A process for the manufacture of the salts of sulfonylaminocarbonyl triazolinones

Abstract: The present invention relates to a process for manufacturing sulfonylaminocarbonyl triazolinones and salts thereof, which are herbicidally active compounds, wherein the process does not require isolation of the intermediate product. In particular, this invention relates to the conversion of a substituted triazolinone to a sulfonylaminocarbonyl triazolinone, and without the isolation of this intermediate product, the sulfonylaminocarbonyl triazolinone is then converted to a salt thereof.

Description: The present invention relates to improvements in the process for manufacturing the salts of certain sulfonylaminocarbonyl triazolinones, which are herbicidally active compounds (e.g. known from US 5,534,468). A new process, wherein a sulfonylaminocarbonyl triazolinone (which is obtained in a previous process step with or without isolation) is converted under pH-controlled conditions to a salt thereof is described. The invention is explained in detail as follows: Sulfonylaminocarbonyl triazolinones are well known in the art, as are processes for their preparation and their use as herbicides. European Patent EP-A 341,489 discloses certain substituted sulfonylamino-carbonyl triazolinones having herbicidal properties. Further, U.S. Patents 5,534,486 and 5,869,681 describe a process for producing sulfonylaminocarbonyl triazolinones which are bonded via oxygen. The process includes the reaction of a triazolinone with a sulfonamide derivative. U.S. Patent 5,750,718 describes intermediates for herbicidal sulfonylaminocarbonyl triazolinones having substituents which are bonded via sulfur. However, the known prior art processes produce sulfonylaminocarbonyl triazolinones in unsatisfactory yield and purity. Thus, there is a need in the art for a process to manufacture sulfonylaminocarbonyl triazolinones in high yield and purity. The present invention is related to a process for the preparation of the salts of sulfonylaminocarbonyl triazolinones. The process comprises the step of: reacting an intermediate product of general formula (III) wherein R 1 represents alkyl, alkenyl or alkynyl having in each case up to 6 carbon atoms, and each of which is unsubstituted or substituted by cyano, halogen, or C 1 -C 4 -alkoxy, or represents cycloalkyl group having 3 to 6 carbon atoms or cycloalkylalkyl group having 3 to 6 carbon atoms in the cycloalkyl moiety and 1 to 4 carbon atoms in the alkyl moiety, each of which is unsubstituted or substituted by halogen or C 1 -C 4 -alkyl, or represents aryl group having 6 or 10 carbon atoms or arylalkyl group having 6 or 10 carbon atoms in the aryl moiety and 1 to 4 carbon atoms in the alkyl moiety, each of which is unsubstituted or substituted by carboxyl, nitro, cyano, halogen, C 1 -C 4 -alkyl, C 1 -C 4 -halogenoalkyl, C 1 -C 4 -alkoxy, C 1 -C 4 -halogenoalkoxy or C 1 -C 4 -alkoxy-carbonyl. and R 2 represents alkyl, alkenyl or alkenyl, each of which has up to 6 carbon atoms, and each of which is unsubstituted or substituted by cyano, halogen or C 1 -C 4 -alkoxy, or represents cycloalkyl having 3 to 6 carbon atoms or cycloalkylalkyl having 3 to 6 carbon atoms in the cycloalkyl moiety and 1 to 4 carbon atoms in the alkyl moiety, each of which is unsubstituted or substituted by halogen or C 1 -C 4 -alkyl, or represents aryl having 6 to 10 carbon