MXPA98007174A

MXPA98007174A - Procedure for the obtaining of amidas of tiocarboxilic, aromatic, substitute acids

Info

Publication number: MXPA98007174A
Application number: MXPA/A/1998/007174A
Authority: MX
Inventors: Wilhelm Drewes Mark; Wroblowsky Heinzjurgen; Andree Rolan
Original assignee: Bayer Ag 51373 Leverkusen De
Priority date: 1996-03-14
Filing date: 1998-09-03
Publication date: 1999-02-24

Abstract

Aromatic, substituted thiocarboxylic acid amides of the general formula (I) are prepared according to a new process. Wherein R1, R2, R3 and Z have the meanings indicated in the description, by reaction of substituted aromatic nitriles (II), with hydrogen sulphide in the presence of a basic organic compound and in the presence of an apolar or moderately polar organic solvent

Description

PROCEDIMENT FOR THE OBTAINING OF AMIDAS OF TIOCARBOXILIC, AROMATIC ACIDS. SUBSTITUTED. Field of the invention. The invention relates to a novel process for the preparation of substituted, aromatic thiocarboxylic acid amides, which are known as compounds with herbicidal activity. Description of the prior art. It is known that thiocarboxylic acid amides can be obtained by reacting nitriles with an alcoholic solution of an alkali metal bisulfide or ammonium bisulphide under high pressure (see Justus Liebigs Ann. Chem. 433. (1923), 201-205 It should be considered as a drawback of this synthesis method the high pressure required for the reaction on an industrial scale It is further known that thiocarbixyl acid amides can be synthesized by reaction of nitriles with hydrogen sulfide in pyridine in the presence of a base strong, such as for example triethylamine (see J. Chem. Soc. 1952, 742-744) In this case the workup is carried out by pouring the reaction mixture into water and separation by suction filtration. as a disadvantage of this method obtaining a REF .: 28179 pyridine and aqueous mother liquors containing auxiliary bases, from which the organic components can be separated only by means of a relatively expensive process. It is further known that thiocarboxylic acid amides can also be obtained by reaction of nitriles with thioacetamide in the presence of hydrogen chloride gas (hydrogen chloride) in dimethylformamide (see J. Am. Chem. Soc. 82 (1960), 2656-2657) . However, in this method, hydrogen gas chlorine must necessarily be used, which is unfavorable for industrial application. It is further known that certain substituted aromatic thiocarboxylic acid amides can be prepared by reaction of the corresponding substituted aromatic nitriles with hydrogen sulphide (hydrogen sulfide, H2S) or with thioacetamide (see WO 95/30661). For working up, it is concentrated by evaporation under reduced pressure and the product remaining in the residue is obtained in a crystalline state by treatment of aqueous hydrochloric acid and / or with a suitable organic solvent. In this case, too, the problem of recovering the organic components of the reaction is not solved.

Detailed description of the invention. It has now been found that substituted, aromatic thiocarboxylic acid amides of the general formula (I) are obtained wherein R1 signifies hydrogen or halogen, R2 signifies the following grouping, -A1-A2-A3 where A1 means a single bond, means oxygen, sulfur, -SO-, -S02-, -CO- or the grouping -N- A4-, where A4 means hydrogen, hydroxy, alkyl, alkoxy, aryl, alkylsulfonyl or arylsulfonyl, or (A1) means alkanediyl, alkenodiyl, alkynediyl, cycloalkanediyl, cycloalkenediyl or arenediyl substituted respectively where appropriate, A2 means a single bond, means oxygen , sulfur, ~ S0, -S02-, -CO- or the grouping -N-A4-, where A4 means hydrogen, hydroxy, alkyl, aryl, alkoxy, alkylsulfonyl or arylsulfonyl, or (A2) means alkanediyl, alkenodiyl, alkynediyl, cycloalkanediyl, cycloalkenediyl or arenediyl substituted respectively where appropriate, and A? 33 means hydrogen, hydroxy, amino, cyano, isocyano, thiocyanate, nitro, carboxy, carbamoyl, thiocarbamoyl, sulfo, chlorosulfonyl, halogen or means, substituted respectively and optionally alkyl, alkoxy, alkylthio, alkylsulfinyl, alkylsulfonyl, alkylamino, dialkylamino, alkoxycarbonyl, dialkoxy (thio) phosphoryl, alkenyl, alkenyloxy, alkenylamino, alkylidenamino, alkenyloxycarbonyl, alkynyl, alkynyloxy, alkylamino, alkynyloxycarbonyl, cycloalkyl, cycloalkyloxy, cycloalkylalkyl , cycloalkylalkoxy, cycloalkylideneamino, cycloalkyloxycarbonyl, cycloalkylalkoxycarbonylaryl, aryloxy, arylalkyl, arylalkoxy, aryloxycarbonyl, arylalkoxycarbonyl, heterocyclyl, heterocyclylalkyl, heterocyclylalkoxy or heterocyclylalcoxycarbonyl, R3 signifies hydrogen, halogen or together with R2 signifies an alkanediyl group or an alkenediyl group, which contains at the beginning (or at the end) or in the interior of the hydrocarbon chain a sulfur oxygen atom, an NH- group, an N-alkyl group, a carbonyl group and / or a thiocarbonyl group, and Z means heterocyclyl, heterocyclylamino or heterocyclicimino saturated or unsaturated, monocyclic or bicyclics, substituted, if appropriate, with very good yields and with high purity, if aromatic, substituted nitriles of the general formula (II) are reacted wherein R1, R2, R3 and Z have the meanings given above, with hydrogen sulphide (hydrogen sulfide, H2S), in the presence of a basic organic compound and in the presence of a moderately polar organic solvent at temperatures between 0 ° C and 150 ° C.

