-ethyl-oxazole-4-carboxamide (cf. EP 569810, Example 366), N-(2-chloro-6-methoxycarbonyl-phenylsulphonyl)-5-ethyl-thiazole-2-carboxamide (cf. EP 569810, Example 441), N-(2-chloro-6-methoxycarbonyl-phenylsulphonyl)-5-methyl-4-methylthio-thiazole-2-carboxamide (cf. EP 569810, Example 532), N-(2-chloro-6-methoxycarbonyl-phenylsulphonyl)-2,5-dimethyl-thiazole-4-carboxamide (cf EP 569810, Example 576), N-(2-chloro-6-methoxycarbonyl-phenylsulphonyl)-2-chloro-thiazole-5-carboxamide (cf. EP 569810, Example 607), N-(2-chloro-6-methoxy-carbonyl-phenylsulphonyl)-1,3,4-oxadiazole-2-carboxamide (cf. EP 569810, Example 641), N-(2-chloro-6-methoxycarbonyl-phenylsulphonyl)-1,3,4-thiadiazole-2-carboxamide (cf. EP 569810, Example 701), N-(2-chloro-6-methoxycarbonyl-phenylsulphonyl)-5-chloro-1,3,4-thiadiazole-2-carboxamide (cf. EP 569810, Example 735), N-(2-chloro-6-methoxycarbonyl-phenylsulphonyl)-5-phenyl-1,3,4-thiadiazole-2-carboxamide (cf. EP 569810, Example 757), N-(2-chloro-6-methoxy-carbonyl-phenylsulphonyl)-5-methyl-isoxazole-3-carboxamide (cf. EP 569810, Example 791), N-(2-chloro-6-methoxycarbonyl-phenylsulphonyl)-isoxazole-3-carboxamide (cf. EP 569810, Example 861), N-(2-chloro-6-methoxycarbonyl-phenylsulphonyl)-isoxazole-5-carboxamide (cf EP 569810, Example 871), N-(2-chloro-6-methoxycarbonyl-phenylsulphonyl)-5-methyl-isoxazole-4-carboxamide (cf. EP 569810, Example 918) and N-(2-chloro-6-methoxycarbonyl-phenylsulphonyl)-3,5-dimethyl-isoxazole-4-carboxamide (cf. EP 569810, Example 925) have herbicidal properties (cf. also EP 341489, EP 422469, EP 425948, EP 431291, EP 507171, EP 534266, DE 4029753). However, the activity of these compounds is not satisfactory in every respect.

[0003] This invention, accordingly, provides the novel substituted sulphonylamino(thio)carbonyl compounds of the general formula (I), 2

[0004] in which

[0005] A represents oxygen, sulphur, NH, N-alkyl, N-aryl, —CH═N— or —N═CH—, or —CH═CH—,

[0006] Q represents oxygen or sulphur,

[0007] R1 represents respectively optionally substituted alkyl, alkenyl, alkinyl, cycloalkyl, cycloalkylalkyl, aryl, arylalkyl, heterocyclyl or heterocyclylalkyl,

[0008] R2 represents cyano, nitro, halogen or represents respectively optionally substituted alkyl, alkoxy, alkoxycarbonyl, alkylthio, alkylsulphinyl, alkyl-sulphonyl, alkenyl, alkinyl, alkenyloxy or alkinyloxy, and

[0009] R3 represents respectively optionally substituted heterocyclyl having 5 ring members of which at least one represents oxygen, sulphur or nitrogen and a further one to three may represent nitrogen,

[0010] and salts of compounds of the formula (I),

[0011] except for the prior art compounds N-(2-chloro-6-methoxycarbonyl-phenyl-sulphonyl)-5-phenyl-1,2,4-oxadiazole-3-carboxamide (cf. EP 569810, Example 204), N-(2-chloro-6-methoxycarbonyl-phenylsulphonyl)-oxazole-2-carboxamide (cf. EP 569810, Example 239), N-(2-chloro-6-methoxycarbonyl-phenylsulphonyl)-4-methyl-oxazole-2-carboxamide (cf. EP 569810, Example 278), N-(2-chloro-6-methoxycarbonyl-phenylsulphonyl)-4-ethyl-5-methyl-oxazole-2-carboxamide (cf EP 569810, Example 329), N-(2-chloro-6-methoxycarbonyl-phenylsulphonyl)-5-ethyl-oxazole-4-carboxamide (cf. EP 569810, Example 366), N-(2-chloro-6-methoxycarbonyl-phenylsulphonyl)-5-ethyl-thiazole-2-carboxamide (cf. EP 569810, Example 441), N-(2-chloro-6-methoxycarbonyl-phenylsulphonyl)-5-methyl-4-methylthio-thiazole-2-carboxamide (cf. EP 569810, Example 532), N-(2-chloro-6-methoxycarbonyl-phenylsulphonyl)-2,5-dimethyl-thiazole-4-carboxamide (cf. EP 569810, Example 576), N-(2-chloro-6-methoxycarbonyl-phenylsulphonyl)-2-chloro-thiazole-5-carboxamide (cf. EP 569810, Example 607), N-(2-chloro-6-methoxycarbonyl-phenylsulphonyl)-1,3,4-oxadiazole-2-carboxamide (cf. EP 569810, Example 641), N-(2-chloro-6-methoxycarbonyl-phenylsulphonyl)-1,3,4-thiadiazole-2-carboxamide (cf. EP 569810, Example 701), N-(2-chloro-6-methoxycarbonyl-phenylsulphonyl)-5-chloro-1,3,4-thiadiazole-2-carboxamide (cf EP 569810, Example 735), N-(2-chloro-6-methoxycarbonyl-phenylsulphonyl)-5-phenyl-1,3,4-thiadiazole-2-carboxamide (cf. EP 569810, Example 757), N-(2-chloro-6-methoxycarbonyl-phenylsulphonyl)-5-methyl-isoxazole-3-carboxamide (cf. EP 569810, Example 791), N-(2-chloro-6-methoxycarbonyl-phenylsulphonyl)-isoxazole-3-carboxamide (cf. EP 569810, Example 861), N-(2-chloro-6-methoxycarbonyl-phenylsulphonyl)-isoxazole-5-carboxamide (cf. EP 569810, Example 871), N-(2-chloro-6-methoxycarbonyl-phenylsulphonyl)-5-methyl-isoxazole-4-carboxamide (cf. EP 569810, Example 918) and N-(2-chloro-6-methoxycarbonyl-phenylsulphonyl)-3,5-dimethyl-isoxazole-4-carboxamide (cf EP 569810, Example 925) which are excluded by disclaimer.

[0012] The novel substituted sulphonylamino(thio)carbonyl compounds of the general formula (I), are obtained when

[0013] (a) sulphonamides of the general formula (II) 3

[0014] in which

[0015] A, R1 and R2 are each as defined above, are reacted with (thio)carboxylic acid derivatives of the general formula (III) 4

[0016] in which

[0017] Q and R3 are each as defined above and

[0018] Z represents halogen, alkoxy, aryloxy or arylalkoxy,

[0019] if appropriate in the presence of an acid acceptor and if appropriate in the presence of a diluent,

[0020] or when

[0021] (b) sulphonyl iso(thio)cyanates of the general formula (IV) 5

[0022] in which

[0023] A, Q, R1 and R2 are each as defined above, are reacted with heterocycles of the general formula (V)

H—R3  (V)

[0024] in which

[0025] R3 is as defined above, if appropriate in the presence of a reaction auxiliary and if appropriate in the presence of a diluent,

[0026] or when

[0027] (c) sulphonyl chlorides of the general formula (VI) 6

[0028] in which

[0029] A, R1 and R2 are each as defined above, are reacted with heterocycles of the general formula (V)

H—R3  (V)

[0030] in which

[0031] R3 is as defined above,

[0032] and metal (thio)cyanates of the general formula (VII)

MQCN  (VII)

[0033] in which

[0034] Q is as defined above,

[0035] if appropriate in the presence of a reaction auxiliary and if appropriate in the presence of a diluent,

[0036] or when

[0037] (d) sulphonyl chlorides of the general formula (VI) 7

[0038] in which

[0039] A, R1 and R2 are each as defined above, are reacted with (thio)carboxamides of the general formula (VIII) 8

[0040] in which

[0041] Q and R3 are each as defined above,

[0042] if appropriate in the presence of an acid acceptor and if appropriate in the presence of a diluent,

[0043] or when

[0044] (e) sulphonylamino(thio)carbonyl compounds of the general formula (IX) 9

[0045] in which

[0046] A, Q, R1 and R2 are each as defined above and

[0047] Z represents halogen, alkoxy, aryloxy or arylalkoxy, are reacted with heterocycles of the general formula (V)

H—R3  (V)

[0048] in which

[0049] R3 is as defined above,

[0050] if appropriate in the presence of an acid acceptor and if appropriate in the presence of a diluent,

[0051] and the compounds of the formula (I) obtained by processes (a), (b), (c), (d) or (e) are, if desired, converted into salts by customary methods.

[0052] The novel substituted sulphonylamino(thio)carbonyl compounds of the general formula (I) have strong herbicidal activity.

[0053] The invention preferably provides compounds of the formula (I) in which

[0054] A represents oxygen, sulphur, NH, N—C1-C4-alkyl, N-phenyl, —CH═N— or —N═CH— or —CH═CH—,

[0055] Q represents oxygen or sulphur,

[0056] R1 represents optionally cyano-, nitro-, halogen- or C1-C4-alkoxy-substituted C1-C6-alkyl, represents respectively optionally cyano- or halogen-substituted C2-C6-alkenyl or C2-C6-alkinyl, represents respectively optionally cyano-, halogen- or C1-C4-alkyl-substituted C3-C6-cycloalkyl, C3-C6-cycloalkyl-C1-C4-alkyl, represents respectively optionally cyano-, nitro-, halogen-, C1-C4-alkyl-, C1-C4-halogenoalkyl-, C1-C4-alkoxy- or C1-C4-halogenoalkoxy-substituted phenyl or phenyl-C1-C4-alkyl, or represents respectively optionally cyano-, nitro-, halogen-, C1-C4-alkyl-, C1-C4-halogenoalkyl-, C1-C4-alkoxy- or C1-C4-halogenoalkoxy-substituted heterocyclyl or heterocyclyl-C1-C4-alkyl, where in each case the heterocyclyl group is selected from the group consisting of oxetanyl, thietanyl, furyl, tetrahydrofuryl, thienyl, tetrahydrothienyl, oxazolyl, isoxazolyl, thiazolyl, oxadiazolyl, thiadiazolyl,

[0057] R2 represents cyano, nitro, halogen, represents respectively optionally cyano-, halogen- or C1-C4-alkoxy-substituted C1-C4-alkyl, C1-C4-alkoxy, C1-C4-alkoxy-carbonyl, C1-C4-alkylthio, C1-C4-alkylsulphinyl or C1-C4-alkylsulphonyl, or represents respectively optionally cyano- or halogen-substituted C2-C4-alkenyl, C2-C4-alkinyl, C2-C4-alkenyloxy or C2-C4-alkinyloxy, and

[0058] R3 represents respectively optionally substituted heterocyclyl of the formulae below, 10

[0059] in which

[0060] Q1, Q2 and Q3 each represent oxygen or sulphur and

[0061] R4 represents hydrogen, hydroxyl, amino, cyano, represents C2-C10-alkylidene-amino, represents optionally fluorine-, chlorine-, bromine-, cyano-, C1-C4-alkoxy-, C1-C4-alkyl-carbonyl- or C1-C4-alkoxy-carbonyl-substituted C1-C6-alkyl, represents respectively optionally fluorine-, chlorine- and/or bromine-substituted C2-C6-alkenyl or C2-C6-alkinyl, represents respectively optionally fluorine-, chlorine-, bromine-, cyano-, C1-C4-alkoxy- or C1-C4-alkoxy-carbonyl-substituted C1-C6-alkoxy, C1-C6-alkylamino or C1-C6-alkyl-carbonyl-amino, represents C3-C6-alkenyloxy, represents di-(C1-C4-alkyl)-amino, represents respectively optionally fluorine-, chlorine-, bromine-, cyano- and/or C1-C4-alkyl-substituted C3-C6-cycloalkyl, C3-C6-cycloalkyl-amino or C3-C6-cycloalkyl-C1-C4-alkyl, or represents respectively optionally fluorine-, chlorine-, bromine-, cyano-, nitro-, C1-C4-alkyl-, trifluoromethyl- and/or C1-C4-alkoxy-substituted phenyl or phenyl-C1-C4-alkyl,

[0062] R5 represents hydrogen, hydroxyl, mercapto, amino, cyano, fluorine, chlorine, bromine, iodine, represents optionally fluorine-, chlorine-, bromine-, cyano-, C1-C4-alkoxy-, C1-C4-alkyl-carbonyl- or C1-C4-alkoxy-carbonyl-substituted C1-C6-alkyl, represents respectively optionally fluorine-; chlorine- and/or bromine-substituted C2-C6-alkenyl or C2-C6-alkinyl, represents respectively optionally fluorine-, chlorine-, cyano-, C1-C4-alkoxy- or C1-C4-alkoxy-carbonyl-substituted C1-C6-alkoxy, C1-C6-alkylthio, C1-C6-alkylamino or C1-C6-alkyl-carbonylamino, represents C3-C6-alkenyloxy, C3-C6-alkinyloxy, C3-C6-alkenylthio, C3-C6-alkinylthio, C3-C6-alkenylamino or C3-C6-alkinylamino, represents di-(C1-C4-alkyl)-amino, represents respectively optionally methyl- and/or ethyl-substituted aziridino, pyrrolidino, piperidino or morpholino, represents respectively optionally fluorine-, chlorine-, bromine-, cyano- and/or C1-C4-alkyl-substituted C3-C6-cycloalkyl, C5-C6-cycloalkenyl, C3-C6-cycloalkyloxy, C3-C6-cycloalkylthio, C3-C6-cycloalkylamino, C3-C6-cycloalkyl-C1-C4-alkyl, C3-C6-cycloalkyl-C1-C4-alkoxy, C3-C6-cycloalkyl-C1-C4-alkylthio or C3-C6-cycloalkyl-C1-C4-alkylamino, or represents respectively optionally fluorine-, chlorine-, bromine-, cyano-, nitro-, C1-C4-alkyl-, trifluoromethyl-, C1-C4-alkoxy- and/or C1-C4-alkoxy-carbonyl-substituted phenyl, phenyl-C1-C4-alkyl, phenoxy, phenyl-C1-C4-alkoxy, phenylthio, phenyl-C1-C4-alkylthio, phenylamino or phenyl-C1-C4-alkylamino, or

[0063] R4 and R5 together represent optionally branched alkanediyl having 3 to 11 carbon atoms, furthermore

[0064] R6, R7 and R8 are identical or different and each represents hydrogen, cyano, fluorine, chlorine, bromine, or represents respectively optionally fluorine-, chlorine-, bromine- or C1-C4-alkoxy-substituted alkyl, alkenyl, alkinyl, alkoxy, alkenyloxy, alkinyloxy, alkylthio, alkenylthio, alkinylthio, alkylsulphinyl or alkylsulphonyl having in each case up to 6 carbon atoms or represent optionally cyano-, fluorine-, chlorine-, bromine- or C1-C4-alkyl-substituted cycloalkyl having 3 to 6 carbon atoms,

[0065] except for the prior art compounds N-(2-chloro-6-methoxycarbonyl-phenylsulphonyl)-5-phenyl-1,2,4-oxadiazole-3-carboxamide (cf. EP 569810, Example 204), N-(2-chloro-6-methoxycarbonyl-phenylsulphonyl)-oxazole-2-carboxamide (cf. EP 569810, Example 239), N-(2-chloro-6-methoxycarbonyl-phenylsulphonyl)-4-methyl-oxazole-2-carboxamide (cf. EP 569810, Example 278), N-(2-chloro-6-methoxycarbonyl-phenylsulphonyl)-4-ethyl-5-methyl-oxazole-2-carboxamide (cf. EP 569810, Example 329), N-(2-chloro-6-methoxycarbonyl-phenylsulphonyl)-5-ethyl-oxazole-4-carboxamide (cf. EP 569810, Example 366), N-(2-chloro-6-methoxycarbonyl-phenylsulphonyl)-5-ethyl-thiazole-2-carboxamide (cf. EP 569810, Example 441), N-(2-chloro-6-methoxycarbonyl-phenylsulphonyl)-5-methyl-4-methylthio-thiazole-2-carboxamide (cf. EP 569810, Example 532), N-(2-chloro-6-methoxycarbonyl-phenylsulphonyl)-2,5-dimethyl-thiazole-4-carboxamide (cf. EP 569810, Example 576), N-(2-chloro-6-methoxycarbonyl-phenylsulphonyl)-2-chloro-thiazole-5-carboxamide (cf. EP 569810, Example 607), N-(2-chloro-6-methoxycarbonyl-phenylsulphonyl)-1,3,4-oxadiazole-2-carboxamide (cf. EP 569810, Example 641), N-(2-chloro-6-methoxycarbonyl-phenylsulphonyl)-1,3,4-thiadiazole-2-carboxamide (cf. EP 569810, Example 701), N-(2-chloro-6-methoxycarbonyl-phenylsulphonyl)-5-chloro-1,3,4-thiadiazole-2-carboxamide (cf EP 569810, Example 735), N-(2-chloro-6-methoxycarbonyl-phenylsulphonyl)-5-phenyl-1,3,4-thiadiazole-2-carboxamide (cf EP 569810, Example 757), N-(2-chloro-6-methoxycarbonyl-phenylsulphonyl)-5-methyl-isoxazole-3-carboxamide (cf. EP 569810, Example 791), N-(2-chloro-6-methoxycarbonyl-phenylsulphonyl)-isoxazole-3-carboxamide (cf. EP 569810, Example 861), N-(2-chloro-6-methoxycarbonyl-phenylsulphonyl)-isoxazole-5-carboxamide (cf. EP 569810,

[0066] Example 871), N-(2-chloro-6-methoxycarbonyl-phenylsulphonyl)-5-methyl-isoxazole-4-carboxamide (cf. EP 569810, Example 918) and N-(2-chloro-6-methoxycarbonyl-phenylsulphonyl)-3,5-dimethyl-isoxazole-4-carboxamide (cf. EP 569810, Example 925) which are excluded by disclaimer.