atoms or arylalkyl having 6 or 10 carbon atoms in the aryl moiety and 1 to 4 carbon atoms in the alkyle moiety, each of which is unsubstituted or substituted by carboxyl, cyano, nitro, halogen, C 1 -C 4 -alkyl, C 1 -C 4 -halogenoalkyl, C 1 -C 4 -alkoxy, C 1 -C 4 -halogenoalkoxy or C 1 -C 4 -alkoxy-carbonyl, and R 3 represents the group wherein R 4 and R 5 are identical or different and represent hydrogen, fluorine, chlorine, bromine, iodine, nitro, C 1 -C 6 -alkyl, which is unsubstituted or substituted by fluorine, chlorine, bromine, cyano, carboxyl, C 1 -C 4 -alkoxycarbonyl, C 1 -C 4 -alkylaminocarbonyl, di-(C 1 -C 4 -alkyl)aminocarbonyl, hydroxyl, C 1 -C 4 -alkoxy, formyloxy, C 1 -C 4 -alkylcarbonyloxy, C 1 -C 4 -alkoxycarbonyloxy, C 1 -C 4 -alkylaminocarbonyloxy, C 1 -C 4 -alkylthio, C 1 -C 4 -alkylsulfinyl, C 1 -C 4 -alkylsulfonyl, di-(C 1 -C 4 -alkyl)-aminosulfonyl, C 3 -C 6 -cycloalkyl or phenyl, or represent C 2 -C 6 -alkenyl which is unsubstituted or substituted by fluorine, chlorine, bromine, cyano, C 1 -C 4 -alkoxycarbonyl, carboxyl or phenyl, or represent C 2 -C 6 -alkynyl which is unsubstituted or substituted by fluorine, chlorine, bromine, cyano, C 1 -C 4 -alkoxycarbonyl, carboxyl or phenyl, or represent C 1 -C 4 -alkoxy which is unsubstituted or substituted by fluorine, chlorine, bromine, cyano, carboxyl, C 1 -C 4 -alkoxycarbonyl, C 1 -C 4 -alkoxy, C 1 -C 4 -alkylthio, C 1 -C 4 -alkylsulfinyl or C 1 -C 4 -alkylsulfonyl, or represent C 1 -C 4 -alkylthio which is unsubstituted or substituted by fluorine, chlorine, bromine, cyano, carboxyl, C 1 -C 4 -alkoxycarbonyl, C 1 -C 4 -alkylthio, C 1 -C 4 -alkylsulfinyl or C 1 -C 4 -alkylsulfonyl, or represent C 3 -C 6 alkenyloxy which is unsubstituted or substituted by fluorine, chlorine, bromine, cyano or C 1 -C 4 -alkoxycarbonyl, or represent C 2 -C 6 -alkenylthio which is unsubstituted or substituted by fluorine, chlorine, bromine, cyano, nitro, C 1 -C 3 -aklylthio or C 1 -C 4 -akoxycarbonyl, C 3 -C 6 -alkynyloxy, C 3 -C 6 -alkynylthio or the radical -S(O) p -R 6 where p represents the numbers 1 or 2, and R 6 represents C 1 C 4 -alkyl which is unsubstituted or substituted by fluorine, chlorine, bromine, cyano or C 1 -C 4 -alkoxy-carbonyl, C 3 -C 6 -alkenyl, C 3 -C 6 -alkynyl, C 1 -C 4 -alkoxy, C 1 -C 4 -alkoxy-C 1 -C 4 -alkylamino, C 1 -C 4 -alkylamino, di-(C 1 -C 4 -alkyl)amino, phenyl or the radical ―NHOR 7 wherein R 7 represents C 1 -C 12 -alkyl which is unsubstituted or substituted by fluorine, chlorine, cyano, C 1 -C 4 -alkoxy, C 1 -C 4 -alkylthio, C 1 -C 4 -alkylsulfinyl, C 1 -C 4 -alkylsulfonyl, C 1 -C 4 -alkyl-carbonyl, C 1 -C 4 -alkoxy-carbonyl, C 1 -C 4 -alkylamino-carbonyl or di-(C 1 -C 4 -alkyl)-amino-carbonyl), or represents C 3 -C 6 -alkenyl which is unsubstituted or substituted by fluorine, chlorine or bromine, C 3 -C 6 -alkynyl, C 3 -C 6 -cycloalkyl, C 3 -C 6 -cycloalkyl-C 1 -C 2 -alkyl, phenyl-C 1 -C 2 -alkyl which is unsubstituted or substituted by fluorine, chlorine, nitro, cyano, C 1 -C 4 -alkyl, C 1 -C 4 -alkoxy or C 1 -C 4 -alkoxy-carbonyl), or represents benzhydryl, or represents phenyl which is unsubstituted or substituted by fluorine, chlorine, nitro, cyano, C 1 -C 4 -alkyl) trifluoromethyl, C 1 -C 4 -alkoxy, C 1 -C 2 -fluoroalkoxy, C 1 -C 4 -alkylthio, trifluoromethylthio or C 1 -C 4 -alkoxy-carbonyl, R 4 and/or R 5 furthermore represent phenyl or phenoxy, or represent C 1 -C 4 -alkylcarbonylamino, C 1 -C 4 -alkoxycarbonyl-amino, C 1 -C 4 -alkylamino-carbonyl-amino, di-(C 1 -C 4 -alkyl)-amino-carbonyl-amino, or the radical -CO-R 8 wherein R 8 represents C 1 -C 6 -alkyl, C 1 -C 6 -alkoxy, C 3 -C 6 -cycloakoxy, C 3 -C 6 -alkenyloxy, C 1 -C 4 -alkylthio, C 1 -C 4 -alkylamino, C 1 -C 4 -alkoxyamino. C 1 -C 4 -alkoxy-C 1 -C 4 -alkyl-amino or di-(C 1 -C 4 -alkyl)-amino which are unsubstituted or substituted by halogen selected from the group consisting of fluorine and chlorine, R 4 and/or R 5 furthermore represent trimethylsilyl, thiazolinyl, C 1 -C 4 -alkylsulfonyloxy, di-(C 1 -C 4 -alkyl)-aminosulfonylamino or the radical -CH=N-R 9 wherein R 9 represents C 1 -C 6 -alkyl which is unsubstituted or substituted by fluorine, chlorine, cyano, carboxyl, C 1 -C 4 -alkoxy, C 1 -C 4 -alkylthio, C 1 -C 4 -alkylsulfinyl or C 1 -C 4 -alkylsulfonyl, or represents benzyl which is unsubstituted or substituted by fluorine or chlorine, or represents C 3 -C 6 -alkenyl or C 3 -C 6 -alkynyl, each of which is unsubstituted or substituted by fluorine or chlorine, or represents phenyl which is unsubstituted or substituted by fluorine, chlorine, bromine, C 1 -C 4 -alkyl, C 1 -C 4 -alkoxy, trifluoromethyl, trifluoromethoxy or trifluoromethylthio, or represents unsubstituted or halogen substituted C 1 -C 6 -alkoxy, C 3 -C 6 -alkenoxy, C 3 -C 6 -alkynoxy or benzyloxy, wherein the halogen is selected from the group consisting of fluorine and chlorine, or represents amino, C 1 -C 4 -alkylamino, di-(C 1 -C 4 -alkyl)-amino, phenylamino, C 1 -C 4 -alkyl-carbonylamino, C 1 -C 4 -alkoxy-carbonylamino or C 1 - C 4 -alkyl-sulfonylamino, or represents phenylsulfonylamino which is unsubstituted or substituted by fluorine, chlorine, bromine or methyl, furthermore R 3 represents the radical wherein R 10 represents hydrogen or C 1 -C 4 -alkyl, wherein R 11 and R 12 are identical or different and represent hydrogen, fluorine, chlorine, bromine, nitro, cyano, C 1 -C 4 -alkyl which is unsubstituted or substituted by halogen selected from the group consisting of fluorine and chlorine, C 1 -C 4 -alkoxy which is unsubstituted or substituted by halogen selected from the group consisting of fluorine and chlorine, carboxyl, C 1 -C 4 -alkoxy-carbonyl, dimethylaminocarbonyl, C 1 -C 4 -alkylsulfonyl or di-(C 1 -C 4 -alkyl)-aminosulfonyl; furthermore R 3 represents the radical wherein R 13 and R 14 are identical or different and represent hydrogen, fluorine, chlorine, bromine, nitro, cyano, C 1 -C 4 -alkyl which is unsubstituted or substituted by halogen selected from the group consisting of fluorine and chlorine, or C 1 -C 4 -alkoxy which is unsubstituted or substituted by halogen selected from the group consisting of fluorine and chlorine; furthermore R 3 represents the radical wherein R 15 and R 16 are identical or different and represent hydrogen, fluorine, chlorine, bromine, nitro, cyano, C 1 -C 4 -alkyl which is unsubstituted or substituted by halogen selected from the group consisting of fluorine and chlorine, C 1 -C 4 -alkoxy which is unsubstituted or substituted by halogen selected from the group consisting of fluorine and chlorine, or represent C 1 -C 4 -alkylthio, C 1 -C 4 -alkylsulfinyl or C 1 C 4 -alkylsulfonyl which are unsubstituted or substituted by halogen selected from the group consisting of fluorine and chlorine, or represent aminosulfonyl, mono-(C 1 -C 4 -alkyl)-aminosulfonyl, di-(C 1 -C 4 -alkyl)-aminosulfonyl or C 1 -C 4 -akoxycarbonyl or dimethylaminocarbonyl; furthermore R 3 represents the radical wherein R 17 and R 18 are identical or different and represent hydrogen, fluorine, chlorine, bromine, C 1 -C 4 -alkyl which is unsubstituted or substituted by halogen selected from the group consistmg of fluorine and bromine, C 1 -C 4 -alkoxy which is unsubstituted or substituted by halogen selected from the group consisting of fluorine and chlorine, C 1 -C 4 -alkylthio, C 1 -C 4 -akylsulfinyl or C 1 -C 4 -alkylsulfonyl which are unsubstituted or substituted by halogen selected from the group consisting of fluorine and chlorine, or represent di-(C 1 -C 4 -alkyl)-aminosulphonyl; furthermore R 3 represents the radical wherein R 19 and R 20 are identical or different and represent hydrogen, fluorine, chlorine, bromine, cyano, nitro, C 1 -C 4 -alkyl which is unsubstituted or substituted by halogen selected from the group consisting of fluorine and chlorine, C 1 -C 4 -alkoxy which is unsubstituted or substituted by halogen selected from the group consisting of fluorine and chlorine, C 1 -C 4 -alkylthio, C 1 -C 4 -alkylsulfinyl or C 1 -C 4 -alkysulfonyl which is unsubstituted or substituted by halogen selected from the group consisting of fluorine and chlorine, di-(C 1 -C 4 -akyl)-aminosulfonyl, C 1 -C 4 -alkoxy-carbonyl or dimethylaminocarbonyl, and A represents oxygen, sulfur or the group N―Z 1 , wherein Z 1 represents hydrogen, C 1 -C 4 -alkyl which is unsubstituted or substituted by fluorine, chlorine, bromine, or cyano, C 3 -C 6 -cycloalkyl, benzyl, phenyl which is unsubstituted or substituted by fluorine, chlorine, bromine or nitro, C 1 -C 4 -alkylcarbonyl, C 1 -C 4 -alkoxy-carbonyl or di-(C 1 -C 4 -alkyl)-amino-carbonyl; furthermore R 3 represents the radical wherein R 21 and R 22 are identical or different and represent hydrogen, C 1 -C 4 -alkyl, halogen, C 1 -C 4 -alkoxycarbonyl, C 1 -C 4 -alkoxy or C 1 -C 4 -halogenoalkoxy, Y 1 represents sulfur or the group N-R 23 , wherein R 23 represents hydrogen or C 1 -C 4 -alkyl; furthermore R 3 represents the radical wherein R 24 represents hydrogen, C 1 -C 4 -alkyl, benzyl, pyridyl, quinolinyl or phenyl, R 25 represents hydrogen, halogen, cyano, nitro, C 1 -C 4 -alkyl which is unsubstituted or substituted by halogen selected from the group consisting of fluorine and chlorine, C 1 -C 4 -alkoxy which is unsubstituted or substituted by halogen selected from the group consisting of fluorine and chlorine, dioxolanyl or C 1 -C 4 -alkoxy-carbonyl, and R 26 represents hydrogen, halogen or C 1 -C 4 -alkyl; furthermore R 3 represents a compound selected from the group consisting of under pH controlled conditions with a base in such way that the base is added in an amount such that the pH of the mixture attained is from 5 to 9, to produce a salt thereof, a final product of the general formula (IV) wherein R 1 , R 2 , and R 3 are as defined above, and M represents an alkali or alkaline earth metal or protonated ammonia derivative. More preferably, R 1 represents methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, each of which is unsubstituted or substituted by cyano, fluorine, chlorine or bromine, methoxy or ethoxy, or represents propenyl, butenyl, propinyl or butinyl, each of which is unsubstituted or substituted by cyano, fluorine, chlorine or bromine, or represents