Surprisingly, the substituted aromatic thioamides of the general formula (I) can be obtained according to the process of the invention with considerably higher yields than at present and with very good quality, the use of pyridine as a solvent being possible and the processing and isolating the reaction products in a very simple manner in general by simple suction filtration. The process according to the invention therefore represents a valuable enrichment of the state of the art. The process according to the invention preferably relates to the preparation of the compounds of the formula (I), in which R 1 signifies hydrogen, fluorine, chlorine or bromine, R 2 signifies the following group, -Ax-A2-A3 in which A1 means a single bond, means oxygen, sulfur, -SO-, -S02-, -CO- or the group -N-A4- where A4 means hydrogen, hydroxy, alkyl with 1 to 4 carbon atoms, alkoxy with 1 to 4 carbon atoms, phenyl, alkylsulfonyl with 1 to 4 carbon atoms or phenylsulfonyl, or (A1) means alkanediyl with the β carbon atoms, alkenodiyl with 2 to 6 carbon atoms, alkynediyl with 2 to 6 carbon atoms, cycloalkanediyl with 3 to 6 carbon atoms, cycloalkenodiyl having 3 to 6 carbon atoms or phenylene substituted, where appropriate, by fluorine or chlorine, A2 means a single bond, means oxygen, sulfur, -SO-, -S02-, -CO- or the grouping -N-A4- where A4 means hydrogen, hydroxy, alkyl co n 1 to 4 carbon atoms, alkoxy with 1 to 4 carbon atoms, phenyl, alkylsulfonyl with 1 to 4 carbon atoms or phenylsulfonyl, or (A2) means alkanediyl with 1 to 6 carbon atoms, alkenodiyl with 2 to 6 atoms of carbon, alkynediyl with 2 to 6 carbon atoms, cycloalkanediyl with 3 to 6 carbon atoms, cycloalkenodiyl or phenylene substituted respectively where appropriate by fluorine or chlorine, A3 means hydrogen, hydroxy, amino, cyano, isocyano, thiocyanate, nitro carboxy, carbamoyl, thiocarbamoyl, sulfo, chlorosulfonyl, halogen, means, optionally substituted by halogen or by alkoxy with 1 to 4 carbon atoms, alkyl, alkoxy, alkylthio, alkylsulfinyl, alkylsulfonyl, alkylamino, dialkylamino, alkoxycarbonyl or dialkoxy (thio) phosphoryl with respectively 1 to 6 carbon atoms in the alkyl groups, means, optionally substituted by halogen, alkenyloxy, alkenylamino, alkylidenamino, alken nyloxycarbonyl, alkynyl, alkynyloxy, alkynylamino or alkynyloxycarbonyl with 2 to 5 carbon atoms in the alkenyl, alkylidene or alkynyl groups respectively means, optionally substituted by halogen, by cyano, by carboxy, by alkyl with 1 to 4 carbon atoms and / or by alkoxycarbonyl having 1 to 4 carbon atoms, cycloalkyl, cycloalkyloxy, cycloalkylalkyl, cycloalkylalkoxy, cycloalkylideneamino, cycloalkyloxycarbonyl or cycloalkylalkoxycarbonyl with 3 to 6 carbon atoms in the cycloalkyl groups and, optionally, 1 to 4 atoms of carbon in the alkyl groups or means, optionally substituted by nitro, by cyano, by carboxy, by halogen, by alkyl with 1 to 4 carbon atoms, by halogenalkyl with 1 to 4 carbon atoms, by alkyloxy by 1 to 4 carbon atoms by halogenalkyloxy having 1 to 4 carbon atoms and / or by alkoxycarbonyl having 1 to 4 carbon atoms, phenyl, phenyl xi, phenyl-C 1 -C 4 -alkyl, phenyl-C 1 -C 4 -alkoxy, phenyl-oxycarbonyl or phenyl-C 1 -C 4 -alkoxycarbonyl, (wholly or partially hydrogenated, if appropriate) pyrrolyl, pyrazolyl, imidazolyl, triazolyl, furyl, thienyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, oxadiazolyl, thiadiazolyl, pyridinyl, pyrimidinyl, triazinyl, pyrazolyl-alkyl with 1 to 4 carbon atoms, furyl-alkyl with 1 to 4 carbon atoms , 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-1-alkyl to 4 carbon atoms, pyrimidinyl-C 1 -C 4 -alkyl, pyrazolylmethoxy, furylmethoxy, means perhydropyranylmethoxy or pyridylmethoxy, R 3 means hydrogen, fluorine, chlorine, bromine, or together with R 2 means an alkanediyl or alkenodiyl group with respectively up to 4 carbon atoms. carbon atoms, which optionally contains at the beginning (or at the end) or in the interior of the hydrocarbon chain an oxygen atom, a sulfur atom, an NH-group, an N-alkyl group with 1 to 4 carbon atoms, carbon, a carbonyl group and / or a thiocarbonyl group, and means heterocyclyl, heterocyclylamino or heterocyclylimino, respectively monocyclic or saturated bicyclic, with respectively 2 to 6 carbon atoms and 1 to 4 hydrogen atoms in the heterocyclic ring system, containing optionally additionally an oxygen or sulfur atom and / or optionally one to three groupings of the series consisting of -CO-, -CS-, SO- and / or -S02-, and which are optionally substituted by one or more groupings of the series