Substituted aromatic thiocarboxylic acid amides and their use as herbicides

Abstract

There is disclosed substituted thiocarboxamides of the general formula (I) useful as herbicides.

1. A substituted aromatic thiocarboxamide of the formula 
                   
       wherein
 R 1  represents hydrogen, fluorine, chlorine or bromine,  
 R 2  represents the following group 
   —A 1 —A 2 —A 3    
 
 
       in which
 A 1  represents a single bond, or represents oxygen, sulphur, —SO—, —SO 2 —, —CO— or the group —N(A 4 )—, in which A 4  represents hydrogen, hydroxyl, C 1 -C 4 -alkyl, C 3 -C 4 -alkenyl, C 3 -C 4 -alkinyl, C 1 -C 4 -alkoxy, phenyl, C 1 -C 4 -alkylsulphonyl or phenylsulphonyl,  
 A 1  additionally represents in each case optionally fluorine- or chlorine-substituted C 1 -C 6 -alkanediyl, C 2 -C 6 -alkenediyl, C 2 -C 6 -alkinediyl, C 3 -C 6 -cycloalkanediyl, C 3 -C 6 -cycloalkenediyl or phenylene,  
 A 2  represents a single bond, or represents oxygen, sulphur, —SO—, —SO 2 —, —CO— or the group —N—(A 4 )—, in which A 4  represents hydrogen, hydroxyl, C 1 -C 4 -alkyl, C 3 -C 4 -alkenyl, C 3 -C 4 -alkinyl, C 1 -C 4 -alkoxy, phenyl, C 1 -C 4 -alkylsulphonyl or phenylsulphonyl,  
 A 2  additionally represents in each case optionally fluorine- or chlorine-substituted C 1 -C 6 -alkanediyl, C 2 -C 6 -alkenediyl, C 2 -C 6 -alkinediyl, C 3 -C 6 -cycloalkanediyl, C 3 -C 6 cycloalkenediyl or phenylene,  
 A 3  represents hydrogen, hydroxyl, amino, cyano, isocyano, thiocyanato, nitro, carboxyl, carbamoyl, thiocarbamoyl, sulpho, chlorosulphonyl, halogen, or represents in each case optionally halogen- or C 1 -C 4 -alkoxy-substituted alkyl, alkoxy, akylthio, alkylsulphinyl, alkylsulphonyl, alkylamino, dialkylamino, alkoxycarbonyl or dialkoxy(thio) phosphoryl having in each case 1 to 6 carbon atoms in the alkyl groups, or represents in each case optionally halogen-substituted alkenyl, alkenyloxy, alkenylamino, alkylideneamino, alkenyloxycarbonyl, alkinyl, alkinyloxy, alkinylamino or alkinyloxycarbonyl having in each case 2 to 6 carbon atoms in the alkenyl, alkylidene or alkinyl groups, or represents in each case optionally halogen-, cyano-, carboxyl-, C 1 -C 4 -alkyl- and/or C 1 -C 4 -alkoxy-carbonyl-substituted cycloalkyl, cycloalkyloxy, cycloalkylalkyl, cycloalkylalkoxy, cycloalkylideneamino, cycloalkyloxycarbonyl or cycloalkylalkoxycarbonyl having in each case 3 to 6 carbon atoms in the cycloalkyl groups and optionally 1 to 4 carbon atoms in the alkyl groups, or represents in each case optionally nitro-, cyano-, carboxyl-, halogen-, C 1 -C 4 -alkyl-, C 1 -C 4 -halogenalkyl-, C 1 -C 4 -alkoxy-, C 1 -C 4 -halogenoalkyloxy- and/or C 1 -C 4 -alkoxy-carbonyl-substituted phenyl, phenyloxy, phenyl-C 1 -C 4 -alkyl, phenyl-C 1 -C 4 -alkoxy, phenyloxycarbonyl or phenyl-C 1 -C 4 -alkoxycarbonyl, (in each case optionally totally or partially hydrogenated) pyrrolyl, pyrazolyl, imidazolyl, triazolyl, furyl, thienyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, oxadiazolyl, thiadiazolyl, pyridinyl, pyrimidinyl, triazinyl, pyrazolyl-C 1 -C 4 -alkyl, furyl-C 1 -C 4 -alkyl, thienyl-C 1 -C 4 -alkyl, oxazolyl-C 1 -C 4 -alkyl isoxazole-C 1 -C 4 -alkyl, thiazole-C 1 -C 4 -alkyl, pyridinyl-C 1 -C 4 -alkyl, pyrimidinyl-C 1 -C 4 -alkyl, pyrazolylmethoxy or furylmethoxy, or represents perhydropyranylmethoxy or pyridylmethoxy,  
 R 3  represents hydrogen, fluorine, chlorine or bromine or together with R 2  represents an alkanediyl or alkenediyl group having in each case up to 4 carbon atoms which optionally contains at the beginning (or end) or within the hydrocarbon chain an oxygen atom, a sulphur atom, an SO 2  group, an NH group, an N—C 1 -C 4 -alkyl group, a carbonyl group and/or a thiocarbonyl group, and  
 Z represents Z 3 : 
                 