cyclopropyl, cyclobutyl or cyclopropylmethyl, each of which is unsubstituted or substituted by fluorine, chlorine, bromine, methyl or ethyl, or represents phenyl or benzyl, each of which is unsubstituted or substituted by cyano, fluorine, chlorine, bromine, methyl, ethyl, trifluoromethyl, methoxy, ethoxy, difluoromethoxy, trifluoromethoxy, methoxycarbonyl or ethoxycarbonyl. Most preferably, R 1 represents methyl. More preferably, R 2 represents methyl, ethyl, n- or i-propyl or n-, i-, s- or t-butyl, each of which is unsubstituted or substituted by cyano, fluorine, chlorine or bromine, methoxy or ethoxy, or represents propenyl, butenyl, propinyl or butinyl, each of which is unsubstituted or substituted by cyano, fluorine, chlorine or bromine, or represents cyclopropyl, or cyclopropylmethyl, each of which is unsubstituted or substituted by fluorine, chlorine, bromine, methyl or ethyl, or represents phenyl or benzyl, each of which is unsubstituted or substituted by cyano, fluorine, chlorine, bromine, methyl, ethyl, trifluoromethyl, methoxy, ethoxy, difluoromethoxy, trifluoromethoxy, methoxycarbonyl or ethoxycarbonyl. Most preferably, R 2 represents methyl, n- or i-propyl. In particular, the invention relates to compounds of the formula (IV) wherein R 1 represents C 1 -C 4 -alkyl which is unsubstituted or substituted by fluorine, cyano, methoxy or ethoxy, or represents allyl, C 3 -C 6 -cycloalkyl, benzyl or phenyl, R 2 represents C 1 -C 4 -alkyl which is unsubstituted or substituted by halogen selected from the group consisting of fluorine and/or chlorine, methoxy or ethoxy, or represents C 3 -C 4 -alkenyl which is optionally substituted by fluorine and chlorine, or represents C 3 -C 6 -cycloalkyl, or represents benzyl which is unsubstituted or substituted by a compound selected from the group consisting of fluorine, chlorine and methyl, and R 3 represents the group wherein R 4 represents fluorine, chlorine, bromine, methyl, trifluoromethyl, methoxy, difluoromethoxy, trifluoromethoxy, 2-chloro-ethoxy, 2-methoxy-ethoxy, C 1 -C 3 -alkythio, C 1 -C 3 -alkysulfinyl, C 1 -C 3 -alkylsulfonyl, dimethylaminosulfonyl, diethylaminosulfonyl, N-methoxy-N-methylaminosulfonyl, methoxyaminosulfonyl, phenyl, phenoxy or C 1 -C 3 -alkoxy-carbonyl and R 5 represents hydrogen, fluorine, chlorine or bromine; furthermore R 3 represents the radical wherein R 10 represents hydrogen, R 11 represents fluorine, chlorine, bromine, methyl, methoxy, difluoromethoxy, trifluorormethoxy, ethoxy, methoxycarbonyl, ethoxycarbonyl, methylsulfonyl or dimethylaminosulfonyl, and R 12 represents hydrogen; furthermore R 3 represents the radical wherein R represents C 1 -C 4 -alkyl, or represents the radical wherein R represents C 1 -C 4 -alkyl. The intermediate of general formula (III) used in this process can be obtained in a previous reaction step with or without isolation by reaction of a triazolinone compound of the general formula (I) wherein R 1 and R 2 each are defined as above, with a sulfonyl isocyanate of the following general formula (II) O=C=N-SO 2 -R 3 wherein R 3 is as defined as above. In a preferred embodiment of the pH-controlled process variant the reaction step for the preparation of the intermediate of the general formula (III) is carried out before the pH-controlled salt production step without isolating the intermediate product of general formula (III). The novel pH-controlled