consisting of nitro, hydroxy, amino, cyano, carboxy, carbamoyl, thiocarbamoyl, halogen, alkyl having 1 to 6 carbon atoms (which is optionally substituted by halogen or by alkoxy with 1 to 4) carbon atoms), alkenyl with 2 to 6 carbon atoms or alkynyl with 2 to 6 carbon atoms (which are respectively substituted, if appropriate, by halogen), alkoxy with the ß carbon atoms or alkoxycarbonyl with the ß carbon atoms ( who are substituted respectively by halogen or by alkoxy with 1 to 4 carbon atoms), alkenyloxy with 2 to 6 carbon atoms or alkynyloxy with 2 to 6 carbon atoms (which are each substituted, if appropriate, by halogen), alkylthio with the ß carbon atoms, alkenylthio with 2 to ß carbon atoms or alkynylthio with 2 to 6 carbon atoms (which are each substituted, if appropriate, by halogen), alkylamino with the ß carbon atoms or di- (alkyl with 1 to 4 carbon atoms) -amino, cycloalkyl with 3 to 6 carbon atoms or cycloalkyl with 3 to 6 carbon atoms-alkyl having 1 to 4 carbon atoms (which are respectively substituted, if appropriate, by halogen and / or by alkyl with 1 to 4 carbon atoms), phenyl, phenoxy, phenylthio, phenylsulfinyl, phenylsulfonyl or phenylamino (which are each substituted, if appropriate, by nitro, by cyano, by halogen, by alkyl with 1 to 4 carbon atoms, by halogen enoalkyl with 1 to 4 carbon atoms, for alkyloxy with 1 to 4 carbon atoms, for haloalkyloxy with 1 to 4 carbon atoms and / or for alkoxycarbonyl with 1 to 4 carbon atoms). The process according to the invention relates in particular to the preparation of the compounds of the formula (I), in which R 1 is hydrogen, fluorine or chlorine, R 2 is the following group, -A 1 -A 2-A3 where A1 is a single bond , means oxygen, sulfur, -SO-, -S02-, -CO-, or the grouping -N-A4- where A4 means hydrogen, hydroxy, methyl, ethyl, n- or i-propyl, methoxy, ethoxy, n- or i-propoxy, methylsulfonyl or ethylsulphonyl, or (A1) means methylene, ethane-1,1-diyl, ethane-1, 2-diyl, propane-1,1-diyl, propane-1,2-diyl, propane- 1, 3-diyl, ethane-1, 2-diyl, propene-1,2-diyl, propene-1,3-diyl, etino-1, 2-diyl or propino-1,3-diyl. A2 means a single bond, means oxygen, sulfur, -SO-, -S02-, -CO- or the grouping -N-A4-, where A4 means hydrogen, hydroxy, methyl, ethyl, n- or i-propyl, methoxy , ethoxy, n- or i-propoxy, methylsulfonyl, ethylsulfonyl, n- or i-propylsulfonyl or phenylsulfonyl, or (A2) means methylene, ethane-1,1-diyl, ethane-1,2-diyl, propane-1, l-diyl, propane-1 , 2-diyl, propane-1,3-diyl, ethane-l, 2-diyl, propene-1,2-diyl, propene-1,3-diyl, etino-l, 2-diyl or propinoyl, -diyl, A3 means hydrogen, hydroxy, amino, cyano, nitro, carboxy, carbamoyl, sulfo, fluorine, chlorine, bromine, means, optionally substituted by fluorine, by chlorine, by methoxy or by ethoxy, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, 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, ethyllium, n- or i-propylthio, n-, i-, s- or t-butylthio, methylsulfinyl, ethylsulfinyl, n- or i-propylsulfinyl, methylsulfonyl, ethylsulfonyl, n- or i-propylsulfonyl, methylamino, ethylamino, n- or i-propylamino, n-, i-, s- or t-butylamino, dimethylamino, diethylamine, methoxycarbonyl, ethoxycarbonyl, n- or i-propoxycarbonyl, dimethoxyphos Foryl, diethoxyphosphoryl, dipropoxyphosphoryl or diisopropoxyphosphoryl, respectively means substituted by fluorine or by chlorine, propenyl, butenyl, propenyloxy, butenyloxy, propenylamino, butenylamino, propylideneamino, butylideneamino, propenyloxycarbonyl, butenyloxycarbonyl, propinyl, butynyl, propynyloxy, butynyloxy, propynylamino, butylamino, propynyloxycarbonyl or butynyloxycarbonyl, means, optionally substituted by fluorine, by chlorine, by cyano, by carboxy, by methyl, by ethyl, by n- or i-propyl, by methoxycarbonyl or by ethoxycarbonyl, cyclopropyl, cyclobutyl, cyclopentyl , cyclohexyl, cyclopropyloxy, cyclobutyloxy, cyclopentyloxy, cyclohexyloxy, cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl, cyclohexylmethyl, cyclopropylmethoxy, cyclobutylmethoxy, cyclopentylmethoxy, cyclohexylmethoxy, cyclopentylidene, cyclohexylideneamino, cyclopentyloxycarbonyl, cyclohexyloxycarbonyl, cyclopentyl ethoxycarbonyl or cyclohexyl methoxycarbonyl, or means, respectively substituted by nitro, by cyano, by carboxy, by fluorine, by chlorine, by: bromine, by methyl, by ethyl, by n- or i-propyl, by trifluoromethyl, by methoxy, by ethoxy, by n- or i-propoxy, by difluoromethoxy, by trifluoromethoxy, by methoxycarbonyl and / or by ethoxycarbonyl, phenyl, phenyloxy, benzyl, phenylethyl, benzyloxy, phenyloxycarbonyl, benzyloxycarbonyl, (respectively wholly