[0067] The invention furthermore preferably provides the sodium, potassium, magnesium, calcium, ammonium, C1-C4-alkyl-ammonium, di-(C1-C4-alkyl)-ammonium, tri-(C1-C4-alkyl)-ammonium, tetra-(C1-C4-alkyl)-ammonium, tri-(C1-C4-alkyl)-sulphonium, C5- or C6-cycloalkyl-ammonium and di-(C1-C2-alkyl)-benzyl-ammonium salts of compounds of the formula (I) in which A, Q, R1, R2 and R3 are each preferably as defined above.

[0068] The invention in particular provides compounds of the formula (I), in which

[0069] A represents sulphur, N-methyl, —CH═N— or —N═CH— or —CH═CH—,

[0070] Q represents oxygen or sulphur,

[0071] R1 represents respectively optionally cyano-, fluorine-, chlorine-, methoxy- or ethoxy-substituted methyl, ethyl, n- or i-propyl, n-, i- or s-butyl, represents respectively optionally cyano-, fluorine- or chlorine-substituted propenyl, butenyl, propinyl or butinyl, represents respectively optionally cyano-, fluorine-, chlorine-, methyl- or ethyl-substituted cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl or cyclo-hexylmethyl, represents respectively optionally cyano-, fluorine-, chlorine-, bromine-, methyl-, ethyl-, trifluoromethyl-, methoxy-, ethoxy-, difluoromethoxy- or trifluoromethoxy-substituted phenyl, phenylmethyl or phenylethyl, or represents respectively optionally cyano-, fluorine-, chlorine-, bromine-, methyl-, ethyl-, methoxy- or ethoxy-substituted heterocyclyl or heterocyclyl-methyl, where in each case the heterocyclyl group is selected from the group consisting of oxetanyl, thietanyl, furyl, tetrahydrofuryl, thienyl, tetrahydrothienyl,

[0072] R2 represents cyano, fluorine, chlorine, bromine, represents respectively optionally cyano-, fluorine-, chlorine-, methoxy- or ethoxy-substituted methyl, ethyl, n- or i-propyl, n-, i- or s-butyl, methoxy, ethoxy, n- or i-propoxy, methoxycarbonyl, ethoxycarbonyl, n- or i-propoxycarbonyl, methylthio, ethylthio, methylsulphinyl, ethylsulphinyl, methylsulphonyl or ethylsulphonyl, or represents respectively, optionally cyano-, fluorine- or chlorine-substituted propenyl, butenyl, propinyl, butinyl, propenyloxy or propinyloxy, and

[0073] R3 represents respectively optionally substituted heterocyclyl of the formulae below, 11

[0074] in which

[0075] Q1, Q2 and Q3 each represent oxygen or sulphur and

[0076] R4 represents hydrogen, hydroxyl, amino, represents respectively optionally fluorine-, chlorine-, cyano-, methoxy- or ethoxy-substituted methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, represents respectively optionally fluorine-, chlorine- or bromine-substituted propenyl, butenyl, propinyl or butinyl, represents respectively optionally fluorine-, chlorine-, cyano-, methoxy- or ethoxy-substituted methoxy, ethoxy, n- or i-propoxy, n-, i-, s- or t-butoxy, methylamino, ethylamino, n- or i-propylamino, n-, i-, s- or t-butylamino, represents propenyloxy or butenyloxy, represents dimethylamino or diethylamino, represents respectively optionally fluorine-, chlorine-, methyl- and/or ethyl-substituted cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopropylamino, cyclobutylamino, cyclopentylamino, cyclohexylamino, cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl or cyclohexylmethyl, or represents respectively optionally fluorine-, chlorine-, methyl-, trifluoromethyl- and/or methoxy-substituted phenyl or benzyl,

[0077] R5 represents hydrogen, hydroxyl, mercapto, amino, fluorine, chlorine, bromine, represents respectively optionally fluorine-, chlorine-, cyano-, methoxy- or ethoxy-substituted methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, represents respectively optionally fluorine-, chlorine- or bromine-substituted ethenyl, propenyl, butenyl, propinyl or butinyl, represents respectively optionally fluorine-, chlorine-, cyano-, methoxy- or ethoxy-substituted methoxy, ethoxy, n- or i-propoxy, n-, i-, s- or t-butoxy, methylthio, ethylthio, n- or i-propylthio, n-, i-, s- or t-butylthio, methylamino, ethylamino, n- or i-propylamino, n-, i-, s- or t-butylamino, represents propenyloxy, butenyloxy, propinyloxy, butinyloxy, propenylthio, propadienylthio butenylthio, propinylthio, butinylthio, propenylamino, butenylamino, propinylamino or butinylamino, represents dimethylamino, diethylamino or dipropylamino, represents respectively optionally fluorine-, chlorine-, methyl- and/or ethyl-substituted cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopentenyl, cyclohexenyl, cyclopropyloxy, cyclobutyloxy, cyclopentyloxy, cyclohexyloxy, cyclopropylthio, cyclobutylthio, cyclopentylthio, cyclohexylthio, cyclopropylamino, cyclobutylamino, cyclopentylamino, cyclohexylamino, cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl, cyclohexylmethyl, cyclopropylmethoxy, cyclobutylmethoxy, cyclopentylmethoxy, cyclohexylmethoxy, cyclopropylmethylthio, cyclobutylmethylthio, cyclopentylmethylthio, cyclohexylmethylthio, cyclopropylmethylamino, cyclobutylmethylamino, cyclopentylmethylamino or cyclohexylmethylamino, or represents respectively optionally fluorine-, chlorine-, methyl-, trifluoromethyl-, methoxy- and/or methoxycarbonyl-substituted phenyl, benzyl, phenoxy, benzyloxy, phenylthio, benzylthio, phenylamino or benzylamino, or

[0078] R4 and R5 together represent optionally branched alkanediyl having 3 to 11 carbon atoms, furthermore

[0079] R6, R7 and R8 are identical or different and each represents hydrogen, cyano, fluorine, chlorine, bromine, or represents respectively optionally fluorine-, chlorine-, methoxy- or ethoxy-substituted methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, propenyl, butenyl, propinyl, butinyl, methoxy, ethoxy, n- or i-propoxy, n-, i-, s- or t-butoxy, propenyloxy, butenyloxy, propinyloxy, butinyloxy, methylthio, ethylthio, n- or i-propylthio, n-, i-, s- or t-butylthio, propenylthio, butenylthio, propinylthio, butinylthio, methylsulphinyl, ethylsulphinyl, methylsulphonyl or ethylsulphonyl, or represents cyclopropyl,

[0080] except for the prior art compounds N-(2-chloro-6-methoxycarbonyl-phenylsulphonyl)-5-phenyl-1,2,4-oxadiazole-3-carboxamide (cf EP 569810, Example 204), N-(2-chloro-6-methoxycarbonyl-phenylsulphonyl)-oxazole-2-carboxamide (cf EP 569810, Example 239), N-(2-chloro-6-methoxycarbonyl-phenylsulphonyl)-4-methyl-oxazole-2-carboxamide (cf EP 569810, Example 278), N-(2-chloro-6-methoxycarbonyl-phenylsulphonyl)-4-ethyl-5-methyl-oxazole-2-carboxamide (cf. EP 569810, Example 329), N-(2-chloro-6-methoxycarbonyl-phenylsulphonyl)-5-ethyl-oxazole-4-carboxamide (cf. EP 569810, Example 366), N-(2-chloro-6-methoxycarbonyl-phenylsulphonyl)-5-ethyl-thiazole-2-carboxamide (cf. EP 569810, Example 441), N-(2-chloro-6-methoxycarbonyl-phenylsulphonyl)-5-methyl-4-methylthio-thiazole-2-carboxamide (cf. EP 569810, Example 532), N-(2-chloro-6-methoxycarbonyl-phenylsulphonyl)-2,5-dimethyl-thiazole-4-carboxamide (cf. EP 569810, Example 576), N-(2-chloro-6-methoxycarbonyl-phenylsulphonyl)-2-chloro-thiazole-5-carboxamide (cf. EP 569810, Example 607), N-(2-chloro-6-methoxycarbonyl-phenylsulphonyl)-1,3,4-oxadiazole-2-carboxamide (cf. EP 569810, Example 641), N-(2-chloro-6-methoxycarbonyl-phenylsulphonyl)-1,3,4-thiadiazole-2-carboxamide (cf. EP 569810, Example 701), N-(2-chloro-6-methoxycarbonyl-phenylsulphonyl)-5-chloro-1,3,4-thiadiazole-2-carboxamide (cf. EP 569810, Example 735), N-(2-chloro-6-methoxycarbonyl-phenylsulphonyl)-5-phenyl-1,3,4-thiadiazole-2-carboxamide (cf. EP 569810, Example 757), N-(2-chloro-6-methoxycarbonyl-phenylsulphonyl)-5-methyl-isoxazole-3-carboxamide (cf. EP 569810, Example 791), N-(2-chloro-6-methoxycarbonyl-phenylsulphonyl)-isoxazole-3-carboxamide (cf. EP 569810, Example 861), N-(2-chloro-6-methoxycarbonyl-phenylsulphonyl)-isoxazole-5-carboxamide (cf. EP 569810, Example 871), N-(2-chloro-6-methoxycarbonyl-phenylsulphonyl)-5-methyl-isoxazole-4-carboxamide (cf. EP 569810, Example 918) and N-(2-chloro-6-methoxycarbonyl-phenylsulphonyl)-3,5-dimethyl-isoxazole-4-carboxamide (cf. EP 569810, Example 925) which are excluded by disclaimer.

[0081] A very particularly preferred group of compounds according to the invention are the compounds of the formula (I) in which

[0082] A represents sulphur or —CH═CH—,

[0083] Q represents oxygen or sulphur,

[0084] R1 represents methyl, ethyl, n- or i-propyl, 2-cyano-ethyl, 2-fluoro-ethyl, 2,2-difluoro-ethyl, 2,2,2-trifluoro-ethyl, 2-chloro-ethyl, 2,2-dichloro-ethyl, 2,2,2-trichloro-ethyl, 2-methoxy-ethyl, 2-ethoxy-ethyl or oxetanyl,

[0085] R2 represents fluorine, chlorine, bromine, methyl, ethyl, n- or i-propyl, n-, i- or s-butyl, trifluoromethyl, methoxy, ethoxy, n- or i-propoxy, difluoromethoxy, trifluoromethoxy or trifluoroethoxy, and

[0086] R3 represents optionally substituted triazolinyl of the formula below 12

[0087] in which

[0088] Q1 represents oxygen or sulphur and

[0089] R4 represents respectively optionally fluorine-, chlorine-, methoxy- or ethoxy-substituted methyl, ethyl, n- or i-propyl, represents respectively optionally fluorine- or chlorine-subsituted propenyl or propinyl, represents methoxy, ethoxy, n- or i-propoxy, methylamino, ethylamino, n- or i-propylamino, represents propenyloxy, represents dimethylamino or represents cyclopropyl,

[0090] R5 represents chlorine or bromine, represents respectively optionally fluorine-, chlorine-, cyano-, methoxy- or ethoxy-substituted methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, represents respectively optionally fluorine-, chlorine- or bromine-substituted ethenyl, propenyl, butenyl, propinyl or butinyl, represents respectively optionally fluorine-, chlorine-, cyano-, methoxy- or ethoxy-subsituted methoxy, ethoxy, n- or i-propoxy, n-, i-, s- or t-butoxy, methylthio, ethylthio, n- or i-propylthio, n-, i-, s- or t-butylthio, methylamino, ethylamino, n- or i-propylamino, n-, i-, s- or t-butylamino, represents propenyloxy, butenyloxy, propinyloxy, butinyloxy, propenylthio, propadienylthio, butenylthio, propinylthio, butinylthio, propenylamino, butenylamino, propinylamino or butinylamino, represents dimethylamino, diethylamino or dipropylamino, represents respectively optionally fluorine-, chlorine-, methyl- and/or ethyl-substituted cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopentenyl, cyclohexenyl, cyclopropyloxy, cyclobutyloxy, cyclopentyloxy, cyclohexyloxy, cyclopropylthio, cyclobutylthio, cyclopentylthio, cyclohexylthio, cyclopropylamino, cyclobutylamino, cyclopentylamino, cyclohexylamino, cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl, cyclohexylmethyl, cyclopropylmethoxy, cyclobutylmethoxy, cyclopentylmethoxy, cyclohexylmethoxy, cyclopropylmethylthio, cyclobutylmethylthio, cyclopentylmethylthio, cyclohexylmethylthio, cyclopropylmethylamino, cyclobutylmethylamino, cyclopentylmethylamino or cyclohexylmethylamino, or represents respectively optionally fluorine-, chlorine-, methyl-, trifluoromethyl-, methoxy- and/or methoxycarbonyl-substituted phenyl, benzyl, phenoxy, benzyloxy, phenylthio, benzylthio, phenylamino or benzylamino, or

[0091] R4 and R5 together represent optionally branched alkanediyl having 3 to 11 carbon atoms.

[0092] The radical definitions listed above, whether general or listed in ranges of preference, apply both to the end products of the formula (I) and, correspondingly, to the starting materials and/or intermediates required in each case for the preparation. These radical definitions can be combined as desired with one another, thus including combinations between the preferred ranges indicated.

[0093] Using, for example, 2-fluoro-6-methoxycarbonyl-benzenesulphonamide and 5-ethoxy-4-methyl-2-phenoxycarbonyl-2,4-dihydro-3H-1,2,4-triazole-3-thione as starting materials, the course of the reaction in the process (a) according to the invention can be illustrated by the following equation: 13

[0094] Using, for example, 4-chloro-2-ethoxycarbonyl-3-thienylsulphonyl isothiocyanate and 5-ethyl-4-methoxy-2,4-dihydro-3H-1,2,4-triazol-3-one as starting materials, the course of the reaction in the process (b) according to the invention can be illustrated by the following equation: 14

[0095] Using, for example, 2-methoxycarbonyl-6-methyl-benzenesulphonyl chloride, 5-ethylthio-4-methoxy-2,4-dihydro-3H-1,2,4-triazol-3-one and potassium cyanate as starting materials, the course of the reaction in the process (c) according to the invention can be illustrated by the following equation: 15

[0096] Using, for example, 2-ethoxycarbonyl-6-trifluoromethyl-benzenesulphonyl chloride and 5-methyl-1,2,4-oxadiazole-3-carboxamide as starting materials, the course of the reaction in the process (d) according to the invention can be illustrated by the following equation: 16

[0097] Using, for example, N-(2-chloro-6-methoxycarbonyl-phenylsulphonyl)-O-methyl-urethane and 4-methyl-5-methylthio-2,4-dihydro-3H-1,2,4-triazol-3-one as starting materials, the course of the reaction in the process (e) according to the invention can be illustrated by the following equation: 17

[0098] A general definition of the sulphonamides to be used as starting materials in the process (a) according to the invention for preparing the compounds of the formula (I) is given by the formula (II). In the formula (II), A, R1 and R2 each preferably or in particular have that meaning which has already been indicated above in connection with the description of the compounds of the formula (I) according to the invention as being preferable or, respectively, particularly preferable for A, R1 and R2.

[0099] The starting materials of the formula (II) are known and/or can be prepared by processes known per se (cf. U.S. Pat. Nos. 4,546,179, 5,084,086, 5,157,119, WO 8909214, WO9115478).

[0100] The sulphonamides of the general formula (IIa) 18

[0101] in which

[0102] R1 and R2 are each as defined above have not yet been disclosed in the literature and, as novel compounds, form part of the subject-matter of the present application.

[0103] The novels sulphonamides of the formula (IIa) are obtained when sulphonyl chlorides of the formula (VIa) 19

[0104] in which

[0105] R1 and R2 are each as defined above,

[0106] are reacted with ammonia, if appropriate in the presence of a diluent such as, for example, water, at temperatures between 0° C. and 50° C. (cf. the Preparation Examples).

[0107] The sulphonyl chlorides of the formula (VIa) have not yet been disclosed in the literature; as novel compounds, they also form part of the subject-matter of the present application.

[0108] The novel sulphonyl chlorides of the formula (VIa) are obtained when corresponding amino compounds of the general formula (X) 20

[0109] in which

[0110] R1 and R2 are each as defined above,

[0111] are reacted with an alkali metal nitrite such as, for example, sodium nitrite, in the presence of hydrochloric acid at temperatures between −10° C. and +10° C. and the resulting diazonium salt solution is reacted with sulphur dioxide in the presence of a diluent such as, for example, dichloromethane, 1,2-dichloro-ethane or acetic acid, and in the.presence of a catalyst such as, for example, copper(I) chloride and/or copper(II) chloride, at temperatures between −10° C. and +50° C. (cf. the Preparation Examples).