reaction step is especially well suited for the preparation of the sodium, potassium, magnesium, calcium, ammonium, C 1 -C 4 -alkyl-ammonium, di-(C 1 -C 4 -alkyl)-ammonium, tri-(C 1 -C 4 -alkyl)-ammonium, C 5 - or C 6 -cycloalkylammonium and di-(C 1 -C 2 -alkyl)-benzyl-ammonium salts of the compounds according to general formula (IV). The pH-controlled process step according to the invention is generally carried out at atmospheric pressure. However, it is also possible to conduct the process under elevated or reduced pressure. The preparation of the compound of general formula (III) by reaction of the substituted triazolinone of the general formula (17 with the sulfonyl isocyanate of the general formula (II) is carried out at a temperature of from about -20°C to about 120°C, and preferably at a temperature of from about 0°C to about 45°C. The reaction time to produce the intermediate product is up to about 48 hours, and preferably from about 1 hour to about 8 hours. Suitable sulfonyl isocyanates for producing the intermediate of formula (III) include 2-(trifluoromethoxy) benzensulfonyl isocyanate, 2-(methoxycarbonyl)benzenesulfonyl isocyanate, benzenesulfonyl isocyanate, ρ-toluenesulfonyl isocyanate, 2-fluoro, 2-chloro-, 2-bromo-, 2-methyl-, 2-methoxy-, 2-trifluoromethyl-, 2-difluoromethoxy-, 2-trifluoro-methoxy-, 2-methylthio-, 2-ethylthio-, 2-propylthio-, 2-methylsulfinyl-, 2-methyl-sulfonyl-, 2-dimethylaminosulfonyl-, 2-diethylamino-sulfonyl-, 2-(N-methoxy-N-methyl-aminosulfonyl-, 2-phenyl-, 2-phenoxy-, 2-methoxycarbonyl-, 2-ethoxycarbonyl, 2-propoxycarbonyl- and 2-isopropoxycarbonylphenylsulfonyl isocyanate, 2-fluoro-, 2-chloro-, 2-difluoromethoxy-, 2-trifluoro-methoxy-, 2-methoxycarbonyl- and 2-ethoxycarbonyl-benzylsulfonyl isocyanate, 2-methoxycarbonyl-3-thienyl-sulfonyl isocyanate, 4-methoxycarbonyl- and 4-ethoxycarbonyl-1-methyl-pyrazol-5-yl-sulfonyl isocyanate. Preferably, the sulfonyl isocyanate is 2-(trifluoromethoxy)benzenesulfonyl isocyanate or 2-(methoxycarbonyl)benzenesulfonyl isocyanate. The reaction of the substituted triazolinone (formula I) with the sulfonyl isocyanate (formula II) is carried out in the presence of a solvent. Suitable solvents include inert organic solvents such as aliphatic and aromatic, unhalogenated or halogenated hydrocarbons such as pentane, hexane, heptane, cyclohexane, methylene chloride, ethylene chloride, benzene, toluene, xylene, chlorobenzene, dichlorobenzene, petroleum ether, hexane, cyclohexane, dichloromethane, chloroform, carbon tetrachloride; ethers such as diethyl ether, diisopropyl ether, dibutyl ether, dioxane, tetrahydrofuran or diglycol dimethyl ether, glycol dimethyl ether or ethylene glycol diethyl ether; ketones such as acetone, butanone, methyl ethyl ketone, methyl isopropyl ketone or methyl isobutyl ketone; nitriles such as acetonitrile, propionitrile or butyronitrile; amides such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-formanilide, N-methyl-pyrrolidone or hexamethylphosphoric triamide; esters such as methyl acetate or ethyl acetate; also dimethyl sulfoxide, tetramethylene sufone and hexamethylphosphoric triamide. Preferably, the solvent used in the process of the invention is methyl isobutyl ketone, or xylene, or a commercially available mixture of xylenes containing ortho-xylene, para-xylene and meta-xylene. The reaction of a sulfonylaminocarbonyl triazolinone product