or partially hydrogenated, if appropriate) pyrrolyl, pyrazolyl, imidazolyl, triazolyl, furyl, thienyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, oxadiazolyl, thiadiazolyl, pyridinyl,. pyrimidinyl, triazinyl, pyrazolylmethyl, furimethyl, thienylmethyl, oxazolylmethyl, isoxazolmethyl, thiazolmethyl, pyridinyl ethyl, pyrimidinylmethyl, pyrazolmethoxy, furylmethoxy or pyridylmethoxy R3 means hydrogen, fluorine, chlorine together with R2 means an alkanediyl or alkenodiyl group with 1 to 3 carbon atoms respectively , which optionally contains at the beginning (or at the end) or in the interior of the hydrocarbon chain an oxygen atom, a sulfur atom, an NH- group, an N-methyl group, a carbonyl group and / or a a thiocarbonyl group and means heterocyclyl, heterocyclylamino or heterocyclylimino, respectively monocyclic or bicyclic, saturated or unsaturated, respectively having 2 to 5 carbon atoms and 1 to 3 nitrogen atoms in the heterocyclic ring system, optionally containing an oxygen atom or a sulfur atom and / or, if appropriate, up to two groupings of the series formed by -co-, -cs- -so- and / or S02-, and which is optionally substituted by one or more groupings of the series consisting of nitro, hydroxy, amino, cyano, carboxy, carbamoyl, thiocarbamoyl, fluorine, chlorine, bromine; methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, (which are optionally substituted by fluorine, chlorine, methoxy or ethoxy); propenyl, butenyl, propynyl or butynyl (which are respectively substituted, if appropriate, by fluorine or by chlorine); methoxy, ethoxy, n- or i-propoxy, n-, i-, s- or t-butoxy, methoxycarbonyl or ethoxycarbonyl (which are respectively substituted, if appropriate, by fluorine, chlorine, methoxy or ethoxy); propenyloxy, butenyloxy, propynyloxy or butynyloxy (which are respectively substituted, if appropriate, by fluorine or by chlorine); methylthio, ethylthio, n- or i-propylthio, n-, i-, s- or t-butylthio, propethylthio, butenylthio, propylthio or butynylthio (which are respectively substituted, if appropriate, by fluorine or chlorine); methylamino, ethylamino, n- or i-propylamino, n-, i-, s- or t-butylamino, dimethylamino or diethylamino, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl or cyclohexylmethyl (which are respectively substituted given by fluorine, chlorine, methyl, ethyl, n- or i-propyl), phenyl, phenoxy, phenylthio, phenylsufinyl, phenylsulfonyl or phenylamino (which are respectively substituted by nitro or by cyano, by fluorine, by chlorine, by bromine, by methyl, by ethyl, by n- or i-propyl, by trifluoromethyl, by methoxy, by ethoxy, by n- or i-propoxy, by difluoromethoxy, by trifluoromethoxy, by methoxycarbonyl or by ethoxycarbonyl). If, for example, 2- (2-fluoro-4-cyano-5-methoxy-phenyl) -4-methyl-5-difluoromethyl-2,4-dihydro-3H-1,2,4-triazole is used, for example, 3-one and hydrogen sulfide as starting materials, the development of the reaction in the process according to the invention can be schematized by means of the scheme of the following formulas: The substituted aromatic nitriles, to be used as starting materials in the process according to the invention for the preparation of the compounds of the general formula (I), are generally defined by the formula (II). In the formula (II) R1, R2, R3 and Z preferably have or especially those meanings which have already been indicated preferably or particularly preferably for R1, R2, R3 and Z above in relation to the description of the compounds of the formula (I). The starting materials of the formula (II) are known and / or can be prepared according to known processes (see EP 370 332, EP 597 360, EP 609 734, EP 648 749). The process according to the invention for the preparation of the substituted aromatic thiocarboxylic acid amides of the formula (I) is carried out in the presence of a basic organic compound. As such, basic nitrogen compounds are primarily suitable. These include especially dialkylamines, trialkylamines, dialkylcycloalkylamines, dicycloalkylamines and alkyldicycloalkylamines, such as, for example, diisopropylamine, diisobutylamine, disbutylamine, dicyclopentylamine, dicyclohexylamine, trimethylamine, triethylamine, tripropylamine, tributylamine, ethyldiisopropylamine, N, N-dimethylcyclohexylamine and ethyldicyclohexylamine, N, N- dialkyl arylamines, such as for example N, N-dimethylbenzylamine, furthermore also organic, basic, (bi) cyclic nitrogen compounds, such as for example N-methylpiperidine, diazabicyclooctane (DABCO), diazabicyclononene (DBN) or diazabicycloundecene (DBU) . In the