[0112] The amino compounds of the formula (X) required as intermediates are known and/or can be prepared by processes known per se (cf. DE 3018134, DE 3804794, EP 298542, Preparation Examples).

[0113] A general definition of the (thio)carboxylic acid derivatives furthermore to be used as starting materials in the process (a) according to the invention for preparing the compounds of the formula (I) is given by the formula (III). In the formula (III), Q and R3 each preferably or in particular have that meaning which has already been indicated above in connection with the description of the compounds of the formula (I) according to the invention as being preferred or, respectively, particularly preferred for Q and R3; Z preferably represents fluorine, chlorine, bromine, C1-C4-alkoxy, phenoxy or benzyloxy, in particular chlorine, methoxy, ethoxy or phenoxy.

[0114] The starting materials of the formula (III) are known and/or can be prepared by processes known per se (cf. EP 459244, EP 341489, EP 422469, EP 425948, EP 431291, EP 507171, EP 534266).

[0115] A general definition of the sulphonyl iso(thio)cyanates to be used as starting materials in the process (b) according to the invention for preparing the compounds of the formula (I) is given by the formula (IV). In the formula (IV), A, Q, R1 and R2 each preferably or in particular have that meaning which has already been indicated above in connection with the description of the compounds of the formula (I) according to the invention as being preferred or, respectively, particularly preferred for A, Q, R1 and R2.

[0116] The starting materials of the formula (IV) are known and/or can be prepared by processes known per se (cf. EP 46626, U.S. Pat. No. 4,701,535, Preparation Examples).

[0117] A general definition of the heterocycles to be used as starting materials in the process (b), (c) and (e) according to the invention for preparing the compounds of the formula (I) is given by the formula (V). In the formula (V), R3 preferably or in particular has that meaning which has already been indicated above in connection with the description of the compounds of the formula (I) according to the invention as being preferred or, respectively, particularly preferred for R3.

[0118] The starting materials of the formula (V) are known and/or can be prepared by known processes (cf. EP 341489, EP 422469, EP 425948, EP 431291, EP 507171, EP 534266).

[0119] A general definition of the sulphonyl chlorides to be used as starting materials in the processes (c) and (d) according to the invention for preparing the compounds of the formula (I) is given by the formula (VI). In the formula (VI), A, R1 and R2 each preferably or in particular have that meaning which has already been indicated above in connection with the description of the compounds of the formula (I) according to the invention as being preferred or, respectively, particularly preferred for A, R1 and R2.

[0120] The starting materials of the formula (VI) are known and/or can be prepared by processes known per se (cf. U.S. Pat. Nos. 4,546,179, 5,084,086, 5,157,119, WO 8909214, WO 9115478, WO 9213845, Preparation Examples). However, as already mentioned, the compounds of the formula (VI) where A═S, i.e. the compunds of the sub-group of the formula (VIa), are novel.

[0121] A general definition of the (thio)carboxamides to be used as starting materials in the process (d) according to the invention for preparing the compounds of the formula (I) is given by the formula (VIII). In the formula (VIII), Q and R3 each preferably or in particular have that meaning which has already been indicated above in connection with the description of the compounds of the formula (I) according to the invention as being preferred or, respectively, particularly preferred for Q and R3.

[0122] The starting materials of the formula (VIII) are known and/or can be prepared by processes known per se (cf. EP 459244).

[0123] A general definition of the sulphonylamino(thio)carbonyl compounds to be used as starting materials in the process (e) according to the invention for preparing the compounds of the formula (I) is given by the formula (IX). In the formula (IX), A, Q, R1 and R2 each preferably or in particular have that meaning which has already been indicated above in connection with the description of the compounds of the formula (I) according to the invention as being preferred or, respectively, particularly preferred for A, Q, R1 and R2; Z preferably represents fluorine, chlorine, bromine, C1-C4-alkoxy, phenoxy or benzyloxy, in particular represents chlorine, methoxy, ethoxy or phenoxy.

[0124] The starting materials of the formula (IX) are known and/or can be prepared by methods known per se.

[0125] The processes (a), (b), (c), (d) and (e) according to the invention for the preparation of the novel compounds of the formula (I) are preferably carried out using diluents. Suitable diluents in this context are virtually all inert organic solvents. These include, preferably, aliphatic and aromatic, optionally halogenated hydrocarbons such as pentane, hexane, heptane, cyclohexane, petroleum ether, benzine, ligroin, benzene, toluene, xylene, methylene chloride, ethylene chloride, chloroform, tetrachloromethane, chlorobenzene and o-dichlorobenzene; ethers such as diethyl ether and dibutyl ether, glycol dimethyl ether and diglycol dimethyl ether, tetrahydrofuran and dioxane; ketones such as acetone, methyl ethyl ketone, methyl isopropyl ketone and methyl isobutyl ketone; esters such as methyl acetate and ethyl acetate; nitriles, for example acetonitrile and propionitrile; amides, for example dimethylformamide, dimethylacetamide and N-methylpyrrolidone, and also dimethyl sulphoxide, tetramethylenesulphone and hexamethylphosphorictriamide.

[0126] Suitable reaction auxiliaries and/or acid acceptors for the processes (a), (b), (c), (d) and (e) according to the invention are all acid-binding agents which are conventionally used for such reactions. Preference is given to alkali metal hydroxides, such as, for example, sodium hydroxide and potassium hydroxide, alkaline earth metal hydroxides such as, for example, calcium hydroxide, alkali metal carbonates and alkoxides, such as sodium carbonate and potassium carbonate, sodium tert-butoxide and potassium tert-butoxide, and also basic nitrogen compounds, such as trimethylamine, triethylamine, tripropylamine, tributylamine, diisobutylamine, dicyclohexylamine, ethyldiisopropylamine, ethyldicyclohexylamine, N,N-dimethylbenzylamine, N,N-dimethyl-aniline, pyridine, 2-methyl-, 3-methyl-, 4-methyl-, 2,4-dimethyl-, 2,6dimethyl-, 2-ethyl-, 4-ethyl- and 5-ethyl-2-methyl-pyridine, 1 ,5-diazabicyclo[4,3,0]-non-5-ene (DBN), 1,8-diazabicyclo[5,4,0]-undec-7-ene (DBU) and 1,4-diazabicyclo-[2,2,2]-octane(DABCO).

[0127] The reaction temperatures in the processes (a), (b), (c), (d) and (e) according to the invention can be varied within a relatively wide range. The processes are in general carried out at temperatures of between −20° C. and +150° C., preferably at temperatures between 0° C. and +100° C.

[0128] The processes (a), (b), (c), (d) and (e) according to the invention are generally carried out under atmospheric pressure. However, it is also possible to operate under elevated or reduced pressure.

[0129] For carrying out processes (a), (b), (c), (d) and (e) according to the invention, the starting materials required in each case are in general employed in approximately equimolar quantities. However, it is also possible to use one of the components employed in each case in a relatively large excess. The reactions are in general carried out in a suitable diluent in the presence of an acid acceptor, and the reaction mixture is stirred for a number of hours at the-particular temperature-required. Work-up in the case of the processes (a), (b), (c), (d) and (e) according to the invention is in each case carried out by customary methods (cf. the Preparation Examples).

[0130] Salts can be prepared, if desired, from the compounds of the general formula (I) according to the invention. 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 (I) in an appropriate solvent, for example methylene chloride, acetone, tert-butyl methyl ether or toluene, and adding an appropriate base. The salts can then—if desired after prolonged stirring—be isolated by concentration or filtration with suction.

[0131] 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, are to be understood all plants which grow in locations where they are not wanted. Whether the substances according to the invention act as total or selective herbicides depends essentially on the amount used.

[0132] The active compounds according to the invention can be used, for example, in connection with the following plants:

[0133] 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.

[0134] Dicotyledonous cultures of the genera: Gossypium, Glycine, Beta, Daucus, Phaseolus, Pisum, Solanum, Linum, Ipomoea, Vicia, Nicotiana, Lycopersicon, Arachis, Brassica, Lactuca, Cucumis and Cucurbita.

[0135] Monocolyledonous 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.

[0136] Monocotyledonous cultures of the genera: Oryza, Zea, Triticum, Hordeum, Avena, Secale, Sorghum, Panicum, Saccharum, Ananas, Asparagus and Allium.

[0137] 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.

[0138] The compounds are suitable, depending on the concentration, for the total control of weeds, for example on industrial terrain and rail tracks, and on paths and squares with or without tree plantings. Equally, the compounds can be employed for controlling weeds in perennial crops, for example afforestations, 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, in lawns, turf and pasture-land, and for the selective control of weeds in annual crops.

[0139] The compounds of the formula (I) according to the invention are particularly suitable for the selective control of monocotyledonous and dicotyledonous weeds in monocotyledenous and dicotyledenous crops, both pre-emergence and post-emergence.

[0140] To some extent, the compounds of the formula (I) also have fungicidal activity, for example against Pyricularia oryzae on rice.

[0141] 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.

[0142] These formulations are produced in a known manner, for example by mixing the active compounds with extenders, that is liquid solvents and/or solid carriers, optionally with the use of surfactants, that is emulsifiers and/or dispersants and/or foam formers.

[0143] If the extender used is water, it is also possible to use for example organic solvents as auxiliary solvents. Suitable liquid solvents essentially include: 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 water.

[0144] 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 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, alkylsulphonates, alkyl sulphates, arylsulphonates and protein hydrolysates; suitable dispersants are: for example lignin-sulphite waste liquors and methylcellulose.

[0145] Tackifiers such as carboxymethylcellulose and natural and synthetic polymers in the form of powders, granules or latices, such as gum arabic, polyvinyl alcohol and polyvinyl acetate, and natural phospholipids, such as cephalins and lecithins, and synthetic phospholipids, can be used in the formulations. Other possible additives are mineral and vegetable oils.

[0146] 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.

[0147] The formulations in general contain between 0.1 and 95 percent by weight of active compound, preferably between 0.5 and 90%.

[0148] 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.

[0149] 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-alkanoicesters, such as, for example, diclofop-methyl, fenoxaprop-ethyl, fluazifop-butyl, haloxyfop-methyl and quizalofop-ethyl; azinones, such as, for example, chloridazon and norflurazon; carbamates, such as, for example, chlorpropham, desmedipham, phenmedipham and propham; chloroacetanilides, such as, for example, alachlor, acetochlor, butachlor, metazachlor, metolachlor, pretilachlor and propachlor; dinitroanilines, such as, for example, oryzalin, pendimethalin and trifluralin; diphenyl ethers, such as, for example, acifluorfen, bifenox, fluoroglycofen, fomesafen, halosafen, lactofen and oxyfluorfen; ureas, such as, for example, chlorotoluron, diuron, fluometuron, isoproturon, linuron and methabenzthiazuron;hydroxylamines, such as, for example, alloxydim, clethodim, cycloxydim, sethoxydim and tralkoxydim; imidazolinones, such as, for example, imazethapyr, imazamethabenz, imazapyr and imazaquin; nitriles, such as, for example, bromoxynil, dichlobenil and ioxynil; oxyacetamides, such as, for example, mefenacet; sulphonylureas, such as amidosulfuron, bensulfuron-methyl, chlorimuron-ethyl, chlorsulfuron, cinosulfuron, metsulfuron-methyl, nicosulfuron, primisulfuron, pyrazosulfuron-ethyl, thifensulfuron-methyl, triasulfuron and tribenuron-methyl; thiocarbamates, such as, for example, butylate, cycloate, diallate, EPTC, esprocarb, molinate, prosulphocarb, thiobencarb and triallate; triazines, such as atrazine, cyanazine, simazine, simetryne, terbutryne and terbutylazine; triazinones, such as hexazinone, metamitron and metribuzin; and others, such as, for example, aminotriazole, benfuresate, bentazone, cinmethylin, clomazone, clopyralid, difenzoquat, dithiopyr, ethofumesate, fluorochloridone, glufosinate, glyphosate, isoxaben, pyridate, quinchlorac, quinmerac, sulphosate and tridiphane.

[0150] 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.

[0151] 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.

[0152] 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.

[0153] The amount of active compound used can vary within a 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 5 kg per ha.

[0154] The preparation and use of the active compounds according to the invention can be seen from the following examples.

PREPARATION EXAMPLES

Example 1

[0155] 21

[0156] (Process (a))

[0157] 7.5 g (32 mmol) of 4-methyl-2-methoxycarbonyl-thiophene-3-sulphonamide and 4.9 g (32 mmol) of 1,8-diazabicyclo-[5,4,0]-undec-7-ene (DBU) are added successively to a solution of 7.9 g (30 mmol) of 5-ethoxy-4-methyl-2-phenoxycarbonyl-2,4-dihydro-3H-1,2,4-triazol-3-one in 150 ml of acetonitrile. The reaction mixture is stirred at room temperature (about 20° C.) for about 15 hours and subsequently concentrated using water pump vacuum. The residue is then taken up in methylene chloride and washed with 1N hydrochloric acid and then with water. The organic phase is dried over magnesium sulphate and filtered. The filtrate is concentrated using water pump vacuum and the residue is recrystallized from isopropanol.

[0158] 9.2 g (76% of theory) of 5-ethoxy-4-methyl-2-(4-methyl-2-methoxycarbonyl-thien-3-yl-sulphonylaminocarbonyl)-2,4-dihydro-3H-1,2,4-triazol-3-one of melting point 169° C. are obtained.

Example 2

[0159] 22

[0160] (Process (b))

[0161] 2.1 g (8 mmol) of 2-ethoxycarbonyl-4-methyl-thien-3-yl-sulphonyl isocyanate are added to a solution of 1.35 g (8 mmol) of 4-methyl-5-propargylthio-2,4-dihydro-3H-1,2,4-triazol-3-one in 50 ml of acetonitrile. The mixture is then heated under reflux for 8 hours and subsequently concentrated using water pump vacuum, the residue is stirred with diethyl ether and the crystalline product is isolated by filtration with suction.

[0162] 1.4 g (40% of theory) of 4-methyl-5-propargylthio-2-(2-ethoxycarbonyl-4-methyl-thien-3-yl-sulphonylaminocarbonyl)-2,4-dihydro-3H-1,2,4-triazol-3-one of melting point 175° C. are obtained.

Example 3

[0163] 23

[0164] (Process (c))

[0165] A solution of 3.8 g (20 mmol) of 4-ethoxy-5-ethylthio-2,4-dihydro-3H-1,2,4-triazol-3-one in 50 ml of acetonitrile is admixed with 6.0 g (24 mmol) of 2-methyl-6-methoxy-carbonyl-benzenesulphonyl chloride, 2.6 g (40 mmol) of sodium cyanate and 1.2 g (15 mmol) of pyridine, and the reaction mixture is stirred at room temperature (about 20° C.) for 3 days. The mixture is then diluted with approximately identical volumina of methylene chloride and water to about three times its volume and then made weakly acidic (pH˜3) using 1N hydrochloric acid. The organic phase is separated off, dried over sodium sulphate and filtered. The filtrate is concentrated and the residue is recrystallized from isopropanol.

[0166] 5.0 g (56% of theory) of 4-ethoxy-5-ethylthio-2-(2-methyl-6-methoxy-carbonyl-phenylsulphonylaminocarbonyl)-2,4-dihydro-3H-1,2,4-triazol-3-one of melting point 135° C. are obtained.

Example 4

[0167] 24

(Process (d))

[0168] At 20° C. to a maximum of 35° C., 2.0 g (36 mmol) of potassium hydroxide powder are added to a solution of 1.52 g (12.0 mmol) of 5-methyl-1,2,4-oxadiazole-3-carboxamide in 150 ml of dioxane. After 30 minutes, about 50 ml of dioxane are distilled off at 30° C. to 35° C. using water pump vacuum. The mixture is subsequently admixed a little at a time with 3.6 g (12.6 mmol) of 4-methyl-2-i-propoxycarbonyl-thiophene-3-sulphonyl chloride and the reaction mixture is stirred at room temperature (about 20° C.) for about 12 hours. The mixture is subsequently concentrated using water pump vacuum and the residue is taken up in water and acidified using 2N hydrochloric acid. The mixture is then extracted twice using 100 ml of methylene chloride each time. The combined organic solutions are washed with water, dried over magnesium sulphate and filtered. The filtrate is concentrated using water pump vacuum and the residue is recrystallized from ethanol.

[0169] 2.3 g (52% of theory) of N-(4-methyl-2-i-propoxycarbonyl-thien-3-yl-sulphonyl)-5-methyl-1,2,4-oxadiazole-3-carboxamide of melting point 142° C. are obtained.