of general formula (III) with a base, to convert the triazolinone product to a salt thereof (final product of the general formula IV) under pH-controlled conditions, is carried out at a temperature of from about -20°C to about 120°C, and preferably from about 0°C to about 45°C. The reaction time for this conversion to the final product is up to about 48 hours, and preferably from about 2 hours to about 8 hours. During this conversion of the sulfonylaminocarbonyl triazolinone product of general formula (III) to a salt thereof (final product of the general formula IV), the reaction is carried out under pH controlled conditions. Thus, the base is added to the reaction mixture in an amount such that the pH of the mixture attained is from about 5 to about 10, preferably from about 5.5 to about 9, and most preferably from about 6 to about 7. Suitable bases for use in this conversion step include bases such as sodium hydroxide, potassium hydroxide, ammonia, or aqueous mixtures thereof. A preferred base is sodium hydroxide, or an aqueous solution of sodium hydroxide. In an embodiment of the invention, the conversion of the triazolinone product of general formula (III) to the final product of general formula (IV) is carried out in the presence of a solvent. Suitable solvents include aliphatic, alicyclic or aromatic, unhalogenated or halogenated hydrocarbons such as benzene, toluene, xylene, chlorobenzene, dichlorobenzene, petroleum ether, hexane, cyclohexane, dichloromethane, chloroform, tetrachloromethane; ethers such as diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran or ethylene glycol dimethyl ether or ethylene glycol diethyl ether; ketones such as acetone, butanone, or methyl isobutyl ketone; nitriles such as acetonitrile, propionitrile or benzonitrile; amides such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methylformanilide, N-methyl-pyrrolidone or hexamethylphosphoric triamide; esters such as methyl acetate or ethyl acetate, sulfoxides such as dimethyl sulfoxide, alcohols such as methanol, ethanol, n- or i-propanol, n-, i-, s-, or t-butanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether; water and mixtures thereof. Preferred solvents include water, methyl isobutyl ketone, propanol, methanol, toluene, a commercially available mixture of xylenes containing ethylbenzene, ortho-xylene, para-xylene, meta-xylene, and mixtures thereof. In a preferred embodiment of the pH-controlled reaction, the conversion of the intermediate product of general formula (III) to the final product of general formula (IV) is carried out in a mixture of water and methyl isobutyl ketone, or a mixture of water, methanol and xylenes. The pH-controlled reaction is especially well suited for the conversion 4,5-dihydro-3-methoxy-4-methyl-5-oxo-N-[[2-(trifluoromethoxy)phenyl]sulfonyl]-1H-1,2,4-triazole-1-carboxamide (MSU) to a salt thereof, preferably to the sodium salt with the common name Flucarbazone-sodium. Further, it is well suited for the conversion of 2-[[[(4,5-dihydro-4-methyl-5-oxo-3-propoxy-1H-1,2,4-triazol-1-yl)carbonyl]amino]sulfonyl)-benzoic acid methyl ester (PSU) to a salt thereof, preferably to the sodium salt with the common name Propoxycarbazone-sodium. In another embodiment of the pH-controlled reaction step, the salt of the MSU is isolated as a monohydrate. EXAMPLES Example 2 - The Preparation of Propoxycarbazone-sodium To a solution (dried