process according to the invention, trialkylamines, such as, for example, trimethylamine, triethylamine, tripropylamine, and tributylamine, and also N, N-dialkylarylalkylamines, such as, for example, N, N, are particularly preferably used as basic organic nitrogen compounds. -dimethylbenzylamine. The process according to the invention is carried out in the presence of an apolar or moderately polar organic solvent. These include especially aliphatic, alicyclic or aromatic hydrocarbons, if appropriate halogenated such as, for example, benzine, benzene, toluene, xylene, chlorobenzene, dichlorobenzene, petroleum ether, hexane, cyclohexane, methylcyclohexane, dichloromethane, chloroform, tetrachloromethane; ethers, such as diethyl ether, diisopropyl ether, diisobutyl ether, dioxane, tetrahydrofuran or ethylene glycol dimethyl or diethylether; ketones, such as acetone, butanone, methyl-isopropyl ketone or methyl isobutyl ketone, nitriles, such as acetonitrile, propionitrile or n-o-butyronitrile; esters such as methyl, ethyl, n- or i-propyl, n-, i- or s-butyl acetate. In the process according to the invention, toluene is preferably used as solvent. The reaction temperatures in carrying out the process according to the invention can vary within wide limits. In general, work is carried out at temperatures between 0 ° C and 150 ° C, preferably at temperatures between 20 ° C and 120 ° C, especially at temperatures between 40 ° C and 90 ° C. The process according to the invention is generally carried out under normal pressure. However, it is also possible to work under higher pressure or at lower pressure, generally between 0.1 bar and 10 bar. For carrying out the process according to the invention, per mol of substituted aromatic nitrile of the formula (II), in general, from 1 to 5 mol, preferably from 1.2 to 2.5 mol, especially from 1.5 to 2.5 moles of hydrogen sulphide (hydrogensulf ro) and from 1.0 to 5.0 moles, preferably from 1.5 to 4.0 moles, especially from 2.0 to 3.0 moles of a suitable basic organic compound. In general, the substituted aromatic nitrile will be placed together with a suitable basic organic compound in a suitable solvent and, after heating to the appropriate reaction temperature, the hydrogen sulfide will be introduced. The mixture is then stirred until the reaction is complete. The processing can be carried out in the usual manner. In most cases, the product is obtained directly in the crystalline state from the reaction mixture and can be isolated by suction filtration. The substituted aromatic thiocarboxylic acid amides of the formula (I) to be obtained according to the process of the invention are already known as compounds with herbicidal activity (see WO 95/30661). Preparation examples: Example 1. .0 g (51 mmol) of the 2- (2-fluoro-4-cyano-5-ethylsulfonylamino-phenyl) -4-methyl-5-trifluoromethyl-2,4-dihydro-3H-1,2 are suspended. 4-triazol-3-one in 100 ml of toluene and, after addition of 28.3 g (153 mmol) of tributylamine, the mixture is heated to about 65 ° C. At this temperature 3.5 g (102 mmol) of hydrogen sulphide are introduced in the course of about 20 minutes and the mixture is then stirred for 60 minutes at 60 ° C to 65 ° C. After removal of the heating source, let cool slowly to room temperature and isolate the crystalline product obtained by suction filtration. 20.7 g (90% of theory) of 2- (2-fluoro-4-thiocarbamoyl-5-ethylsulfonylamino-phenyl) -4-methyl-5-trifluoromethyl-2,4-dihydro-3H-1 are obtained. , 2,4-triazol-3-one with a melting point of 202 ° C. Example 2 A mixture of 21.0 g (50 mmol) of l- (4-cyano-5-ethylsulfonylamino-2-fluorophenyl) -3, β-dihydro-2,6-dioxo- is heated to approximately 65 ° C. 3-methyl-4-trifluoromethyl-1 (2H) -pyrimidine, 27.8 g (150 mmol) of tributylamine and 100 ml of toluene, and 3.4 g (100 mmol) of hydrogen sulphide are introduced at this temperature the course of approximately 30 minutes. The reaction mixture is then stirred for approximately another 60 minutes at about 65 ° C. After removal from the heating source, it is allowed to cool slowly to room temperature and the obtained crystalline product is isolated by suction filtration. The mixture is stirred with diisopropyl ether and again separated by suction filtration. .9 g (90% of theory) of l- (5-ethylsulfonylamino-2-fluoro-4-thiocarbamoyl-phenyl) -3,6-dihydro-2,6-dioxo-3-methyl-4 is obtained -trif lúormetil-1 (2H) -pirimidina with a melting point of 208QC. According to the aforementioned methods, the thiocarboxylic acid amides indicated in the following table are also obtained. Table.