[0170] Similar to Examples 1 to 4, and according to the general description of the preparation processes according to the invention, it is also possible to prepare for example the compounds of the formula (I) listed in Table 1 below. 25 1 TABLE 1 Examples of compounds of the formula (I) Ex. Melting No. A Q R1 R2 R3 point (° C.) 5 S O CH3 CH3 26 178 6 S O CH3 CH3 27 192 7 CH═CH O C2H5 CH3 28 154 8 CH═CH O C3H7-i CH3 29 124 9 CH═CH O CH3 CH3 30 115 10 CH═CH O C2H5 CH3 31  85 11 CH═CH O C3H7-n CH3 32  59 12 CH═CH O C3H7-i CH3 33 (amorphous) 13 S O CH3 CH3 34 157 14 S O CH3 CH3 35 158 15 CH═CH O C2H5 CH3 36 168 16 CH═CH O C3H7-i CH3 37 144 17 CH═CH O C3H7-i CH3 38 122 18 CH═CH O C3H7-i CH3 39 167 19 CH═CH O C3H7-i CH3 40 114 20 CH═CH O C3H7-n CH3 41 142 21 CH═CH O C3H7-n CH3 42 106 22 CH═CH O C3H7-n CH3 43 105 23 CH═CH O C3H7-n CH3 44 112 24 CH═CH O C3H7-n CH3 45 115 25 CH═CH O C3H7-n CH3 46  77 26 CH═CH O C3H7-i CH3 47 131 27 S O CH3 CH3 48 158 28 S O CH3 CH3 49 175 29 S O CH3 CH3 50 151 30 S O CH3 CH3 51 155 31 S O CH3 CH3 52 184 32 S O CH3 CH3 53 151 33 S O CH3 CH3 54 191 34 S O CH3 CH3 55 142 35 S O CH3 CH3 56 122 36 S O CH3 CH3 57 121 37 S O CH3 CH3 58 187 38 S O CH3 CH3 59 163 39 S O CH3 CH3 60 124 40 S O CH3 CH3 61 162 41 S O CH3 CH3 62 144 42 CH═CH O C3H7-i CH3 63 125 43 CH═CH O C3H7-i CH3 64 120 44 CH═CH O C3H7-i CH3 65 121 45 CH═CH O C3H7-n CH3 66 118 46 CH═CH O C3H7-i CH3 67 130 47 CH═CH O C3H7-n CH3 68 107 48 CH═CH O C3H7-n CH3 69  87 49 CH═CH O CH2CF3 CH3 70 113 50 CH═CH O C3H7-n CH3 71 122 51 S O CH3 CH3 72 137 52 S O CH3 CH3 73 185 53 S O CH3 CH3 74 184 54 S O C2H5 CH3 75 161 55 S O C2H5 CH3 76 131 56 S O C2H5 CH3 77 158 57 S O C2H5 CH3 78 178 58 S O C2H5 CH3 79 133 59 S O C2H5 CH3 80 131 60 S O C2H5 CH3 81 159 61 S O C2H5 CH3 82 132 62 S O C2H5 CH3 83 150 63 S O C2H5 CH3 84 142 64 S O C2H5 CH3 85 108 65 S O C2H5 CH3 86 123 66 S O C2H5 CH3 87 135 67 S O C2H5 CH3 88  77 68 S O C2H5 CH3 89 130 69 S O C2H5 CH3 90 141 70 S O C2H5 CH3 91 141 71 CH═CH O C3H7-i CF3 92  73 72 S O C2H5 CH3 93 139 73 CH═CH O CH3 OCF3 94 181 74 CH═CH O CH3 OCF3 95 107 75 S O C3H7-n CH3 96 114 76 S O C3H7-i CH3 97 152 77 S O C3H7-i CH3 98 146 78 S O C3H7-i CH3 99 164 79 S O C3H7-n CH3 100 167 80 S O C3H7-n CH3 101 113 81 S O C3H7-i CH3 102 131 82 S O C3H7-i CH3 103 173 83 S O C3H7-i CH3 104  87 84 S O C3H7-i CH3 105 125 85 S O C3H7-i CH3 106 127 86 S O C3H7-i CH3 107 126 87 S O C3H7-i CH3 108 136 88 S O C2H5 CH3 109 106 89 S O C3H7-n CH3 110 117 90 S O C3H7-n CH3 111  90 91 S O C3H7-n CH3 112 134 92 S O C3H7-n CH3 113 141 93 S O C3H7-n CH3 114 142 94 S O C3H7-n CH3 115  90 95 S O C3H7-n CH3 116 119 96 S O C3H7-i CH3 117 159 97 S O C3H7-i CH3 118 130 98 S O C3H7-i CH3 119 145 99 S O C3H7-n CH3 120 109 100 S O C3H7-n CH3 121  95 101 S O C3H7-n CH3 122  84 102 S O C3H7-n CH3 123  89 103 S O C3H7-n CH3 124 135 104 S O C2H5 CH3 125 155 105 S O C2H5 CH3 126 116 106 S O C2H5 CH3 127 136 107 S O C3H7-i CH3 128 135 108 S O C3H7-i CH3 129  98 109 S O C3H7-i CH3 130 120 110 S O C3H7-i CH3 131 140 111 S O C3H7-i CH3 132 137 112 S O C3H7-i CH3 133 145 113 S O C3H7-i CH3 134 124 114 S O C3H7-n CH3 135 108 115 S O C3H7-n CH3 136 138 116 S O C3H7-n CH3 137  93 117 S O C3H7-n CH3 138 130 118 S O C3H7-n CH3 139 128 119 S O CH3 CH3 140 248 (Na salt) 120 CH═CH O CH3 Cl 141  78 121 CH═CH O CH3 CH3 142 120 122 CH═CH O CH3 Cl 143  68 123 CH═CH O CH3 CH3 144  54 124 CH═CH O CH3 Cl 145 147 125 CH═CH O CH3 CH3 146 118 126 CH═CH O CH3 Cl 147  63 127 CH═CH O CH3 Cl 148 167 128 CH═CH O C2H5 Cl 149 128 129 CH═CH O CH3 Cl 150  95 130 CH═CH O CH3 Cl 151 153 131 CH═CH O C2H5 Cl 152 145 132 CH═CH O C3H7-n Cl 153  98 133 CH═CH O C3H7-n Cl 154  89 134 CH═CH O C3H7-n Cl 155 110 135 CH═CH O CH3 OCH3 156 175 136 CH═CH O CH3 OCH3 157 190 137 CH═CH O C3H7-i Cl 158  89 138 CH═CH O 159 CH3 160 146 139 CH═CH O 161 CH3 162 158 140 CH═CH O CH3 CH3 163 150 141 CH═CH O CH3 CH3 164 142 142 CH═CH O CH3 CH3 165 145 143 CH═CH O CH3 CH3 166 148 144 CH═CH O CH3 CH3 167 155 (Na salt) 145 CH═CH O CH3 CH3 168 185 (Na salt) 146 CH═CH O CH3 CH3 169 163 147 CH═CH O CH3 CH3 170 122 148 CH═CH O CH3 CH3 171 137 149 CH═CH O CH3 CH3 172 156 150 CH═CH O CH3 CH3 173 122 151 CH═CH O CH3 CH3 174 166 152 CH═CH O CH3 CH3 175 125 153 CH═CH O CH3 CH3 176 137 154 CH═CH O CH3 CH3 177 179 (Na salt) 155 CH═CH O CH3 CH3 178 153 156 CH═CH O CH3 CH3 179 172 157 CH═CH O CH3 CH3 180 124 158 CH═CH O CH3 CH3 181 157 159 CH═CH O CH3 CH3 182 156 160 CH═CH O CH3 CH3 183 138 161 CH═CH O CH3 CH3 184 137 162 CH═CH O CH3 CH3 185 160 163 CH═CH O CH3 CH3 186 139 164 CH═CH O CH3 CH3 187 174 165 CH═CH O CH3 CH3 188 119 166 CH═CH O CH3 CH3 189 158 167 CH═CH O CH3 CH3 190 148 168 CH═CH O CH3 CH3 191 128 169 CH═CH O CH3 CH3 192 145 170 CH═CH O CH3 CH3 193 161 171 CH═CH O CH3 CH3 194 129 172 CH═CH O CH3 CH3 195 136 173 CH═CH O CH3 CH3 196 155 174 CH═CH O CH3 CH3 197 129 175 CH═CH O CH3 CH3 198 150 176 CH═CH O CH3 CH3 199 148 177 CH═CH O CH3 CH3 200 149 178 CH═CH O CH3 CH3 201  99 179 CH═CH O CH3 CH3 202 115 180 CH═CH O CH3 CH3 203 114 181 CH═CH O CH3 CH3 204 125 182 CH═cH O CH3 CH3 205 124 183 CH═CH O CH3 CH3 206 105 184 CH═CH O CH3 CH3 207 131 185 CH═CH O CH3 CH3 208 149 186 S O C3H7-n CH3 209 187 CH═CH O CH3 NO2 210 180

[0171] The compound listed as Example 119 in Table 1 can be prepared for example as follows: 211

[0172] (Salt Formation)

[0173] A mixture of 2.0 g (5 mmol) of 5-ethoxy-4-methyl-2-(4methyl-2-methoxy-carbonyl-thien-3-yl-sulfonylaminocarbonyl)-2,4-dihydro-3H-1,2,4-triazol-3-one and 75 ml of acetonitrile is admixed with 0.17 g (5.5 mmol) of sodium hydride (80% strength), and the mixture is stirred at room temperature (about 20° C.) for about 60 minutes. The crystalline product is then isolated by filtration with suction

[0174] 2.0 g (94% of theory) of the sodium salt of 5-ethoxy-4-methyl-2-(4-methyl-2-methoxycarbonyl-thien-3-yl-sulfonylaminocarbonyl)-2,4-dihydro-3H-1,2,4-triazol-3-one are obtained as a colourless crystalline product of melting point 248° C.

[0175] Starting Materials of the Formula (II):

Example (II-1)

[0176] 212

[0177] 12.0 g (42.6 mmol) of 4-methyl-2-i-propoxycarbonyl-thiophene-3-sulfonyl chloride are dissolved in 100 ml of methylene chloride and admixed with 8.2 g (85.4 mmol) of ammonium carbonate. The mixture is stirred at room temperature (about 20° C.) for about 24 hours. The undissolved salt is filtered off by suction, the filtrate is concentrated using water pump vacuum, the residue is digested with diethyl ether and the crystalline product is isolated by filtration with suction.

[0178] 9.1 g (91% of theory) of 4-methyl-2-i-propoxycarbonyl-thiophene-3-sulphonamide are obtained as a light-yellow solid of melting point 76° C.

[0179] Similarly, it is possible to prepare for example the following compounds of the formula (II):

[0180] 4-methyl-2-methoxycarbonyl-thiophene-3-sulphonamide (mp.: 54° C.),

[0181] 4-methyl-2-ethoxycarbonyl-thiophene-3-sulphonamide (mp.: 65° C.),

[0182] 4-methyl-2-n-propoxycarbonyl-thiophene-3-sulphonamide (mp.: 90° C.),

[0183] 4-methyl-2-(oxetan-2-yl-oxycarbonyl)-thiophene-3-sulphonamide,

[0184] 4-ethyl-2-methoxycarbonyl-thiophene-3-sulphonamide,

[0185] 4-ethyl-2-ethoxycarbonyl-thiophene-3-sulphonamide,

[0186] 4-ethyl-2-n-propoxycarbonyl-thiophene-3-sulphonamide,

[0187] 4-ethyl-2-i-propoxycarbonyl-thiophene-3-sulphonamide,

[0188] 4-ethyl-2-(oxetan-2-yl-oxycarbonyl)-thiophene-3-sulphonamide,

[0189] 4-fluoro-2-methoxycarbonyl-thiophene-3-sulphonamide,

[0190] 4-fluoro-2-ethoxycarbonyl-thiophene-3-sulphonamide,

[0191] 4-fluoro-2-n-propoxycarbonyl-thiophene-3-sulphonamide,

[0192] 4-fluoro-2-i-propoxycarbonyl-thiophene-3-sulphonamide,

[0193] 4-fluoro-2-(oxetan-2-yl-oxycarbonyl)-thiophene-3-sulphonamide,

[0194] 4-chloro-2-methoxycarbonyl-thiophene-3-sulphonamide,

[0195] 4-chloro-2-ethoxycarbonyl-thiophene-3-sulphonamide,

[0196] 4-chloro-2-n-propoxycarbonyl-thiophene-3-sulphonamide,

[0197] 4-chloro-2-i-propoxycarbonyl-thiophene-3-sulphonamide,

[0198] 4-chloro-2-(oxetan-2-yl-oxycarbonyl)-thiophene-3-sulphonamide,

[0199] 4-bromo-2-methoxycarbonyl-thiophene-3-sulphonamide,

[0200] 4-bromo-2-ethoxycarbonyl-thiophene-3-sulphonamide,

[0201] 4-bromo-2-n-propoxycarbonyl-thiophene-3-sulphonamide,

[0202] 4-bromo-2-i-propoxycarbonyl-thiophene-3-sulphonamide,

[0203] 4-bromo-2-(oxetan-2-yl-oxycarbonyl)-thiophene-3-sulphonamide,

[0204] 4-methoxy-2-methoxycarbonyl-thiophene-3-sulphonamide,

[0205] 4-methoxy-2-ethoxycarbonyl-thiophene-3-sulphonamide,

[0206] 4-methoxy-2-n-propoxycarbonyl-thiophene-3-sulphonamide,

[0207] 4-methoxy-2-i-propoxycarbonyl-thiophene-3-sulphonamide,

[0208] 4-methoxy-2-(oxetan-2-yl-oxycarbonyl)-thiophene-3-sulphonamide,

[0209] 4-methylthio-2-methoxycarbonyl-thiophene-3-sulphonamide,

[0210] 4-methylthio-2-ethoxycarbonyl-thiophene-3-sulphonamide,

[0211] 4-methylthio-2-n-propoxycarbonyl-thiophene-3-sulphonamide,

[0212] 4-methylthio-2-i-propoxycarbonyl-thiophene-3-sulphonamide,

[0213] 4-methylthio-2-(oxetan-2-yl-oxycarbonyl)-thiophene-3-sulphonamide,

[0214] 4-trifluoromethyl-2-methoxycarbonyl-thiophene-3-sulphonamide,

[0215] 4-trifluoromethyl-2-ethoxycarbonyl-thiophene-3-sulphonamide,

[0216] 4-trifluoromethyl-2-n-propoxycarbonyl-thiophene-3-sulphonamide,

[0217] 4-trifluoromethyl-2-i-propoxycarbonyl-thiophene-3-sulphonamide,

[0218] 4-trifluoromethyl-2-(oxetan-2-yl-oxycarbonyl)-thiophene-3-sulphonamide,

[0219] 4-difluoromethoxy-2-methoxycarbonyl-thiophene-3-sulphonamide,

[0220] 4-difluoromethoxy-2-ethoxycarbonyl-thiophene-3-sulphonamide,

[0221] 4-difluoromethoxy-2-n-propoxycarbonyl-thiophene-3-sulphonamide,

[0222] 4-difluoromethoxy-2-i-propoxycarbonyl-thiophene-3-sulphonamide,

[0223] 4-difluoromethoxy-2-(oxetan-2-yl-oxycarbonyl)-thiophene-3-sulphonamide,

[0224] 4-trifluoromethoxy-2-methoxycarbonyl-thiophene-3-sulphonamide,

[0225] 4-trifluoromethoxy-2-ethoxycarbonyl-thiophene-3-sulphonamide,

[0226] 4-trifluoromethoxy-2-n-propoxycarbonyl-thiophene-3-sulphonamide,

[0227] 4-trifluoromethoxy-2-i-propoxycarbonyl-thiophene-3-sulphonamide,

[0228] 4-trifluoromethoxy-2-(oxetan-2-yl-oxycarbonyl)-thiophene-3-sulphonamide.

[0229] 6-methyl-2-methoxycarbonyl-benzenesulphonamide (mp.: 118° C.),

[0230] 6-methyl-2-ethoxycarbonyl-benzenesulphonamide (mp.: 277° C.),

[0231] 6-methyl-2-n-propoxycarbonyl-benzenesulphonamide,

[0232] 6-methyl-2-i-propoxycarbonyl-benzenesulphonamide (mp.:122° C.),

[0233] 6-methyl-2-(oxetan-2-yl-oxycarbonyl)-benzenesulphonamide,

[0234] 6-ethyl-2-methoxycarbonyl-benzenesulphonamide,

[0235] 6-ethyl-2-ethoxycarbonyl-benzenesulphonamide,

[0236] 6-ethyl-2-n-propoxycarbonyl-benzenesulphonamide,

[0237] 6-ethyl-2-i-propoxycarbonyl-benzenesulphonamide,

[0238] 6-ethyl-2-(oxetan-2-yl-oxycarbonyl)-benzenesulphonamide,

[0239] 6-fluoro-2-methoxycarbonyl-benzenesulphonamide,

[0240] 6-fluoro-2-ethoxycarbonyl-benzenesulphonamide,

[0241] 6-fluoro-2-n-propoxycarbonyl-benzenesulphonamide,

[0242] 6-fluoro-2-i-propoxycarbonyl-benzenesulphonamide,

[0243] 6-fluoro-2-(oxetan-2-yl-oxycarbonyl)-benzenesulphonamide,

[0244] 6-chloro-2-methoxycarbonyl-benzenesulphonamide,

[0245] 6-chloro-2-ethoxycarbonyl-benzenesulphonamide,

[0246] 6-chloro-2-n-propoxycarbonyl-benzenesulphonamide,

[0247] 6-chloro-2-i-propoxycarbonyl-benzenesulphonamide,

[0248] 6-chloro-2-(oxetan-2-yl-oxycarbonyl)-benzene-sulphonamide,

[0249] 6-bromo-2-methoxycarbonyl-benzenesulphonarnide,

[0250] 6-bromo-2-ethoxycarbonyl-benzenesulphonarnide,

[0251] 6-bromo-2-n-propoxycarbonyl-benzenesulphonamide,

[0252] 6-bromo-2-i-propoxycarbonyl-benzenesulphonamide,

[0253] 6-bromo-2-(oxetan-2-yl-oxycarbonyl)-benzenesulphonamide,

[0254] 6-methoxy-2-methoxycarbonyl-benzenesulphonamide,

[0255] 6-methoxy-2-ethoxycarbonyl-benzenesulphonamide,

[0256] 6-methoxy-2-n-propoxycarbonyl-benzenesulphonamide,

[0257] 6-methoxy-2-i-propoxycarbonyl-benzenesulphonarnide,

[0258] 6-methoxy-2-(oxetan-2-yl-oxycarbonyl)-benzenesulphonamide,

[0259] 6-methylthio-2-methoxycarbonyl-benzenesulphonamide,

[0260] 6-methylthio-2-ethoxycarbonyl-benzenesulphonamide,

[0261] 6-methylthio-2-n-propoxycarbonyl-benzenesulphonamide,

[0262] 6-methylthio-2-i-propoxycarbonyl-benzenesulphonamide,

[0263] 6-methylthio-2-(oxetan-2-yl-oxycarbonyl)-benzenesulphonamide,

[0264] 6-trifluoromethyl-2-methoxycarbonyl-benzenesulphonamide,

[0265] 6-trifluoromethyl-2-ethoxycarbonyl-benzenesulphonamide,

[0266] 6-trifluoromethyl-2-n-propoxycarbonyl-benzenesulphonamide,

[0267] 6-trifluoromethyl-2-i-propoxycarbonyl-benzenesulphonamide,

[0268] 6-trifluoromethyl-2-(oxetan-2-yl-oxycarbonyl)-benzenesulphonamide,

[0269] 6-difluoromethoxy-2-methoxycarbonyl-benzenesulphonamide,

[0270] 6-difluoromethoxy-2-ethoxycarbonyl-benzenesulphonamide,

[0271] 6-difluoromethoxy-2-n-propoxycarbonyl-benzenesulphonamide,

[0272] 6-difluoromethoxy-2-i-propoxycarbonyl-benzenesulphonamide,

[0273] 6-difluoromethoxy-2-(oxetan-2-yl-oxycarbonyl)-benzenesulphonamide,

[0274] 6-trifluoromethoxy-2-methoxycarbonyl-benzenesulphonamide,

[0275] 6-trifluoromethoxy-2-ethoxycarbonyl-benzenesulphonamide,

[0276] 6-trifluoromethoxy-2-n-propoxycarbonyl-benzenesulphonamide,

[0277] 6-trifluoromethoxy-2-i-propoxycarbonyl-benzenesulphonamide,

[0278] 6-trifluoromethoxy-2-(oxetan-2-yl-oxycarbonyl)-benzenesulphonamide.