 
 
       wherein:
 Q 1  represents a group from the series —CO—, —CS—, —CH 2 —, —CH(OH)—, —CHCl—, —CHBr—, —C(═CH 2 )—, —C(═CHF)—, —C(═CF 2 )—, —C(═CHCl)—, —C(═CHBr)—, —C(═CHOCHF 3 )—, —C (═CHOCF 3 )—, —C(═CHOCH 2 CF 3 )—,  
 
       R 6  represents hydrogen, amino, nitro, cyano, carboxyl, carbamoyl, fluorine, chlorine, bromine, methyl, ethyl, n- or i-propyl, cyclopropyl, difluoromethyl, trifluoromethyl, chlorodifluoromethyl, methoxy, ethoxy, n- or i-propoxy, difluoromethoxy, trifluoromethoxy, chlorodifluoro-methoxy, methylthio, ethylthio, n- or i-propylthio, difluoromethylthio, trifluoromethylthio, chlorodifluoromethylthio, methylamino, ethylamino, n- or i-propylamino, dimethylamino, diethylamino, methoxycarbonyl or ethoxycarbonyl, and 
 R 7  represents hydrogen, hydroxyl, amino, cyano, methyl, ethyl, n- or i-propyl, difluoromethyl, methoxy, ethoxy, n- or i-propoxy.  
 
     
     
       2. A substituted aromatic thiocarboxamide of the formula (I) 
                 
 
       wherein
 R 1  represents hydrogen, fluorine, chlorine or bromine,  
 R 2  represents the following group 
   —A 1 —A 2 —A 3    
 
 
       in which
 A 1  represents a single bond, or represents oxygen, sulphur, —SO—, —SO 2 —, —CO— or the group —N(A 4 )—, in which A 4  represents hydrogen, hydroxyl, C 1 -C 4 -alkyl, C 3 -C 4 -alkenyl, C 3 -C 4 -alkinyl, C 1 -C 4 -alkoxy, phenyl, C 1 -C 4 -alkylsulphonyl or phenylsulphonyl,  
 A 1  additionally represents in each case optionally fluorine- or chlorine-substituted C 1 -C 6 -alkendiyl, C 2 -C 6 -alkenediyl, C 2 -C 6 -alkinediyl, C 3 -C 6 -cycloalkanediyl, C 3 -C 6 -cycloalkenediyl or phenylene,  
 A 2  represents a single bond, or represents oxygen, sulphur, —SO—, —SO 2 —, —CO— or the group —N(A 4 )—, in which A 4  represents hydrogen, hydroxyl, C 1 -C 4 -alkyl, C 3 -C 4 -alkenyl, C 3 -C 4 -alkinyl, C 1 -C 4 -alkoxy, phenyl, C 1 -C 4 -alkylsulphonyl or phenylsulphonyl,  
 A 2  additionally represents in each case optionally fluorine- or chlorine-substituted C 1 -C 6 -alkanediyl, C 2 -C 6 -alkenediyl, C 2 -C 6 -alkinediyl, C 3 -C 6 -cycloalkanediyl, C 3 -C 6 -cycloalkenediyl or phenylene,  
 A 3  represents hydrogen, hydroxyl, amino, cyano, isocyano, thiocyanato, nitro, carboxyl, carbamoyl, thiocarbamoyl, sulpho, chlorosulphonyl, halogen, or represents in each case optionally halogen- or C 1 -C 4 -alkoxy-substituted alkyl, alkoxy, alkylthio, alkylsulphinyl, alkylsulphonyl, alkylamino, dialkylamino, alkoxycarbonyl or dialkoxy(thio)phosphoryl having in each case 1 to 6 carbon atoms in the alkyl groups, or represents in each case optionally halogen-substituted alkenyl, alkenyloxy, alkenylamino, alkylideneamino, alkenyloxycarbonyl, alkinyl, alkinyloxy, alkinylamino or alkinyloxycarbonyl having in each case 2 to 6 carbon atoms in the alkenyl, alkylidene or alkinyl groups, or represents in each case optionally halogen-, cyano-, carboxyl-, C 1 -C 4 -alkyl- and/or C 1 -C 4 -alkoxy-carbonyl-substituted cycloalkyl, cycloalkyloxy, cycloalkylalkyl, cycloalkylalkoxy, cycloalkylideneamino, cycloalkyloxycarbonyl or cycloalkylalkoxycarbonyl having in each case 3 to 6 carbon atoms in the cycloalkyl groups and optionally 1 to 4 carbon atoms in the alkyl groups, or represents in each case optionally nitro-, cyano-, carboxyl-, halogen, C 1 -C 4 -alkyl-, C 1 -C 4 -halogenoalkyl-, C 1 -C 4 -alkyloxy-, C 1 -C 4 -halogenoalkyloxy- and/or C 1 -C 4 -alkoxy-carbonyl-substituted phenyl, phenyloxy, phenyl-C 1 -C 4 -alkyl, phenyl-C 1 -C 4 -alkoxy, phenyloxycarbonyl or phenyl-C 1 -C 4 -alkoxycarbonyl, (in each case optionally totally or partially hydrogenated) pyrrolyl, pyrazolyl, imidazolyl, triazolyl, furyl, thienyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, oxadiazolyl, thiadiazolyl, pyridinyl, pyrimidinyl, triazinyl, pyrazolyl-C 1 -C 4 -alkyl, furyl-C 1 -C 4 -alkyl, thienyl-C 1 -C 4 -alkyl, oxazolyl-C 1 -C 4 -alkyl, isoxazole-C 1 -C 4 -alkyl, thiazole-C 1 -C 4 -alkyl, pyridinyl-C 1 -C 4 -alkyl, pyrimidinyl-C 1 -C 4 -alkyl, pyrazolylmethoxy or furylmethoxy, or represents perhydropyranylmethoxy or pyridylmethoxy,  
 R 3  represents hydrogen, fluorine, chlorine or bromine or together with R 2  represents an alkanediyl or alkenediyl group having in each case up to 4 carbon atoms which optionally contains at the beginning (or end) or within the hydrocarbon chain an oxygen atom, a sulphur atom, an SO 2  group, an NH group, an N—C 1 -C 4 -alkyl group, a carbonyl group and/or thiocarbonyl group, and  
 Z represents Z 3 : 
                 