It is noted that in relation to this date, the best method known to the applicant to carry out the aforementioned invention, is that which is clear from the present description of the invention. Having described the invention as above, the content of the following is claimed as property:

Claims

CLAIMS 1. Process for the preparation of substituted, aromatic thiocarboxylic acid amides of the general formula (I) wherein R1 signifies hydrogen or halogen, R2 signifies the following grouping, -A1-A2-A3 where A1 means a single bond, means oxygen, sulfur, -SO-, -S02-, -CO- or the grouping -N- A4-, wherein A4 means hydrogen, hydroxy, alkyl, alkoxy, aryl, alkylsulfonyl or arylsulfonyl, or (A1) means alkanediyl, alkenodiyl, alkynediyl, cycloalkanediyl, cycloalkenediyl or arenediyl substituted respectively where appropriate, A2 means a single bond, means oxygen , sulfur, -SO-, -S02-, CO- or the grouping -N-A4-, where A4 means hydrogen, hydroxy, alkyl, aryl, alkoxy, alkylsulfonyl or arylsulfonyl, or (A2) means alkanediyl, alkenodiyl, alkynediyl, cycloalkanediyl, cycloalkenediyl or arenediyl substituted respectively where appropriate, and A3 signifies hydrogen, hydroxy, amino, cyano, isocyano, thiocyanate, nitro, carboxy, carbamoyl, thiocarbamoyl, sulfo, chlorosulfonyl, halogen or means, respectively substituted optionally alkyl, alkoxy, alkylthio, alkylsulfinyl, alkylsulfonyl, alkylamino, dialkylamino, alkoxycarbonyl, dialkoxy (thio) phosphoryl, alkenyl, alkenyloxy, alkenylamino, alkylidenamino, alkenyloxycarbonyl, alkynyl, alkynyloxy, alkylamino alkynyloxycarbonyl, cycloalkyl cycloalkyloxy, cycloalkylalkyl, cycloalkylalkoxy, cycloalkylideneamino, cycloalkyloxycarbonyl, cycloalkylalkoxycarbonyl, aryl, aryloxy, arylalkyl, arylalkoxy, aryloxycarbonyl, arylalkoxycarbonyl, heterocyclyl, heterocyclylalkyl, heterocyclylalkoxy or heterocyclylalkoxycarbonyl, R3 signifies hydrogen, halogen or together with R2 signifies an alkanediyl group or an alkenediyl group, which contains at the beginning (or at the end) or in the interior of the hydrocarbon chain an oxygen atom, a sulfur atom, an NH- group, an N-alkyl group, a carbonyl group and / or a thiocarbonyl group, and Z means heterocyclyl, heterocyclylamino or heterocyclic saturated or unsaturated, monocyclic or bicyclic, substituted respectively where appropriate, characterized in that substituted aromatic nitriles of the general formula (II) are reacted wherein R1, R2, R3 and Z have the above meanings indicated, with hydrogen sulphide (hydrogen sulfide, H2S), in the presence of a basic organic compound and in the presence of a moderately polar organic solvent at temperatures between 0 ° C and 150 ° C.
2. Process according to claim 1, characterized in that substituted aromatic nitriles of the formula (II) are used, in which R1 signifies hydrogen, fluorine, chlorine or bromine, R2 means the following grouping, -Ax-A2-A3 in which A1 means a simple bond means oxygen, sulfur, -SO-, -S02-, -CO- or the group -N-A4- where A4 means hydrogen, hydroxy, alkyl with 1 to 4 carbon atoms, alkoxy, with 1 to 4 carbon atoms, phenyl, alkylsulfonyl with 1 to 4 carbon atoms or phenylsulfonyl, or (A1) means alkanediyl with the β carbon atoms, alkenodiyl with 2 to 6 carbon atoms, alkynediyl with 2 to 6 carbon atoms, cycloalkanediyl with 3 to 6 carbon atoms, cycloalkenodiyl having 3 to 6 carbon atoms or phenylene substituted, where appropriate, by fluorine or chlorine, A2 means a single bond, means oxygen, sulfur, -SO-, -S02-, -CO- or the grouping -N-A4- where A4 means hydrogen, hydrox i, alkyl having 1 to 4 carbon atoms, alkoxy with 1 to 4 carbon atoms, phenyl, alkylsulfonyl with 1 to 4 carbon atoms or phenylsulfonyl, or (A2) means alkanediyl with 1 to 6 carbon atoms, alkenediyl with 2 to 6 carbon atoms, alkynediyl with 2 to 6 carbon atoms, cycloalkanediyl with 3 to 6 carbon atoms, cycloalkenodiyl or phenylene substituted, where appropriate, by fluorine or chlorine, respectivelyis hydrogen, hydroxy, amino, cyano, isocyano, thiocyanato, nitro, carboxy, carbamoyl, thiocarbamoyl, sulfo, chlorosulfonyl, halogen, means, optionally substituted by halogen or by alkoxy with 1 to 4 carbon atoms, alkyl, alkoxy, alkylthio, alkylsulfinyl, alkylsulfonyl, alkylamino, dialkylamino, alkoxycarbonyl or dialkoxy (thio) phosphoryl with respectively 1 to 6 carbon atoms in the alkyl groups, means, optionally substituted by halogen, alkenyl, alkenyloxy, alkenylamino, alkylidenamino, alkenyloxycarbonyl, alkynyl, alkynyloxy, alkynylamino or alkynyloxycarbonyl with 2 to 6 carbon atoms in the alkenyl, alkylidene or alkynyl groups, respectively. means substituted, if appropriate, by halogen, cyano, carboxy, alkyl having 1 to 4 carbon atoms and / or alkoxycarbonyl having 1 to 4 carbon atoms, cycloalkyl, cycloalkyloxy, cycloalkylalkyl, cycloalkylalkoxy, cycloalkylidene, cycloalkyloxycarbonyl