[0279] Starting Materials of the Formula (IV):

Example (IV-1)

[0280] 213

[0281] A mixture of 25 g (95 mmol) of 4-methyl-2-methoxycarbonyl-thiophene-3-sulphonamide, 9.4 g (95 mmol) of n-butyl isocyanate and 100 ml of chlorobenzene is heated to boiling point, and at reflux temperature, phosgene is introduced for 4 hours. The mixture is subsequently concentrated using water pump vacuum and the residue is purified by distillation under reduced pressure (2 mbar).

[0282] 11 g (40% of theory) of 4-methyl-2-methoxycarbonyl-thiophen-3-yl-sulfonyl isocyanate of a boiling range of 140° C.-145° C. (at 2 mbar), which solidify to give colourless crystals, are obtained.

[0283] Similarly, it is possible to prepare for example the following compounds of the formula (II):

[0284] 4-methyl-2-ethoxycarbonyl-thiophen-3-yl-sulphonyl isocyanate,

[0285] 4-methyl-2-n-propoxycarbonyl-thiophen-3-yl-sulphonyl isocyanate,

[0286] 4-methyl-2-i-propoxycarbonyl-thiophen-3-yl-sulphonyl isocyanate,

[0287] 4-methyl-2-(oxetan-2-yl-oxycarbonyl)-thiophen-3-yl-sulphonyl isocyanate,

[0288] 4-ethyl-2-methoxycarbonyl-thiophen-3-yl-sulphonyl isocyanate,

[0289] 4-ethyl-2-ethoxycarbonyl-thiophen-3-yl-sulphonyl isocyanate,

[0290] 4-ethyl-2-n-propoxycarbonyl-thiophen-3-yl-sulphonyl isocyanate,

[0291] 4-ethyl-2-i-propoxycarbonyl-thiophen-3-yl-sulphonyl isocyanate,

[0292] 4-ethyl-2-(oxetan-2-yl-oxycarbonyl)-thiophen-3-yl-sulphonyl isocyanate,

[0293] 4-fluoro-2-methoxycarbonyl-thiophen-3-yl-sulphonyl isocyanate,

[0294] 4-fluoro-2-ethoxycarbonyl-thiophen-3-yl-sulphonyl isocyanate,

[0295] 4-fluoro-2-n-propoxycarbonyl-thiophen-3-yl-sulphonyl isocyanate,

[0296] 4-fluoro-2-i-propoxycarbonyl-thiophen-3-yl-sulphonyl isocyanate,

[0297] 4-fluoro-2-(oxetan-2-yl-oxycarbonyl)-thiophen-3-yl-sulphonyl isocyanate,

[0298] 4-chloro-2-methoxycarbonyl-thiophen-3-yl-sulphonyl isocyanate,

[0299] 4-chloro-2-ethoxycarbonyl-thiophen-3-yl-sulphonyl isocyanate,

[0300] 4-chloro-2-n-propoxycarbonyl-thiophen-3-yl-sulphonyl isocyanate,

[0301] 4-chloro-2-i-propoxycarbonyl-thiophen-3-yl-sulphonyl isocyanate,

[0302] 4-chloro-2-(oxetan-2-yl-oxycarbonyl)-thiophen-3-yl-sulphonyl isocyanate,

[0303] 4-bromo-2-methoxycarbonyl-thiophen-3-yl-sulphonyl isocyanate,

[0304] 4-bromo-2-ethoxycarbonyl-thiophen-3-yl-sulphonyl isocyanate,

[0305] 4-bromo-2-n-propoxycarbonyl-thiophen-3-yl-sulphonyl isocyanate,

[0306] 4-bromo-2-i-propoxycarbonyl-thiophen-3-yl-sulphonyl isocyanate,

[0307] 4-bromo-2-(oxetan-2-yl-oxycarbonyl)-thiophen-3-yl-sulphonyl isocyanate,

[0308] 4-methoxy-2-methoxycarbonyl-thiophen-3-yl-sulphonyl isocyanate,

[0309] 4-methoxy-2-ethoxycarbonyl-thiophen-3-yl-sulphonyl isocyanate,

[0310] 4-methoxy-2-n-propoxycarbonyl-thiophen-3-yl-sulphonyl isocyanate,

[0311] 4-methoxy-2-i-propoxycarbonyl-thiophen-3-yl-sulphonyl isocyanate,

[0312] 4-methoxy-2-(oxetan-2-yl-oxycarbonyl)-thiophen-3-yl-sulphonyl isocyanate,

[0313] 4-methylthio-2-methoxycarbonyl-thiophen-3-yl-sulphonyl isocyanate,

[0314] 4-methylthio-2-ethoxycarbonyl-thiophen-3-yl-sulphonyl isocyanate,

[0315] 4-methylthio-2-n-propoxycarbonyl-thiophen-3-yl-sulphonyl isocyanate,

[0316] 4-methylthio-2-i-propoxycarbonyl-thiophen-3-yl-sulphonyl isocyanate,

[0317] 4-methylthio-2-(oxetan-2-yl-oxycarbonyl)-thiophen-3-yl-sulphonyl isocyanate,

[0318] 4-trifluoromethyl-2-methoxycarbonyl-thiophen-3-yl-sulphonyl isocyanate,

[0319] 4-trifluoromethyl-2-ethoxycarbonyl-thiophen-3-yl-sulphonyl isocyanate,

[0320] 4-trifluoromethyl-2-n-propoxycarbonyl-thiophen-3-yl-sulphonyl isocyanate,

[0321] 4-trifluoromethyl-2-i-propoxycarbonyl-thiophen-3-yl-sulphonyl isocyanate,

[0322] 4-trifluoromethyl-2-(oxetan-2-yl-oxycarbonyl)-thiophen-3-yl-sulphonyl isocyanate,

[0323] 4-difluoromethoxy-2-methoxycarbonyl-thiophen-3-yl-sulphonyl isocyanate,

[0324] 4-difluoromethoxy-2-ethoxycarbonyl-thiophen-3-yl-sulphonyl isocyanate,

[0325] 4-difluoromethoxy-2-n-propoxycarbonyl-thiophen-3-yl-sulphonyl isocyanate,

[0326] 4-difluoromethoxy-2-i-propoxycarbonyl-thiophen-3-yl-sulphonyl isocyanate,

[0327] 4-difluoromethoxy-2-(oxetan-2-yl-oxycarbonyl)-thiophen-3-yl-sulphonyl isocyanate,

[0328] 4-trifluoromethoxy-2-methoxycarbonyl-thiophen-3-yl-sulphonyl isocyanate,

[0329] 4-trifluoromethoxy-2-ethoxycarbonyl-thiophen-3-yl-sulphonyl isocyanate,

[0330] 4-trifluoromethoxy-2-n-propoxycarbonyl-thiophen-3-yl-sulphonyl isocyanate,

[0331] 4-trifluoromethoxy-2-i-propoxycarbonyl-thiophen-3-yl-sulphonyl isocyanate,

[0332] 4-trifluoromethoxy-2-(oxetan-2-yl-oxycarbonyl)-thiophen-3-yl-sulphonyl isocyanate,

[0333] 6-methyl-2-methoxycarbonyl-phenylsulphonyl isocyanate,

[0334] 6-methyl-2-ethoxycarbonyl-phenylsulphonyl isocyanate,

[0335] 6-methyl-2-n-propoxycarbonyl-phenylsulphonyl isocyanate,

[0336] 6-methyl-2-i-propoxycarbonyl-phenylsulphonyl isocyanate,

[0337] 6-methyl-2-(oxetan-2-yl-oxycarbonyl)-phenylsulphonyl isocyanate,

[0338] 6-ethyl-2-methoxycarbonyl-phenylsulphonyl isocyanate,

[0339] 6-ethyl-2-ethoxycarbonyl-phenylsulphonyl isocyanate,

[0340] 6-ethyl-2-n-propoxycarbonyl-phenylsulphonyl isocyanate,

[0341] 6-ethyl-2-i-propoxycarbonyl-phenylsulphonyl isocyanate,

[0342] 6-ethyl-2-(oxetan-2-yl-oxycarbonyl)-phenylsulphonyl isocyanate,

[0343] 6-fluoro-2-methoxycarbonyl-phenylsulphonyl isocyanate,

[0344] 6-fluoro-2-ethoxycarbonyl-phenylsulphonyl isocyanate,

[0345] 6-fluoro-2-n-propoxycarbonyl-phenylsulphonyl isocyanate,

[0346] 6-fluoro-2-i-propoxycarbonyl-phenylsulphonyl isocyanate,

[0347] 6-fluoro-2-(oxetan-2-yl-oxycarbonyl)-phenylsulphonyl isocyanate,

[0348] 6-chloro-2-methoxycarbonyl-phenylsulphonyl isocyanate,

[0349] 6-chloro-2-ethoxycarbonyl-phenylsulphonyl isocyanate,

[0350] 6-chloro-2-n-propoxycarbonyl-phenylsulphonyl isocyanate,

[0351] 6-chloro-2-i-propoxycarbonyl-phenylsulphonyl isocyanate,

[0352] 6-chloro-2-(oxetan-2-yl-oxycarbonyl)-phenylsulphonyl isocyanate,

[0353] 6-bromo-2-methoxycarbonyl-phenylsulphonyl isocyanate,

[0354] 6-bromo-2-ethoxycarbonyl-phenylsulphonyl isocyanate,

[0355] 6-bromo-2-n-propoxycarbonyl-phenylsulphonyl isocyanate,

[0356] 6-bromo-2-i-propoxycarbonyl-phenylsulphonyl isocyanate,

[0357] 6-bromo-2-(oxetan-2-yl-oxycarbonyl)-phenylsulphonyl isocyanate,

[0358] 6-methoxy-2-methoxycarbonyl-phenylsulphonyl isocyanate,

[0359] 6-methoxy-2-ethoxycarbonyl-phenylsulphonyl isocyanate,

[0360] 6-methoxy-2-n-propoxycarbonyl-phenylsulphonyl isocyanate,

[0361] 6-methoxy-2-i-propoxycarbonyl-phenylsulphonyl isocyanate,

[0362] 6-methoxy-2-(oxetan-2-yl-oxycarbonyl)-phenylsulphonyl isocyanate,

[0363] 6-methylthio-2-methoxycarbonyl-phenylsulphonyl isocyanate,

[0364] 6-methylthio-2-ethoxycarbonyl-phenylsulphonyl isocyanate,

[0365] 6-methylthio-2-n-propoxycarbonyl-phenylsulphonyl isocyanate,

[0366] 6-methylthio-2-i-propoxycarbonyl-phenylsulphonyl isocyanate,

[0367] 6-methylthio-2-(oxetan-2-yl-oxycarbonyl)-phenylsulphonyl isocyanate,

[0368] 6-trifluoromethyl-2-methoxycarbonyl-phenylsulphonyl isocyanate,

[0369] 6-trifluoromethyl-2-ethoxycarbonyl-phenylsulphonyl isocyanate,

[0370] 6-trifluoromethyl-2-n-propoxycarbonyl-phenylsulphonyl isocyanate,

[0371] 6-trifluoromethyl-2-i-propoxycarbonyl-phenylsulphonyl isocyanate,

[0372] 6-trifluoromethyl-2-(oxetan-2-yl-oxycarbonyl)-phenylsulphonyl isocyanate,

[0373] 6-difluoromethoxy-2-methoxycarbonyl-phenylsulphonyl isocyanate,

[0374] 6-difluoromethoxy-2-ethoxycarbonyl-phenylsulphonyl isocyanate,

[0375] 6-difluoromethoxy-2-n-propoxycarbonyl-phenylsulphonyl isocyanate,

[0376] 6-difluoromethoxy-2-i-propoxycarbonyl-phenylsulphonyl isocyanate,

[0377] 6-difluoromethoxy-2-(oxetan-2-yl-oxycarbonyl)-phenylsulphonyl isocyanate,

[0378] 6-trifluoromethoxy-2-methoxycarbonyl-phenylsulphonyl isocyanate,

[0379] 6-trifluoromethoxy-2-ethoxycarbonyl-phenylsulphonyl isocyanate,

[0380] 6-trifluoromethoxy-2-n-propoxycarbonyl-phenylsulphonyl isocyanate,

[0381] 6-trifluoromethoxy-2-i-propoxycarbonyl-phenylsulphonyl isocyanate,

[0382] 6-trifluoromethoxy-2-(oxetan-2-yl-oxycarbonyl)-phenylsulphonyl isocyanate.

[0383] Starting Materials of the Formula (VI):

Example (VI-1)

[0384] 214

[0385] A solution of 21.2 g (90 mmol) of i-propyl 3-amino-4-methyl-thiophene-2-carboxylate hydrochloride in 60 ml of conc. hydrochloric acid is cooled to about −10° C., and a solution of 6.9 g (100 mmol) of sodium nitrite in 13 ml of water is then added dropwise with stirring to this mixture at −10° C. to −5° C. The reaction mixture is stirred at −5° C. to 0° C. for about 60 minutes. The resulting diazonium salt solution is added dropwise at about 15° C. to a solution of 50 g of sulphur dioxide in 110 ml of acetic acid containing 10 ml of a saturated aqueous solution of copper(II) chloride. The mixture is stirred at room temperature (about 20° C.) for 12 hours and then diluted with about 500 ml of methylene chloride, washed twice with ice-water, dried over magnesium sulphate and filtered. The filtrate is concentrated using water pump vacuum, the residue is digested with petroleum ether and the resulting crystalline product is isolated by filtration with suction.