 
 
       wherein
 Q 1  represents a group from the series —CO—, —CS—, —CH 2 —, —CH(OH)—, —CHCl—, —CHBr—, —C(═CH 2 )—, —C(═CHF)—, —C(═CF 2 )—, —C(═CHCl)—, —C(═CHBr)—, —C(═CHOCHF 2 )—, —C(═CHOCF 3 )—, —C(═CHOCH 2 CF 3 )—,  
 R 6  represents hydrogen, amino, nitro, cyano, carboxyl, carbamoyl, fluorine, chlorine, bromine, methyl, ethyl, n- or i-propyl, cyclopropyl, difluoromethyl, trifluoromethyl, chlorodifluoromethyl, methoxy, ethoxy, n- or i-propoxy, difluoromethoxy, trifluoromethoxy, chlorodifluoro-methoxy, methylthio, ethylthio, n- or i-propylthio, difluoromethylthio, trifluoromethylthio, chlorodifluoromethylthio, methylamino, ethylamino, n- or i-propylamino, dimethylamino, diethylamino, methoxycarbonyl or ethoxycarbonyl, and  
 R 7  represents hydrogen, hydroxyl, amino, cyano, methyl, ethyl, n- or i-propyl, difluoromethyl, methoxy, ethoxy, n- or i-propoxy.  
 
     
     
       3. A substituted aromatic thiocarboxamide of the formula (I) according to  claim 2 , wherein
 R 1  represents hydrogen, fluorine, or chlorine,  
 R 2  represents the following group 
   —A 1 —A 2 —A 3    
 