or cycloalkylalkoxycarbonyl having 3 to 6 carbon atoms in the cycloalkyl groups and, optionally, 1 to 4 carbon atoms in the alkyl groups or, respectively, optionally substituted by nitro, by cyano, by carboxy, by halogen, alkyl having 1 to 4 carbon atoms, halogen alkyl having 1 to 4 carbon atoms, alkyloxy having 1 to 4 carbon atoms, haloalkyloxy having 1 to 4 carbon atoms and / or alkoxy carbonyl having 1 to 4 carbon atoms. carbon, phenyl, phenyloxy, phenyl-C 1 -C 4 -alkyl, phenyl-C 1 -C 4 -alkoxy, phenyl-oxycarbonyl or phenyl-C 1 -C 4 -alkoxycarbonyl, (respec fully or partially hydrogenated, if appropriate) pyrrolyl, pyrazolyl, imidazolyl, triazolyl, furyl, thienyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, oxadiazolyl, thiadiazolyl, pyridinyl, pyrimidinyl, triazinyl, pyrazolyl-alkyl with 1 to 4 carbon atoms, furyl-C 1 -C 4 -alkyl, thienyl-C 1 -C 4 -alkyl, oxazolyl-C 1 -C 4 -alkyl, isoxazole-C 1 -C 4 -alkyl, thiazol-alkyl with 1 a 4 carbon atoms, pyridinyl-C 1 -C 4 -alkyl, pyrimidinyl-C 1 -C 4 -alkyl, pyrazolylmethoxy, furylmethoxy, means perhydropyranylmethoxy or pyridylmethoxy, R 3 means hydrogen, fluorine, chlorine, bromine, or together with R 2 means an alkanediyl or alkenodiyl group with, respectively, up to 4 carbon atoms, which optionally contains at the beginning (or at the end) or in the interior of the hydrocarbon chain an oxygen atom, a sulfur atom, an NH group- an N-alkyl group with 1 to 4 carbon atoms, a carbonyl group and / or a thiocarbonyl group, and Z means heterocyclyl, heterocyl-amino or heterocyclylimino, respectively monocyclic or saturated bicyclic, with 2 to 6 carbon atoms respectively and 1 to 4 hydrogen atoms in the hetericyl cyclic ring system, optionally containing, in addition, an oxygen or sulfur atom and / or optionally one to three groupings of the series consisting of -CO-, -CS-, - SO- and / or S02-, and which are optionally substituted by one or more groupings of the series consisting of nitro, hydroxy, amino, cyano, carboxy, carbamoyl, thiocarbamoyl halogen, alkyl with the β carbon atoms (which is optionally substituted by halogen or by alkoxy with 1 to 4 carbon atoms), alkenyl with 2 to 6 carbon atoms or alkynyl with 2 to 6 carbon atoms (which are each substituted, where appropriate, by halogen), alkoxy with the ß atoms d carbon or alkoxycarbonyl with the ß carbon atoms (which are respectively substituted, if appropriate, by halogen or by alkoxy with 1 to 4 carbon atoms), alkenyloxy with 2 to 6 carbon atoms or alkynyloxy with 2 to 6 carbon atoms ( which are respectively substituted, if appropriate, by halogen), alkylthio with the ß carbon atoms, alkenylthio with 2 to 6 carbon atoms, alkenylthio with 2 to 6 carbon atoms or alkynylthio with 2 to 6 carbon atoms (which are each substituted, if appropriate, by halogen), alkylamino with the β carbon atoms or di- (C 1 -C 4) alkyl -amino, cycloalkyl with 3 to 6 carbon atoms or cycloalkyl with 3 to 6 carbon atoms-alkyl with 1 to 4 carbon atoms (which are substituted respectively, optionally halogen and / or alkyl having 1 to 4 carbon atoms), phenyl, phenoxy, phenylthio, phenylsulfinyl, phenylsulphonyl or phenylamino (which are respectively substituted by nitro, by cyano, by halogen, by alkyl) with 1 to 4 carbon atoms, for halogenalkyl with 1 to 4 carbon atoms, for alkyloxy with 1 to 4 carbon atoms, for haloalkyloxy with 1 to 4 carbon atoms and / or for alkoxycarbonyl with 1 to 4 carbon atoms) .
3. Process according to claim 1, characterized in that substituted aromatic nitriles of the formula (II) are used, in which R1 signifies hydrogen, fluorine or chlorine, R2 means the following grouping, -A1-A2-A3 where A1 means in bond simple, means oxygen, sulfur, -SO-, -S02-, -CO-, or the group -N-A4- where A4 means hydrogen, hydroxy, methyl, ethyl, n- or i-propyl, methoxy, ethoxy n- or i-propoxy, methylsulfonyl or ethylsulphonyl, or (A1) means methylene, ethane-1,1-diyl, ethane-1, 2-diyl, propane-1,1-diyl, propane-1,2-diyl, propane- 1,3-diyl, ethane-1,2-diyl, propene-1,2-diyl, propene-1,3-diyl, etino-1,2-diyl or propino-1,3-diyl. A2 means a single bond, means oxygen, sulfur, -SO-, -SO2-, -CO- or the grouping -N-A4-, where A4 means hydrogen, hydroxy, methyl, ethyl, n- or i-propyl, methoxy , ethoxy, n- or i-propoxy, methylsulfonyl, ethenylsulfonyl, n- or i-propylsulfonyl or phenylsulfonyl, or (A2) means methylene, ethane-1,1-diyl, ethane-1, 2-diyl, propane-1, 1-diyl, propane-1, 2-diyl, propane-1,3-diyl, ethane-1, 2-diyl, propene-1, 2-diyl, pro-ene-1,3-diyl, etino-1, 2-diyl or propino-1,3-diyl means hydrogen, hydroxy, amino, cyano, nitro, carboxy, carbamoyl, sulfo, fluorine, chlorine, bromine, means, optionally substituted by fluorine, by chlorine, by methoxy or by ethoxy, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, 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 , not i-propylthio, n-, i-, s- or t-butylthio, methylsulphinyl, etisulfinyl, n- or i-propylsulfinyl, methylsulphinyl, ethylsulphonyl, n- or i-propylsulphonyl, methylamino, ethylamino, n- or i- propylamino, n-, i-, s- or t-butylamino, dimethylamino, diethylamino, methoxycarbonyl, ethoxycarbonyl, n- or i-propoxycarbonyl, dimethoxyphosphoryl, diethoxyphosphoryl, dipropoxyphosphoryl or diisopropoxyphosphoryl, mean respectively substituted by fluorine or by chlorine, propenyl, butenyl, propenyloxy, butenyloxy, propenylamino, butenylamino, propylidene, butylideneamino, propenyloxycarbonyl, butenyloxycarbonyl, propynyl, butynyl, propynyloxy, butynyloxy, propynylamino, butynylamino, propynyloxycarbonyl or butynyloxycarbonyl, means, optionally substituted by fluorine, by chlorine, by cyano, by carboxy, by methyl, by ethyl, by n- or i-propyl, by methoxycarbonyl or ethoxycarbonyl, cyclopropyl, cyclobutyl, cyclopentyl, ciciohexilo, cyclopropyloxy, cyclobutyloxy, cyclopentyloxy, cyclohexyloxy, cyclopropylmethyl, cyclobutylmethyl, cyclopentyl ethyl, cyclohexylmethyl, cyclopropylmethoxy, cyclobutylmethoxy, cyclopentylmethoxy, cyclohexylmethoxy, cyclopentylideneamino, ciclohexilidenamino, cyclopentyloxycarbonyl, cyclohexyloxycarbonyl, ciclopentilmetoxicarbonilo or ciclohexilmetoxicarbonilo, or means, respectively substituted, if appropriate, by nitro, by cyano, by carboxy, by fluorine, by chlorine, by bromine, by methyl, by ethyl, by n- or i-propyl, by trifluoromethyl, by methoxy, by ethoxy, by n- or i-propoxy, by difluoromethoxy, by trifluoromethoxy, by methoxycarbonyl, and / or by ethoxycarbonyl, phenyl, phenyloxy, benzyl, phenylethyl, benzyloxy, phenyloxycarbonyl, benzyloxycarbonyl, (respectively total or partially hydrogenated, if appropriate) pyrrolyl, pyrazolyl, imidazolyl, triazolyl, furyl, thienyl oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, oxadiazolyl, thiadiazolyl, pyridinyl, pyrimidinyl, triazinyl, pyrazolylmethyl, furylmethyl, thienylmethyl, oxazolylmethyl, isoxazolmethyl, thiazolmethyl, pyridinylmethyl, pyrimidinylmethyl, pyrazolemethoxy, furylmethoxy or pyridylmethoxy, R3 means hydrogen, fluorine, chlorine together with R2 means an alkanediyl or alkenidiyl group with 1 to 3 carbon atoms, which may be present at the beginning (or at the end) or in the interior of the hydrocarbon chain an oxygen atom, a sulfur atom, an NH- group, an N-methyl group, a carbonyl group and / or a thiocarbonyl group and Z means heterocyclyl, heterocyclylamino or heterocyclylimino, respectively monocyclic, or bicyclic, saturated or unsaturated, with respectively 2 to 5 carbon atoms and 1 to 3 nitrogen atoms in the heterocyclic ring system, additionally contains, if appropriate, an oxygen atom or a sulfur atom and / or, if appropriate, up to two groupings of the series consisting of -CO-, -CS- ~ S0- and / or S02-, and which is case given by one or several groupings of the series formed by nitro, hydroxy, amino, cyano, carboxy, carbamoyl, thiocarbamoyl, fluorine, chlorine, bromine; methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, (which are optionally substituted by fluorine, chlorine, methoxy or ethoxy); propenyl, butenyl, propynyl or butynyl (which are respectively substituted, if appropriate, by fluorine or by chlorine); methoxy, ethoxy, n- or i-propoxy, n-, i-, s- or t-butoxy, methoxycarbonyl or ethoxycarbonyl, (which are each respectively substituted by fluorine, by chlorine, by methoxy or by ethoxy); propenyloxy, butenyloxy, propynyloxy or butynyloxy (which are respectively substituted, if appropriate, by fluorine or by chlorine); methylthio, ethylthio, n- or i-propylthio, n-, i-, s- or t-butylthio, propethylthio, butenylthio, propylthio or butynylthio (which are respectively substituted, if appropriate, by fluorine or chlorine), methylamino, ethylamino, n- or i-propylamino, n-, i-, s- or t-butylamino, dimethylamino or diethylamino, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl or cyclohexylmethyl (which are each respectively substituted by fluorine, by chlorine, by methyl, by ethyl, by n- or i-propyl), phenyl, phenoxy, phenylthio phenylsulfinyl, phenylsulfonyl or phenylamino (which are each optionally substituted by nitro or by cyano, by fluorine, by chlorine, by bromine , by methyl, by ethyl, by n- or i-propyl, by trifluoromethyl, by methoxy, by ethoxy, by n- or i-propoxy, by difluoromethoxy, by trifluoromethoxy, by methoxycarbonyl or by ethoxycarbonyl). R E S U M E Prepared, according to a new process, substituted aromatic thiocarboxylic acid amides of the general formula (I) Wherein R1, R2, R3 and Z have the meanings indicated in the description, by reaction of substituted aromatic nitriles of the formula (II) with hydrogen sulphide in the presence of a basic organic compound and in the presence of an apolar or moderately polar organic solvent.