[0386] 17.0 g of (67% of theory) of 4-methyl-2-i-propoxycarbonyl-thiophene-3-sulphonyl chloride are obtained as a yellow solid of melting point 58° C. Similarly, it is possible to prepare for example the following compounds of the formula (VI):

[0387] 4-methyl-2-methoxycarbonyl-thiophene-3-sulphonyl chloride (mp.: 56° C.),

[0388] 4-methyl-2-ethoxycarbonyl-thiophene-3-sulphonyl chloride (mp.: 47° C.),

[0389] 4-methyl-2-n-propoxycarbonyl-thiophene-3-sulphonyl chloride (mp.: 42° C.),

[0390] 4-methyl-2-(oxetan-2-yl-oxycarbonyl)-thiophene-3-sulphonyl chloride,

[0391] 4-ethyl-2-methoxycarbonyl-thiophene-3-sulphonyl chloride,

[0392] 4-ethyl-2-ethoxycarbonyl-thiophene-3-sulphonyl chloride,

[0393] 4-ethyl-2-n-propoxycarbonyl-thiophene-3-sulphonyl chloride,

[0394] 4-ethyl-2-i-propoxycarbonyl-thiophene-3-sulphonyl chloride,

[0395] 4-ethyl-2-(oxetan-2-yl-oxycarbonyl)-thiophene-3-sulphonyl chloride,

[0396] 4-fluoro-2-methoxycarbonyl-thiophene-3-sulphonyl chloride,

[0397] 4-fluoro-2-ethoxycarbonyl-thiophene-3-sulphonyl chloride,

[0398] 4-fluoro-2-n-propoxycarbonyl-thiophene-3-sulphonyl chloride,

[0399] 4-fluoro-2-i-propoxycarbonyl-thiophene-3-sulphonyl chloride,

[0400] 4-fluoro-2-(oxetan-2-yl-oxycarbonyl)-thiophene-3-sulphonyl chloride,

[0401] 4-chloro-2-methoxycarbonyl-thiophene-3-sulphonyl chloride,

[0402] 4-chloro-2-ethoxycarbonyl-thiophene-3-sulphonyl chloride,

[0403] 4-chloro-2-n-propoxycarbonyl-thiophene-3-sulphonyl chloride,

[0404] 4-chloro-2-i-propoxycarbonyl-thiophene-3-sulphonyl chloride,

[0405] 4-chloro-2-(oxetan-2-yl-oxycarbonyl)-thiophene-3-sulphonyl chloride,

[0406] 4-bromo-2-methoxycarbonyl-thiophene-3-sulphonyl chloride,

[0407] 4-bromo-2-ethoxycarbonyl-thiophene-3-sulphonyl chloride,

[0408] 4-bromo-2-n-propoxycarbonyl-thiophene-3-sulphonyl chloride,

[0409] 4-bromo-2-i-propoxycarbonyl-thiophene-3-sulphonyl chloride,

[0410] 4-bromo-2-(oxetan-2-yl-oxycarbonyl)-thiophene-3-sulphonyl chloride,

[0411] 4-methoxy-2-methoxycarbonyl-thiophene-3-sulphonyl chloride,

[0412] 4-methoxy-2-ethoxycarbonyl-thiophene-3-sulphonyl chloride,

[0413] 4-methoxy-2-n-propoxycarbonyl-thiophene-3-sulphonyl chloride,

[0414] 4-methoxy-2-i-propoxycarbonyl-thiophene-3-sulphonyl chloride,

[0415] 4-methoxy-2-(oxetan-2-yl-oxycarbonyl)-thiophene-3-sulphonyl chloride,

[0416] 4-methylthio-2-methoxycarbonyl-thiophene-3-sulphonyl chloride,

[0417] 4-methylthio-2-ethoxycarbonyl-thiophene-3-sulphonyl chloride,

[0418] 4-methylthio-2-n-propoxycarbonyl-thiophene-3-sulphonyl chloride,

[0419] 4-methylthio-2-i-propoxycarbonyl-thiophene-3-sulphonyl chloride,

[0420] 4-methylthio-2-(oxetan-2-yl-oxycarbonyl)-thiophene-3-sulphonyl chloride,

[0421] 4-trifluoromethyl-2-methoxycarbonyl-thiophene-3-sulphonyl chloride,

[0422] 4-trifluoromethyl-2-ethoxycarbonyl-thiophene-3-sulphonyl chloride,

[0423] 4-trifluoromethyl-2-n-propoxycarbonyl-thiophene-3-sulphonyl chloride,

[0424] 4-trifluoromethyl-2-i-propoxycarbonyl-thiophene-3-sulphonyl chloride,

[0425] 4-trifluoromethyl-2-(oxetan-2-yl-oxycarbonyl)-thiophene-3-sulphonyl chloride,

[0426] 4-difluoromethoxy-2-methoxycarbonyl-thiophene-3-sulphonyl chloride,

[0427] 4-difluoromethoxy-2-ethoxycarbonyl-thiophene-3-sulphonyl chloride,

[0428] 4-difluoromethoxy-2-n-propoxycarbonyl-thiophene-3-sulphonyl chloride,

[0429] 4-difluoromethoxy-2-i-propoxycarbonyl-thiophene-3-sulphonyl chloride,

[0430] 4-difluoromethoxy-2-(oxetan-2-yl-oxycarbonyl)-thiophene-3-sulphonyl chloride,

[0431] 4-trifluoromethoxy-2-methoxycarbonyl-thiophene-3-sulphonyl chloride,

[0432] 4-trifluoromethoxy-2-ethoxycarbonyl-thiophene-3-sulphonyl chloride,

[0433] 4-trifluoromethoxy-2-n-propoxycarbonyl-thiophene-3-sulphonyl chloride,

[0434] 4-trifluoromethoxy-2-i-propoxycarbonyl-thiophene-3-sulphonyl chloride,

[0435] 4-trifluoromethoxy-2-(oxetan-2-yl-oxycarbonyl)-thiophene-3-sulphonyl chloride.

[0436] 6-methyl-2-methoxycarbonyl-benzenesulphonyl chloride (mp.: 109° C.),

[0437] 6-methyl-2-ethoxycarbonyl-benzenesulphonyl chloride (mp.: 82° C.),

[0438] 6-methyl-2-n-propoxycarbonyl-benzenesulphonyl chloride (mp.: 52° C.),

[0439] 6-methyl-2-i-propoxycarbonyl-benzenesulphonyl chloride (mp.: 51° C.),

[0440] 6-methyl-2-(oxetan-2-yl-oxycarbonyl)-benzenesulphonyl chloride,

[0441] 6-ethyl-2-methoxycarbonyl-benzenesulphonyl chloride,

[0442] 6-ethyl-2-ethoxycarbonyl-benzenesulphonyl chloride,

[0443] 6-ethyl-2-n-propoxycarbonyl-benzenesulphonyl chloride,

[0444] 6-ethyl-2-i-propoxycarbonyl-benzenesulphonyl chloride,

[0445] 6-ethyl-2-(oxetan-2-yl-oxycarbonyl)-benzenesulphonyl chloride,

[0446] 6-fluoro-2-methoxycarbonyl-benzenesulphonyl chloride,

[0447] 6-fluoro-2-ethoxycarbonyl-benzenesulphonyl chloride,

[0448] 6-fluoro-2-n-propoxycarbonyl-benzenesulphonyl chloride,

[0449] 6-fluoro-2-i-propoxycarbonyl-benzenesulphonyl chloride,

[0450] 6-fluoro-2-(oxetan-2-yl-oxycarbonyl)-benzenesulphonyl chloride,

[0451] 6-chloro-2-methoxycarbonyl-benzenesulphonyl chloride,

[0452] 6-chloro-2-ethoxycarbonyl-benzenesulphonyl chloride,

[0453] 6-chloro-2-n-propoxycarbonyl-benzenesulphonyl chloride,

[0454] 6-chloro-2-i-propoxycarbonyl-benzenesulphonyl chloride,

[0455] 6-chloro-2-(oxetan-2-yl-oxycarbonyl)-benzene-sulphonyl chloride,

[0456] 6-bromo-2-methoxycarbonyl-benzenesulphonyl chloride,

[0457] 6-bromo-2-ethoxycarbonyl-benzenesulphonyl chloride,

[0458] 6-bromo-2-n-propoxycarbonyl-benzenesulphonyl chloride,

[0459] 6-bromo-2-i-propoxycarbonyl-benzenesulphonyl chloride,

[0460] 6-bromo-2-(oxetan-2-yl-oxycarbonyl)-benzenesulphonyl chloride,

[0461] 6-methoxy-2-methoxycarbonyl-benzenesulphonyl chloride,

[0462] 6-methoxy-2-ethoxycarbonyl-benzenesulphonyl chloride,

[0463] 6-methoxy-2-n-propoxycarbonyl-benzenesulphonyl chloride,

[0464] 6-methoxy-2-i-propoxycarbonyl-benzenesulphonyl chloride,

[0465] 6-methoxy-2-(oxetan-2-yl-oxycarbonyl)-benzenesulphonyl chloride,

[0466] 6-methylthio-2-methoxycarbonyl-benzenesulphonyl chloride,

[0467] 6-methylthio-2-ethoxycarbonyl-benzenesulphonyl chloride,

[0468] 6-methylthio-2-n-propoxycarbonyl-benzenesulphonyl chloride,

[0469] 6-methylthio-2-i-propoxycarbonyl-benzenesulphonyl chloride,

[0470] 6-methylthio-2-(oxetan-2-yl-oxycarbonyl)-benzenesulphonyl chloride,

[0471] 6-trifluoromethyl-2-methoxycarbonyl-benzenesulphonyl chloride,

[0472] 6-trifluoromethyl-2-ethoxycarbonyl-benzenesulphonyl chloride (amorphous),

[0473] 6-trifluoromethyl-2-n-propoxycarbonyl-benzenesulphonyl chloride,

[0474] 6-trifluoromethyl-2-i-propoxycarbonyl-benzenesulphonyl chloride (mp.: 64° C.),

[0475] 6-trifluoromethyl-2-(oxetan-2-yl-oxycarbonyl)-benzenesulphonyl chloride,

[0476] 6-difluoromethoxy-2-methoxycarbonyl-benzenesulphonyl chloride,

[0477] 6-difluoromethoxy-2-ethoxycarbonyl-benzenesulphonyl chloride,

[0478] 6-difluoromethoxy-2-n-propoxycarbonyl-benzenesulphonyl chloride,

[0479] 6-difluoromethoxy-2-i-propoxycarbonyl-benzenesulphonyl chloride,

[0480] 6-difluoromethoxy-2-(oxetan-2-yl-oxycarbonyl)-benzenesulphonyl chloride,

[0481] 6-trifluoromethoxy-2-methoxycarbonyl-benzenesulphonyl chloride,

[0482] 6-trifluoromethoxy-2-ethoxycarbonyl-benzenesulphonyl chloride,

[0483] 6-trifluoromethoxy-2-n-propoxycarbonyl-benzenesulphonyl chloride,

[0484] 6-trifluoromethoxy-2-i-propoxycarbonyl-benzenesulphonyl chloride,

[0485] 6-trifluoromethoxy-2-(oxetan-2-yl-oxycarbonyl)-benzenesulphonyl chloride.

[0486] Starting Materials of the Formula (X):

Example (X-1)

[0487] 215

[0488] With shaking, a mixture of 192 g (1.43 mol) of i-propyl mercaptoacetate and 183 g (1.43 mol) of i-propyl methacrylate is admixed with 5 drops of piperidine. The mixture is heated to 50° C., admixed with a further 20 drops of piperidine and stirred at a bath temperature of 100° C. for 12 hours. The mixture is subsequently distilled under reduced pressure.

[0489] 288 g (77% of theory) of i-propyl 2-methyl-3-(i-propoxycarbonylmethylthio)-propionate are obtained as a colourless oil of a boiling range of 135° C. to 140° C. at 2 mbar.

[0490] Similarly, it is possible to prepare for example the following compounds:

[0491] methyl 2-methyl-3-(methoxycarbonylmethylthio)-propionate,

[0492] ethyl 2-methyl-3-(ethoxycarbonylmethylthio)-propionate (bp.: 105° C. to 112° C. at 1 mbar),

[0493] n-propyl 2-methyl-3-(n-propoxycarbonylmethylthio)-propionate (bp.: 145° C. to 147° C. at 3 mbar),

[0494] methyl 2-methyl-3-(ethoxycarbonylmethylthio)-propionate (bp.: 150° C. to 152° C. at 0.1 mbar),

[0495] methyl 2-methyl-3-(n-propoxycarbonylmethylthio)-propionate (bp.: 158° C. to 160° C. at 0.1 mbar),

[0496] methyl 2-methyl-3 -(i-propoxycarbonylmethylthio)-propionate (bp.: 162° C. to 165° C. at 0.1 mbar),

[0497] methyl 2-ethyl-3-(methoxycarbonylmethylthio)-propionate,

[0498] ethyl 2-ethyl-3-(ethoxycarbonylmethylthio)-propionate,

[0499] n-propyl 2-ethyl-3-(n-propoxycarbonylmethylthio)-propionate,

[0500] i-propyl 2-ethyl-3-(i-propoxycarbonylmethylthio)-propionate,

[0501] methyl 2-ethyl-3-(ethoxycarbonylmethylthio)-propionate,

[0502] methyl 2-ethyl-3-(n-propoxycarbonylmethylthio)-propionate,

[0503] methyl 2-ethyl-3-(i-propoxycarbonylmethylthio)-propionate,

[0504] methyl 2-trifluoromethyl-3-(methoxycarbonylmethylthio)-propionate,

[0505] ethyl 2-trifluoromethyl-3-(ethoxycarbonylmethylthio)-propionate,

[0506] n-propyl 2-trifluoromethyl-3-(n-propoxycarbonylmethylthio)-propionate,

[0507] i-propyl 2-trifluoromethyl-3-(i-propoxycarbonylmethylthio)-propionate,

[0508] methyl 2-trifluoromethyl-3-(ethoxycarbonylmethylthio)-propionate,

[0509] methyl 2-trifluoromethyl-3-(n-propoxycarbonylmethylthio)-propionate,

[0510] methyl 2-trifluoromethyl-3 -(i-propoxycarbonylmethylthio)-propionate,

[0511] methyl 2-chloro-3-(methoxycarbonylmethylthio)-propionate,

[0512] ethyl 2-chloro-3-(ethoxycarbonylmethylthio)-propionate,

[0513] n-propyl 2-chloro-3-(n-propoxycarbonylmethylthio)-propionate,

[0514] i-propyl 2-chloro-3-(i-propoxycarbonylmethylthio)-propionate,

[0515] methyl 2-chloro-3-(ethoxycarbonylmethylthio)-propionate,

[0516] methyl 2-chloro-3-(n-propoxycarbonylmethylthio)-propionate,

[0517] methyl 2-chloro-3-(i-propoxycarbonylmethylthio)-propionate.

[0518] Step 2 216

[0519] At room temperature (about 20° C.), 480 g (1.83 mol) of i-propyl 2-methyl-3-(i-propoxycarbonylmethylthio)-propionate are added dropwise to a suspension of 246 g (3.0 mol) of sodium i-propoxide in 1 litre of toluene, and the mixture is then stirred at about 90° C. for about 12 hours. The mixture is subsequently poured into ice-cold 2N hydrochloric acid. This mixture is then extracted three times with diethyl ether and the combined extracts are washed twice with water. The organic phase is dried over magnesium sulphate and filtered. The filtrate is concentrated using water pump vacuum and the residue is distilled under reduced pressure.

[0520] 254 g (69% of theory) of i-propyl 4-methyl-3-oxo-tetrahydrothiophene-2-carboxylate are obtained as a light-yellow oil of boiling point 11 9° C. to 120° C. at I mbar.

[0521] Similarly, it is possible to prepare for example the following compounds:

[0522] methyl 4-methyl-3-oxo-tetrahydrothiophene-2-carboxylate,

[0523] ethyl 4-methyl-3-oxo-tetrahydrothiophene-2-carboxylate (bp.: 112° C. at 4 mbar),

[0524] n-propyl 4-methyl-3-oxo-tetrahydrothiophene-2-carboxylate (bp.: 127° C. to 128° C. at 1 mbar),

[0525] methyl 4-ethyl-3 -oxo-tetrahydrothiophene-2-carboxylate,

[0526] ethyl 4-ethyl-3-oxo-tetrahydrothiophene-2-carboxylate,

[0527] n-propyl 4-ethyl-3-oxo-tetrahydrothiophene-2-carboxylate,

[0528] i-propyl 4-ethyl-3-oxo-tetrahydrothiophene-2-carboxylate,

[0529] methyl 4-trifluoromethyl-3-oxo-tetrahydrothiophene-2-carboxylate,

[0530] ethyl 4-trifluoromethyl-3-oxo-tetrahydrothiophene-2-carboxylate,

[0531] n-propyl 4-trifluoromethyl-3-oxo-tetrahydrothiophene-2-carboxylate,

[0532] i-propyl 4-trifluoromethyl-3-oxo-tetrahydrothiophene-2-carboxylate,

[0533] methyl 4-chloro-3-oxo-tetrahydrothiophene-2-carboxylate,

[0534] ethyl 4-chloro-3-oxo-tetrahydrothiophene-2-carboxylate,

[0535] n-propyl 4-chloro-3-oxo-tetrahydrothiophene-2-carboxylate,

[0536] i-propyl 4-chloro-3-oxo-tetrahydrothiophene-2-carboxylate.

[0537] Step 3 217

[0538] A mixture of 505 g (2.5 mol) of i-propyl 4-methyl-3-oxo-tetrahydrothiophene-2-carboxylate, 497 g (7.2 mol) of hydroxylamine hydrochloride, 753 g (3.8 mol) of barium carbonate and 2.5 litres of isopropanol is heated under reflux for about 12 hours. The mixture is subsequently filtered off with suction, the filter cake is washed with hot isopropanol and the filtrate is concentrated using water pump vacuum. The residue is taken up in 2 litres of diethyl ether, washed twice with water, dried over magnesium sulphate and filtered. The solvent is carefully distilled off from the filtrate using water pump vacuum.

[0539] 445 g (82% of theory) of 1-propyl 4-methyl-3-hydroximino-tetrahydrothiophene-2-carboxylate are obtained as a light-yellow oily crude product which is employed without any further purification for the next step.

[0540] Similarly, it is possible to prepare for example the following compounds:

[0541] methyl 4-methyl-3-hydroximino-tetrahydrothiophene-2-carboxylate,

[0542] ethyl 4-methyl-3-hydroximino-tetrahydrothiophene-2-carboxylate (colourless oil),

[0543] n-propyl 4-methyl-3-hydroximino-tetrahydrothiophene-2-carboxylate (light-yellow oil),

[0544] methyl 4-ethyl-3-hydroximino-tetrahydrothiophene-2-carboxylate,

[0545] ethyl 4-ethyl-3-hydroximino-tetrahydrothiophene-2-carboxylate,

[0546] n-propyl 4-ethyl-3 -hydroximino-tetrahydrothiophene-2-carboxylate,

[0547] i-propyl 4-ethyl-3-hydroximino-tetrahydrothiophene-2-carboxylate,

[0548] methyl 4-trifluoromethyl-3-hydroximino-tetrahydrothiophene-2-carboxylate,

[0549] ethyl 4-trifluoromethyl-3-hydroximino-tetrahydrothiophene-2-carboxylate,

[0550] n-propyl 4-trifluoromethyl-3-hydroximino-tetrahydrothiophene-2-carboxylate,

[0551] i-propyl 4-trifluoromethyl-3-hydroximino-tetrahydrothiophene-2-carboxylate,

[0552] methyl 4-chloro-3-hydroximino-tetrahydrothiophene-2-carboxylate,

[0553] ethyl 4-chloro-3-hydroximino-tetrahydrothiophene-2-carboxylate,

[0554] n-propyl 4-chloro-3-hydroximino-tetrahydrothiophene-2-carboxylate,

[0555] i-propyl 4-chloro-3-hydroximino-tetrahydrothiophene-2-carboxylate.