 
       in which
 A 1  represents a single bond, or represents oxygen, sulphur, —SO—, —SO 2 —, —CO— or the group —N(A 4 )—, in which A 4  represents hydrogen, hydroxyl, methyl, ethyl, n- or i-propyl, methoxy, ethoxy, n- or i-propoxy, methylsulphonyl or ethylsulphonyl,  
 A 1  additionally represents methylene, ethane-1,1-diyl, ethane-1,2-diyl, propane-1,1-diyl, propane-1,2-diyl, propane-1,3-diyl, ethene-1,2-diyl, propene-1,2-diyl, propene-1,3-diyl, ethine-1,2-diyl, propine-1,2-diyl or propine-1,3-diyl,  
 A 2  represents a single bond, or represents oxygen, sulphur, —SO—, —SO 2 —, —CO— or the group —N(A 4 )—, in which A 4  represents hydrogen, hydroxyl, methyl, ethyl, n- or i-propyl, methoxy, ethoxy, n- or i-propoxy, methylsulphonyl, ethylsulphonyl, n- or i-propylsulphonyl or phenylsulphonyl,  
 A 2  additionally represents methylene, ethane-1,1-diyl, ethane-1,1-diyl, ethane-1,2-diyl, propane-1,1-diyl, propane-1,2-diyl, propane-1,3-diyl, ethene-1,2-diyl, propene-1,2-diyl, propene-1,3-diyl, ethine-1,2-diyl, propine-1,2-diyl or propine-1,3-diyl,  
 A 3  represents hydrogen, hydroxyl, amino, cyano, nitro, carboxyl, carbamoyl, sulpho, fluorine, chlorine, bromine, or represents in each case optionally fluorine-, chlorine-, methoxy- or ethoxy-substituted methyl, ethyl, n- or i-propyl, n-, i-, s- or t-bytyl, n-, i-, s- or t-pentyl, methoxy, ethoxy, n- or i-propoxy, n-, i-, s- or t-butoxy, n-, i-, s- or t-pentyloxy, methylthio, ethylthio, n- or i-propylthio, n-, i-, s-, or t-butylthio, methylsulphinyl, ethylsulphinyl, n- or i-propylsulphinyl, methylsulphonyl, ethylsulphonyl, n- or i-propylamino, n-, i-, s- or t-butylamino, dimethylamino, diethylamino, methoxycarbonyl, ethoxycarbonyl, n- or i-propoxycarbonyl, dimethoxy-phosphoryl, diethoxyphosphoryl, dipropoxy-phosphoryl or diisopropoxyphosphoryl, or represents in each case optionally fluorine- or chlorine-substituted propenyl, butenyl, propenyloxy, butenyloxy, propenylamino, butenylamino, propylideneamino, butylideneamino, propenyloxycarbonyl, butenyloxycarbonyl, propinyl, butinyl, propinyloxy, butinyloxy, propinylamino, butinylamino, propinyloxycarbonyl or butinyloxycarbonyl, or represents in each case optionally fluorine-, chlorine-, cyano-, carboxyl-, methyl-, ethyl-, n- or i-propyl-, methoxycarbonyl- or ethoxycarbonyl-substituted cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopropyloxy, cyclobutyloxy, cyclopentyloxy, cyclohexyloxy, cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl, cyclohexylmethyl, cyclopropylmethoxy, cyclobutylmethoxy, cyclopentylmethoxy, cyclohexylmethoxy, cyclopentylideneamino, cyclohexylideneamino, cyclopentyloxycarbonyl, cyclohexyloxycarbonyl, cyclopentylmethoxycarbonyl or cyclohexylmethoxycarbonyl, pr represents in each case optionally nitro-, cyano-, carboxyl-, fluorine-, chlorine-, bromine-, methyl-, ethyl-, n- or i-propyl, thifluoromethyl-, methoxy-, ethoxy-, n- or i-propoxy-, difluoromethoxy-, trifluoromethoxy-, methoxycarbonyl- and/or ethoxycarbonyl-substituted phenyl, phenyloxy, benzyl, phenylethyl, benzyloxy, phenyloxycarbonyl, benzyloxycarbonyl, (in each case optionally completely or partially hydrogenated) pyrrolyl, pyrazolyl, imidazolyl, triazolyl, furyl, thienyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, oxadiazolyl, thiadiazolyl, pyridinyl, pyrimidinyl, triazinyl, pyrazolylmethyl, furylmethyl, thienylmethyl, oxazolylmethyl, isoxazolemethyl, thiazolmethyl, pyridinylmethyl, pyrimidinylmethyl, pyrazlylmethoxy, furylmethoxy or pyridylmethoxy, and  
 R 3  represents hydrogen, fluorine or chlorine or together with R 2  represents an alkanediyl or alkenediyl group having in each case 1 to 3 carbon atoms which optionally contains at the beginning (or end) or within the hydrocarbon chain an oxygen atom, a sulphur atom, an NH group, an N-methyl group, a carbonyl group and/or a thiocarbonyl group.  
 
     
     
       4. A process for the preparation of a substituted aromatic thiocarboxamide of the formula (I) 
                 
 
       in which R 1 , R 2 , R 3  and Z have the meanings given in  claim 2 , comprising reacting a substituted aromatic nitrile of the formula (II) 
                 
 
       in which
 R 1 , R 2 , R 3  and Z have the meanings indicated above, with hydrogen sulphide (H 2 S) or with thioacetamide, optionally in the presence of a reaction auxiliary and optionally in the presence of a diluent.  
 
     
     
       5. A method of combatting unwanted plants comprising applying to said plants and/or heir habitat a herbicidally effective amount of at least one substituted aromatic thiocarboxamide of the formula (I) according to  claim 1  or  2 . 
     
     
       6. A herbicidal composition comprising a herbicidally effective amount of at least one substituted aromatic thiocarboxamide of the formula ( I )  according to    claim 2    or    3    and at least one extender and/or surfactant.    
     
     
       7. A method of combatting unwanted plants comprising applying to said plants and/or their habitat a herbicidally effective amount of at least one substituted aromatic thiocarboxamide of the formula ( I )  according to    claim 2    or    3   .