[0556] Step 4 218

[0557] 334 g (1.54 mol) of i-propyl 4-methyl-3-hydroximino-tetrahydrothiophene-2-carboxylate are dissolved in 5 litres of methyl tert-butyl ether and cooled using an ice bath. Hydrogen chloride is then—after the ice bath had been removed—introduced with stirring for two hours. The mixture is subsequently concentrated using water pump vacuum and the amorphous residue is crystallized from acetone.

[0558] 358 g (99% of theory) of i-propyl 3-amino-4-methyl-thiophene-2-carboxylate hydrochloride are obtained as a beige-coloured solid of melting point 153° C.

[0559] Similarly, it is possible to prepare for example the following compounds:

[0560] ethyl 3-amino-4-methyl-thiophene-2-carboxylate hydrochloride (mp.: 133° C.),

[0561] n-propyl 3-amino-4-methyl-thiophene-2-carboxylate hydrochloride (mp.: 152° C.),

[0562] ethyl 3-amino-4-ethyl-thiophene-2-carboxylate hydrochloride,

[0563] n-propyl 3-amino-4-ethyl-thiophene-2-carboxylate hydrochloride,

[0564] i-propyl 3-amino-4-ethyl-thiophene-2-carboxylate hydrochloride,

[0565] ethyl 3-amino-4-trifluoromethyl-thiophene-2-carboxylate hydrochloride,

[0566] n-propyl 3-amino-4-trifluoromethyl-thiophene-2-carboxylate hydrochloride,

[0567] i-propyl 3-amino-4-trifluoromethyl-thiophene-2-carboxylate hydrochloride,

[0568] ethyl 3-amino-4-chloro-thiophene-2-carboxylate hydrochloride,

[0569] n-propyl 3-amino-4-chloro-thiophene-2-carboxylate hydrochloride,

[0570] i-propyl 3-amino-4-chloro-thiophene-2-carboxylate hydrochloride.

[0571] Step 5 219

[0572] 11.75 g (50 mmol) of i-propyl 3-amino-4-methyl-thiophene-2-carboxylate hydrochloride are dissolved in 100 ml of water. 150 ml of methylene chloride are added to this solution, and sodium bicarbonate is then added a little at a time until a pH of 7 has been exceeded. The mixture is stirred for 8 hours and the organic phase is separated off, washed with water, dried with magnesium sulphate and filtered. The filtrate is concentrated using water pump vacuum and the amorphous residue is crystallized from petroleum ether.

[0573] 7.2 g (73% of theory) of i-propyl 3-amino-4-methyl-thiophene-2-carboxylate are obtained as a beige-coloured solid of melting point 40° C.

[0574] Similarly, it is possible to prepare for example the following compounds:

[0575] ethyl 3-amino-4-methyl-thiophene-2-carboxylate (mp.: 133° C.),

[0576] n-propyl 3-amino-4-methyl-thiophene-2-carboxylate (amorphous),

[0577] ethyl 3-amino-4-ethyl-thiophene-2-carboxylate,

[0578] n-propyl 3-amino-4-ethyl-thiophene-2-carboxylate,

[0579] i-propyl 3-amino-4-ethyl-thiophene-2-carboxylate,

[0580] ethyl 3-amino-4-trifluoromethyl-thiophene-2-carboxylate,

[0581] n-propyl 3-amino-4-trifluoromethyl-thiophene-2-carboxylate,

[0582] i-propyl 3-amino-4-trifluoromethyl-thiophene-2-carboxylate,

[0583] ethyl 3-amino-4-chloro-thiophene-2-carboxylate,

[0584] n-propyl 3-amino-4-chloro-thiophene-2-carboxylate,

[0585] i-propyl 3-amino-4-chloro-thiophene-2-carboxylate.

[0586] Use Examples:

Example A

[0587] Pre-emergence test

[0588] Solvent: 5 parts by weight of acetone

[0589] Emulsifier: 1 part by weight of alkylaryl polyglycol ether

[0590] To produce a suitable preparation of the 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.

[0591] Seeds of the test plants are sown in normal soil. After about 24 hours, the soil is watered with the preparation of 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 appliation rate per unit area matters.

[0592] After three weeks, the degree of damage to the plants is rated in % damage in comparison to the development of the untreated control.

[0593] The figures denote:

[0594] 0% no action (like untreated control)

[0595] 100%=total destruction

[0596] In this test, very strong activity against weeds is shown, for example, by the compounds of Preparation Examples 1, 3, 5, 6, 7, 8, 9, 10, 12, 13, 16, 17, 18, 19, 20, 21, 22, 23, 28, 30, 31, 32, 33, 34, 35, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 51, 53, 54, 55, 56, 57, 58, 59, 61, 62, 63, 64, 65, 66, 67, 68, 70, 72, 76, 77, 80, 81, 82, 84, 85, 86, 89, 93, 108, 121, 129, 130, 131, 134, 135, 136, 140, 141, 142, 143, 144, 145, 146, 147, 148, 149, 150, 151, 152, 153, 154, 155, 156, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167 and 172, combined with predominantly good tolerance by crop plants such as, for example, maize and soya beans.

[0597] “ai.”=active compound (“active ingredient”) 2 TABLE A Pre-emergence test/Greenhouse Active compound of Application Preparation rate Soya Example (g of ai./ha) Maize beans Lolium Poa Sorghum Ambrosia Matricaria Solanum 5 30 0 20 95 95 90 95 95 95 1 30 10 — 95 95 90 95 95 95 6 125 0 — 95 95 95 95 95 95 7 60 0 0 95 — 95 95 95 — 8 60 30 0 95 90 80 90 95 95 9 125 0 — 80 80 60 95 90 95 10 250 0 20 80 90 70 95 95 95 12 125 0 0 80 80 60 95 95 95 13 125 30 — 90 80 70 95 95 90 16 30 — 0 95 95 90 95 95 95 17 30 — 0 80 95 60 95 95 95 18 60 10 0 80 95 90 95 95 95 19 60 0 0 95 95 — 95 95 90 20 125 10 0 95 95 90 95 95 95 21 125 0 0 95 95 95 95 95 95 22 125 20 10 95 95 80 95 95 95 23 125 0 0 — 80 60 90 95 90 28 60 0 — 95 95 95 95 95 95 30 30 0 — 95 95 80 95 95 95 31 15 10 — 95 95 80 95 95 95 32 60 20 20 95 95 60 95 95 95 33 125 10 — — 90 80 90 95 95 34 60 10 0 60 70 80 90 95 90 35 60 0 — 95 95 95 95 100 95 37 60 10 10 90 70 — 80 95 90 38 60 0 — 95 70 60 95 95 95 39 60 0 20 95 90 — 95 70 90 40 60 10 30 90 95 — 95 95 95 41 60 0 — 60 80 60 95 95 90 42 60 10 10 95 95 — 95 95 95 43 60 — 10 95 95 80 95 95 95 44 8 30 0 95 95 95 95 95 95 45 125 10 20 90 95 — 95 90 95 46 8 0 — 80 95 80 95 95 95 47 125 10 10 90 90 60 95 95 95 48 125 30 20 95 95 — 95 100 95 51 125 0 30 80 80 80 95 95 95 53 125 0 — 95 95 — 95 95 95 54 30 0 — 95 95 80 95 95 95 55 125 10 — 100 90 60 100 100 100 56 125 — 0 60 80 — — 100 95 57 60 0 — 95 95 95 — 95 95 58 125 20 — 80 95 — — 100 95 59 125 0 — 100 70 — 95 100 95 61 125 0 — 95 95 80 100 95 95 62 125 0 — 80 90 60 — 95 95 63 60 10 — 100 95 80 100 100 100 64 60 10 30 90 60 — 100 100 100 65 125 20 — 80 80 80 — 95 95 66 125 0 — 100 — 100 — 100 100 67 60 0 — 100 — 90 — 100 100 68 125 5 10 80 90 60 95 100 95 70 60 10 — 90 90 — 90 100 100 72 125 10 — 90 70 — 95 100 100 76 60 0 30 95 — 95 — 100 95 77 60 0 — 95 — 90 — 100 90 80 125 0 — 95 — 90 — 100 95 81 60 — — 100 — 95 — 100 100 82 60 0 — 60 — 90 — 100 100 84 125 5 30 95 — 90 — 95 100 85 125 60 — 95 — 95 — 100 100 86 125 10 40 80 — 70 — 100 95 89 125 0 — 100 — 90 — 100 100 93 60 0 — 90 — 80 — 95 90 108 125 5 — 90 — 95 — 95 90 121 500 10 — 70 — 80 — 90 95 129 250 10 10 95 95 90 60 90 95 130 250 10 0 95 95 80 95 95 95 131 250 0 0 95 90 90 95 80 95 134 500 0 20 95 90 70 80 90 95 135 125 — 40 95 95 90 90 90 95 136 125 30 20 95 95 90 80 90 95 140 30 — 10 — 95 95 80 80 95 141 15 30 0 90 80 80 90 80 90 142 15 20 10 95 80 — 80 80 80 143 60 20 0 90 90 90 80 — 90 144 125 — — 90 90 95 80 95 95 145 60 0 0 95 95 95 95 60 95 3 60 10 20 90 70 — 80 95 80 146 60 0 10 80 90 — 80 80 90 147 15 30 0 95 90 — 70 70 80 148 60 40 0 80 95 90 80 80 95 149 125 0 30 95 95 80 95 95 95 150 125 — 10 80 90 80 70 80 80 151 15 20 10 90 90 50 80 90 90 152 125 — 20 95 95 95 95 80 95 153 125 0 30 — 95 — 95 70 95 154 60 0 0 95 95 95 70 70 90 155 60 — 40 95 95 95 90 80 95 156 60 0 10 70 90 70 70 95 70 157 60 0 20 90 80 80 95 100 90 158 30 10 — 95 95 60 95 95 95 159 30 10 — 90 95 60 95 95 95 160 60 30 10 90 90 60 90 95 90 161 60 0 20 95 95 — 95 95 95 162 60 — 0 95 95 90 80 95 95 163 4 20 0 80 95 60 80 — 90 164 8 20 0 95 95 90 100 70 95 165 8 0 10 — 90 70 80 90 80 166 15 40 — 90 90 70 80 95 90 167 60 — 30 80 95 95 90 95 90 172 125 — 60 90 95 90 90 95 95

Example B

[0598] Post-emergence Test

[0599] Solvent: 5 parts by weight of acetone

[0600] Emulsifier: 1 part by weight of alkylaryl polyglycol ether

[0601] 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.

[0602] 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 spray liquor is chosen so that the particular amounts of active compound desired are applied in 2000 1 of water/ha.

[0603] After three weeks, the degree of damage to the plants is rated in % damage in comparison to the development of the untreated control.

[0604] The figures denote:

[0605] 0%=no action (like untreated control)

[0606] 100%=total destruction

[0607] In this test, very strong activity against weeds is shown, for example, by the compounds of Preparation Examples 1, 5, 6, 7, 28, 30, 31, 32, 38, 44, 54, 63, 140, 141, 144, 151, 159, 162, 163, 164, 165 and 166, combined with predominantly good tolerance by crop plants such as, for example, maize. 3 TABLE B Post-emergence test/greenhouse Active compound of Application Preparation rate Example (g of ai./ha) Maize Digitaria Echinochloa Lolium Sorghum Amaranthus Gallium Matricaria Stellaria 5 30 10 95 80 70 90 100 — 95 90 1 125 60 95 95 90 95 100 — 100 100 6 400 20 90 95 95 80 100 90 100 100 7 60 15 95 95 95 100 — 95 95 100 28 60 10 90 80 60 95 100 80 90 100 30 60 15 90 70 60 95 100 85 100 100 31 30  5 95 95 90 80 100 80 100 95 32 60 70 70 100  70 95  95 70 80 90 38 60 10 70 90 — 95 100 — 95 95 44 60 50 60 90 70 100 100 95 95 — 54 60 30 — 95 95 95 100 85 100 100 63 60 — 50 90 70 80 100 90 95 100 140 250 — 95 90 — 95 100 95 90 70 141 30 10 70 90 — 90 100 90 70 95 144 250 — 95 95 70 95 100 95 70 95 151 30 60 90 70 60 90  95 90 90 90 159 60 — 60 80 60 70  95 95 100 100 162 60 — 70 80 90 80 — — 60 90 163 60 60 80 70 80 95 100 95 100 95 164 60 — 60 80 70 95 100 90 100 95 165 60 — 50 80 50 90  95 95 95 95 166 60 — 70 70 50 90  95 95 100 95

Claims

1. Substituted sulphonylamino(thio)carbonyl compounds of the general formula (I),

220

in which

A represents oxygen, sulphur, NH, N-alkyl, N-aryl, —CH═N—, or —N═CH— or —CH═CH—,

Q represents oxygen or sulphur,

R1 represents respectively optionally substituted alkyl, alkenyl, alkinyl, cycloalkyl, cycloalkylalkyl, aryl, arylalkyl, heterocyclyl or heterocyclylalkyl,

R2 represents cyano, nitro, halogen or represents respectively optionally substituted alkyl, alkoxy, alkoxycarbonyl, alkylthio, alkylsulphinyl, alkylsulphonyl, alkenyl, alkinyl, alkenyloxy or alkinyloxy, and

R3 represents respectively optionally substituted heterocyclyl having 5 ring members of which at least one represents oxygen, sulphur or nitrogen and a further one to three may represent nitrogen,

and salts of compounds of the formula (I),

except for the compounds N-(2-chloro-6-methoxycarbonyl-phenylsulphonyl)-5-phenyl-1,2,4-oxadiazole-3-carboxamide, N-(2-chloro-6-methoxycarbonyl-phenylsulphonyl)-oxazole-2-carboxamide, N-(2-chloro-6-methoxycarbonyl-phenylsulphonyl)-4-methyl-oxazole-2-carboxamide, N-(2-chloro-6-methoxycarbonyl-phenylsulphonyl)-4-ethyl-5-methyl-oxazole-2-carboxamide, N-(2-chloro-6-methoxycarbonyl-phenylsulphonyl)-ethyl-oxazole-4-carboxamide, N-(2-chloro-6-methoxycarbonyl-phenylsulphonyl)-5-ethyl-thiazole-2-carboxamide, N-(2-chloro-6-methoxycarbonyl-phenylsulphonyl)-5-methyl-4-methylthio-thiazole-2-carboxamide, N-(2-chloro-6-methoxycarbonyl-phenylsulphonyl)-2,5-dimethyl-thiazole-4-carboxamide, N-(2-chloro-6-methoxycarbonyl-phenylsulphonyl)-2-chloro-thiazole-5-carboxamide, N-(2-chloro-6-methoxycarbonyl-phenylsulphonyl)-1,3,4-oxadiazole-2-carboxamide, N-(2-chloro-6-methoxycarbonyl-phenylsulphonyl)-1,3,4-thiadiazole-2-carboxamide, N-(2-chloro-6-methoxycarbonyl-phenylsulphonyl)-5-chloro-1,3,4-thiadiazole-2-carboxamide, N-(2-chloro-6-methoxycarbonyl-phenylsulphonyl)-5-phenyl-1,3,4-thiadiazole-2-carboxamide, N-(2-chloro-6-methoxycarbonyl-phenylsulphonyl)-5-methyl-isoxazole-3-carboxamide, N-(2-chloro-6-methoxycarbonyl-phenylsulphonyl)-isoxazole-3-carboxamide, N-(2-chloro-6-methoxycarbonyl-phenylsulphonyl)-isoxazole-5-carboxamide, N-(2-chloro-6-methoxycarbonyl-phenylsulphonyl)-methyl-isoxazole-4-carboxamide and N-(2-chloro-6-methoxycarbonyl-phenylsulphonyl)-3,5-dimethyl-isoxazole-4-carboxamide.

2. Compounds of the formula (I) according to claim 1, characterized in that

A represents oxygen, sulphur, NH, N-C1-C4-alkyl, N-phenyl, —CH═N— or —N═CH— or —CH═CH—,

Q represents oxygen or sulphur,

R1 represents optionally cyano-, nitro-, halogen- or C1-C4-alkoxy-substituted C1-C6-alkyl, represents respectively optionally cyano- or halogen-substituted C2-C6-alkenyl or C2-C6-alkinyl, represents respectively optionally cyano-, halogen- or C1-C4-alkyl-substituted C3-C6-cycloalkyl, C3-C6-cycloalkyl-C1-C4-alkyl, represents respectively optionally cyano-, nitro-, halogen-, C1-C4-alkyl-, C1-C4-halogenoalkyl-, C1-C4-alkoxy- or C1-C4-halogenoalkoxy-substituted phenyl or phenyl-C1-C4-alkyl, or represents respectively optionally cyano-, nitro-, halogen-, C1 -C4-alkyl-, C1-C4-halogenoalkyl-, C1 -C4-alkoxy- or C1-C4-halogenoalkoxy-substituted heterocyclyl or heterocyclyl-C1-C4-alkyl, where in each case the heterocyclyl group is selected from the group consisting of oxetanyl, thietanyl, furyl, tetrahydrofuryl, thienyl, tetrahydrothienyl, oxazolyl, isoxazolyl, thiazolyl, oxadiazolyl, thiadiazolyl,

R2 represents cyano, nitro, halogen, represents respectively optionally cyano-, halogen- or C1-C4-alkoxy-substituted C1-C4-alkyl, C1-C4-alkoxy, C1-C4-alkoxy-carbonyl, C1-C4-alkylthio, C1-C4-alkylsulphinyl or C1-C4-alkylsulphonyl, or represents respectively optionally cyano- or halogen-substituted C2-C4-alkenyl, C2-C4-alkinyl, C2-C4-alkenyloxy or C2-C4-alkinyloxy, and

R3 represents respectively optionally substituted heterocyclyl of the formulae below,

221

in which

Q1, Q2 and Q3 each represent oxygen or sulphur and

R4 represents hydrogen, hydroxyl, amino, cyano, represents C2-C10-alkylidene-amino, represents optionally fluorine-, chlorine-, bromine-, cyano-, C1-C4-alkoxy-, C1-C4-alkyl-carbonyl- or C1-C4-alkoxy-carbonyl-substituted C1-C6-alkyl, represents respectively optionally fluorine-, chlorine- and/or bromine-substituted C2-C6-alkenyl or C2-C6-alkinyl, represents respectively optionally fluorine-, chlorine-, bromine-, cyano-, C1-C4-alkoxy- or C1-C4-alkoxy-carbonyl-substituted C1-C6-alkoxy, C1-C6-alkylamino or C1-C6-alkyl-carbonyl-amino, represents C3-C6-alkenyloxy, represents di-(C1-C4-alkyl)-amino, represents respectively optionally fluorine-, chlorine-, bromine-, cyano- and/or C1-C4-alkyl-substituted C3-C6-cycloalkyl, C3-C6-cycloalkyl-amino or C3-C6-cycloalkyl-CI-C4-alkyl, or represents respectively optionally fluorine-, chlorine-, bromine-, cyano-, nitro-, C1-C4-alkyl-, trifluoromethyl- and/or C1-C4-alkoxy-substituted phenyl or phenyl-C1-C4-alkyl,

R5 represents hydrogen, hydroxyl, mercapto, amino, cyano, fluorine, chlorine, bromine, iodine, represents optionally fluorine-, chlorine-, bromine-, cyano-, C1-C4-alkoxy-, C1-C4-alkyl-carbonyl- or C1-C4-alkoxy-carbonyl-substituted C1-C6-alkyl, represents espectively optionally fluorine-, chlorine- and/or bromine-substituted C2-C6-alkenyl or C2-C6-alkinyl, represents respectively optionally fluorine-, chlorine-, cyano-, C1-C4-alkoxy- or C1-C4-alkoxy-carbonyl-substituted C1-C6-alkoxy, C1-C6-alkylthio, C1-C6-alkylamino or C1-C6-alkyl-carbonylamino, represents C3-C6-alkenyloxy, C3-C6-alkinyloxy, C3-C6-alkenylthio, C3-C6-alkinylthio, C3-C6-alkenylamino or C3-C6-alkinylamino, represents di-(C1-C4-alkyl)-amino, represents respectively optionally methyl- and/or ethyl-substituted aziridino, pyrrolidino, piperidino or morpholino, represents respectively optionally fluorine-, chlorine-, bromine-, cyano- and/or C1-C4-alkyl-substituted C3-C6-cycloalkyl, C5-C6-cycloalkenyl, C3-C6-cycloalkyloxy, C3-C6-cycloalkylthio, C3-C6-cycloalkylamino, C3-C6-cycloalkyl-C1-C4-alkyl, C3-C6-cycloalkyl-C1-C4-alkoxy, C3-C6-cycloalkyl-C1-C4-alkylthio or C3 -C6-cycloalkyl-C1-C4-alkylamino, or represents respectively optionally fluorine-, chlorine-, bromine-, cyano-, nitro-, C1-C4-alkyl-, trifluoromethyl-, C1-C4-alkoxy- and/or C1-C4-alkoxy-carbonyl-substituted phenyl, phenyl-C1-C4-alkyl, phenoxy, phenyl-C1-C4-alkoxy, phenylthio, phenyl-C1-C4-alkylthio, phenylamino or phenyl-C1-C4-alkylamino, or

R4 and R5 together represent optionally branched alkanediyl having 3 to 11 carbon atoms, furthermore

R6, R7 and R8 are identical or different and each represents hydrogen, cyano, fluorine, chlorine, bromine, or represents respectively optionally fluorine-, chlorine-, bromine- or C1-C4-alkoxy-substituted alkyl, alkenyl, alkinyl, alkoxy, alkenyloxy, alkinyloxy, alkylthio, alkenylthio, alkinylthio, alkylsulphinyl or alkylsulphonyl having in each case up to 6 carbon atoms or represent optionally cyano-, fluorine-, chlorine-, bromine- or C1-C4-alkyl-substituted cycloalkyl having 3 to 6 carbon atoms,

and the sodium, potassium, magnesium, calcium, ammonium, C1-C4-alkyl-ammonium, di-(C1-C4-alkyl)-ammonium, tri-(C1-C4-alkyl)-ammonium, tetra-(C1-C4-alkyl)-ammonium, tri-(CI-C4-alkyl)-sulphonium, C5- or C6-cycloalkyl-ammonium and di-(C1-C2-alkyl)-benzyl-ammonium salts of compounds of the formula (I),

except for the individual compounds mentioned in claim 1.

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

A represents sulphur, N-methyl, —CH═N— or —N═CH— or —CH═CH—,

Q represents oxygen or sulphur,

R1 represents respectively optionally cyano-, fluorine-, chlorine-, methoxy- or ethoxy-substituted methyl, ethyl, n- or i-propyl, n-, i- or s-butyl, represents respectively optionally cyano-, fluorine- or chlorine-substituted propenyl, butenyl, propinyl or butinyl, represents respectively optionally cyano-, fluorine-, chlorine-, methyl- or ethyl-substituted cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl or cyclo-hexylmethyl, represents respectively optionally cyano-, fluorine-, chlorine-, bromine-, methyl-, ethyl-, trifluoromethyl-, methoxy-, ethoxy-, difluoromethoxy- or trifluoromethoxy-substituted phenyl, phenylmethyl or phenylethyl, or represents respectively optionally cyano-, fluorine-, chlorine-, bromine-, methyl-, ethyl-, methoxy- or ethoxy-substituted heterocyclyl or heterocyclyl-methyl, where in each case the heterocyclyl group is selected from the group consisting of oxetanyl, thietanyl, furyl, tetrahydrofuryl, thienyl, tetrahydrothienyl,

R2 represents cyano, fluorine, chlorine, bromine, represents respectively optionally cyano-, fluorine-, chlorine-, methoxy- or ethoxy-substituted methyl, ethyl, n- or i-propyl, n-, i- or s-butyl, methoxy, ethoxy, n- or i-propoxy, methoxycarbonyl, ethoxycarbonyl, n- or i-propoxycarbonyl, methylthio, ethylthio, methylsulphinyl, ethylsulphinyl, methylsulphonyl or ethylsulphonyl, or represents respectively optionally cyano-, fluorine- or chlorine-substituted propenyl, butenyl, propinyl, butinyl, propenyloxy or propinyloxy, and

R3 represents respectively optionally substituted heterocyclyl of the formulae below,

222

in which

Q1, Q2 and Q3 each represent oxygen or sulphur and

R4 represents hydrogen, hydroxyl, amino, represents respectively optionally fluorine-, chlorine-, cyano-, methoxy- or ethoxy-substituted methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, represents respectively optionally fluorine-, chlorine- or bromine-substituted propenyl, butenyl, propinyl or butinyl, represents respectively optionally fluorine-, chlorine-, cyano-, methoxy- or ethoxy-substituted methoxy, ethoxy, n- or i-propoxy, n-, i-, s- or t-butoxy, methylamino, ethylamino, n- or i-propylamino, n-, i-, s- or t-butylamino, represents propenyloxy or butenyloxy, represents dimethylamino or diethylamino, represents respectively optionally fluorine-, chlorine-, methyl- and/or ethyl-substituted cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopropylamino, cyclobutylamino, cyclopentylamino, cyclohexylamino, cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl or cyclohexylmethyl, or represents respectively optionally fluorine-, chlorine-, methyl-, trifluoromethyl- and/or methoxy-substituted phenyl or benzyl,

R5 represents hydrogen, hydroxyl, mercapto, amino, fluorine, chlorine, bromine, represents respectively optionally fluorine-, chlorine-, cyano-, methoxy- or ethoxy-substituted methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, represents respectively optionally fluorine-, chlorine- or bromine-substituted ethenyl, propenyl, butenyl, propinyl or butinyl, represents respectively optionally fluorine-, chlorine-, cyano-, methoxy- or ethoxy-substituted methoxy, ethoxy, n- or i-propoxy, n-, i-, s- or t-butoxy, methylthio, ethylthio, n- or i-propylthio, n-, i-, s- or t-butylthio, methylamino, ethylamino, n- or i-propylamino, n-, i-, s- or t-butylamino, represents propenyloxy, butenyloxy, propinyloxy, butinyloxy, propenylthio, propadienylthio butenylthio, propinylthio, butinylthio, propenylamino, butenylamino, propinylamino or butinylamino, represents dimethylamino, diethylamino or dipropylamino, represents respectively optionally fluorine-, chlorine-, methyl- and/or ethyl-substituted cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopentenyl, cyclohexenyl, cyclopropyloxy, cyclobutyloxy, cyclopentyloxy, cyclohexyloxy, cyclopropylthio, cyclobutylthio, cyclopentylthio, cyclohexylthio, cyclopropylamino, cyclobutylamino, cyclopentylamino, cyclohexylamino, cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl, cyclohexylmethyl, cyclopropylmethoxy, cyclobutylmethoxy, cyclopentylmethoxy, cyclohexylmethoxy, cyclopropylmethylthio, cyclobutylmethylthio, cyclopentyl-methylthio, cyclohexylmethylthio, cyclopropylmethylamino, cyclobutylmethylamino, cyclopentylmethylamino or cyclohexyl-methylamino, or represents respectively optionally fluorine-, chlorine-, methyl-, trifluoromethyl-, methoxy- and/or methoxy-carbonyl-substituted phenyl, benzyl, phenoxy, benzyloxy, phenylthio, benzylthio, phenylamino or benzylamino, or

R4 and R5 together represent optionally branched alkanediyl having 3 to 11 carbon atoms, furthermore

R6, R7 and R8 are identical or different and each represents hydrogen, cyano, fluorine, chlorine, bromine, or represents respectively optionally fluorine-, chlorine-, methoxy- or ethoxy-substituted methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, propenyl, butenyl, propinyl, butinyl, methoxy, ethoxy, n- or i-propoxy, n-, i-, s- or t-butoxy, propenyloxy, butenyloxy, propinyloxy, butinyloxy, methylthio, ethylthio, n- or i-propylthio, n-, i-, s- or t-butylthio, propenylthio, butenylthio, propinylthio, butinylthio, methylsulphinyl, ethylsulphinyl, methylsulphonyl or ethylsulphonyl, or represents cyclopropyl, except for the individual compounds mentioned in claim 1.

4. Compounds of the formula (I) according to claim 1, characterized in that

A represents sulphur or —CH═CH—,

Q represents oxygen or sulphur,

R1 represents methyl, ethyl, n- or i-propyl, 2-cyano-ethyl, 2-fluoro-ethyl, 2,2-difluoro-ethyl, 2,2,2-trifluoro-ethyl, 2-chloro-ethyl, 2,2-dichloro-ethyl, 2,2,2-trichloro-ethyl, 2-methoxy-ethyl, 2-ethoxy-ethyl or oxetanyl,

R2 represents fluorine, chlorine, bromine, methyl, ethyl, n- or i-propyl, n-, i- or s-butyl, trifluoromethyl, methoxy, ethoxy, n- or i-propoxy, difluoromethoxy, trifluoromethoxy or trifluoroethoxy, and

R3 represents optionally substituted triazolinyl of the formula below

223

in which

Q1 represents oxygen or sulphur and

R4 represents respectively optionally fluorine-, chlorine-, methoxy- or ethoxy-substituted methyl, ethyl, n- or i-propyl, represents respectively optionally fluorine- or chlorine-subsituted propenyl or propinyl, represents methoxy, ethoxy, n- or i-propoxy, methylamino, ethylamino, n- or i-propylamino, represents propenyloxy, represents dimethylamino or represents cyclopropyl,

R5 represents chlorine or bromine, represents respectively optionally fluorine-, chlorine-, cyano-, methoxy- or ethoxy-substituted methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, represents respectively optionally fluorine-, chlorine- or bromine-substituted ethenyl, propenyl, butenyl, propinyl or butinyl, represents respectively optionally fluorine-, chlorine-, cyano-, methoxy- or ethoxy-subsituted methoxy, ethoxy, n- or i-propoxy, n-, i-, s- or t-butoxy, methylthio, ethylthio, n- or i-propylthio, n-, i-, s- or t-butylthio, methylamino, ethylamino, n- or i-propylamino, n-, i-, s- or t-butylamino, represents propenyloxy, butenyloxy, propinyloxy, butinyloxy, propenylthio, propadienylthio, butenylthio, propinylthio, butinylthio, propenylamino, butenylamino, propinylamino or butinylamino, represents dimethylamino, diethylamino or dipropylamino, represents respectively optionally fluorine-, chlorine-, methyl- and/or ethyl-substituted cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopentenyl, cyclohexenyl, cyclopropyloxy, cyclobutyloxy, cyclopentyloxy, cyclohexyloxy, cyclopropylthio, cyclobutylthio, cyclopentylthio, cyclohexylthio, cyclopropylamino, cyclobutylamino, cyclopentylamino, cyclohexylamino, cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl, cyclohexylmethyl, cyclopropylmethoxy, cyclobutylmethoxy, cyclopentylmethoxy, cyclohexylmethoxy, cyclopropylmethylthio, cyclobutylmethylthio, cyclopentyl-methylthio, cyclohexylmethylthio, cyclopropylmethylamino, cyclobutylmethylamino, cyclopentylmethylamino or cyclohexyl-methylamino, or represents respectively optionally fluorine-, chlorine-, methyl-, trifluoromethyl-, methoxy- and/or methoxycarbonyl-substituted phenyl, benzyl, phenoxy, benzyloxy, phenylthio, benzylthio, phenylamino or benzylamino, or

R4 and R5 together represent optionally branched alkanediyl having 3 to 11 carbon atoms.

5. Process for preparing compounds of the formula (I) according to claim 1, characterized in that

(a) sulphonarnides of the general formula (II)

224

in which

A, R1 and R2 are each as defined in claim 1, are reacted with (thio)carboxylic acid derivatives of the general formula (III)

225

in which

Q and R3 are each as defined in claim 1 and

Z represents halogen, alkoxy, aryloxy or arylalkoxy,

if appropriate in the presence of an acid acceptor and if appropriate in the presence of a diluent,

or in that

(b) sulphonyl iso(thio)cyanates of the general formula (IV)

226

in which

A, Q, R1 and R2 are each as defined above,

are reacted with heterocycles of the general formula (V)

H—R3  (V)

in which

R3 is as defined above,

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

or in that

(c) sulphonyl chlorides of the general formula (VI)

227

in which

A, R1 and R2 are each as defined above,

are reacted with heterocycles of the general formula (V)

H—R3  (V)

in which

R3 is as defined above,

and metal (thio)cyanates of the general formula (VII)

MQCN  (VII)

in which

Q is as defined above,

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

or in that

(d) sulphonyl chlorides of the general formula (VI)

228

in which

A, R1 and R2 are each as defined above,

are reacted with (thio)carboxamides of the general formula (VIII)

229

in which

Q and R3 are each as defined above,

if appropriate in the presence of an acid acceptor and if appropriate in the presence of a diluent,

or in that

(e) sulphonylamino(thio)carbonyl compounds of the general formula (IX)

230

in which

A, Q, R1 and R2 are each as defined above and

Z represents halogen, alkoxy, aryloXy or arylalkoxy,

are reacted with heterocycles of the general formula (V)

H—R3  (V)

in which

R3 is as defined above,

if appropriate in the presence of an acid acceptor and if appropriate in the presence of a diluent,

and the compounds of the formula (I) obtained by processes (a), (b), (c), (d) or (e) are, if desired, converted into salts by customary methods.

6. Herbicidal composition, characterized in that it contains at least one compound of the formula (I) or a salt thereof according to claim 1.

7. The use of compounds of the general formula (I) or of salts thereof according to claim I for controlling unwanted vegetation.

8. Process for controlling weeds, characterized in that compounds of the general formula (I) or salts thereof according to claim 1 are allowed to act on the weeds or their habitat.

9. Method for preparing herbical compositions, characterized in that compounds of the general formula (I) or salts thereof according to claim 1 are mixed with extenders and/or surfactants.

10. Sulphonamides of the formula (IIa) and sulphonyl chlorides of the formula (VIa)

231

in which in each case

R1 represents respectively optionally substituted alkyl, alkenyl, alkinyl, cycloalkyl, cycloalkylalkyl, aryl, arylalkyl, heterocyclyl or heterocyclylalkyl and

R2 represents cyano, nitro, halogen or represents respectively optionally substituted alkyl, alkoxy, alkoxycarbonyl, alkylthio, alkylsulphinyl, alkylsulphonyl, alkenyl, alkinyl, alkenyloxy or alkinyloxy.