by azeotropic distillation) containing 62.8 grams (0.40 moles) of 5-propoxy-4-methyl-2,4-dihydro-3H-1,2,4-triazol-3-one (PMT) in about 250 grams of methyl isobutyl ketone (MIBK) was added a solution of 160.8 grams (0.40 moles) of 60% pure 2-methoxycarbonylbenzenesulfonyl isocyanate in 80 grams of MIBK at a temperature of from about 30°C to about 32°C, over a time period of about 2 hours. After the addition was complete, the reaction mixture was allowed to come to room temperature and the mixture was stirred for about 16 hours to complete the formation of PSU. To convert the PSU to Propoxycarbazone-sodium, the reaction mixture was diluted with 10 grams of water and then treated with 50% aqueous NaOH solution over a period of about 6 hours, until all the PSU was converted into its sodium salt, i.e., Propoxycarbazone-sodium. To isolate the product, the reaction mixture was filtered under vacuum, washed twice with 400 grams of warm (45°C) MIBK and dried under vacuum at room temperature to give 160.8 grams (87% pure) Propoxycarbazone-sodium. The net isolated yield based on PMT was 83.3%. The purity of the isolated Propoxycarbazone-sodium was only 87% mainly because the isocyanate contained about 15-20% of 2-methoxycarbonyl- benzenesulfonyl chloride as impurity. Some of this hydrolyzed under the reaction conditions to the corresponding sulfonic acid which then formed the sodium salt and ended up in the product. Example 3 - The Preparation of Propoxycarbazone-sodium - PSU Isolated In a 1000 ml flask with mechanical stirrer and thermometer, 119.8 grams (0.2 moles) of isolated PSU and 200 ml of methyl isobutyl ketone (MIBK) were charged. The mixture was agitated and then 10 ml of water was added. The initial pH of the reaction mixture was 2.8. Then 50% sodium hydroxide (NaOH) was added to ambient temperature over a 2 hour time period, at pH controlled conditions. During this addition step, the pH of the reaction mixture was from about 4.6 to about 4.8. The pH of the reaction mixture stabilized at about 7.7. The mixture was agitated from about 1 hour and the solids were isolated by vacuum filtration. The net yield based on PSU was 97.5%. Example 4. The Preparation of Flucarbazone-sodium hydrate - MSU Not Isolated 261.0 grams (1.74 moles) of 98% pure 5-methoxy-4-methyl-2,4-dihydro-3H-1,2,4-triazol-3-one (MMT) hydrate in about 2600 grams of methyl isobutyl ketone (MIBK) was dried by azeotropic distillation of part of the MIBK under reduced pressure (with a pot temperature of about 80°C) and then cooled to room temperature under a nitrogen atmosphere. To the resulting MMT slurry in MIBK was added 534.0 grams (1.74 moles) of 87.0% pure 2-(trifluoromethoxy) benzenesulfonyl isocyanate over a period of about 2 hours. The reaction mixture was stirred at room temperature for about 6 hours. The conversion reaction of the MMT (to MSU) was monitored using a liquid chromatograph. About 140.0 grams of water were added to the reaction mixture. The mixture was then treated with 50% aqueous sodium hydroxide (NaOH). The NaOH was added over a period of about 4 hours in an amount such that the pH of the reaction mixture was between about 6 and about 7. The reaction mixture was stirred for about 1 hour. The mixture was then filtered, and washed with about 500 grams of MIBK and dried to isolate the Flucarbazone-sodium hydrate. The yield of Flucarbazone-sodium hydrate was about 93.0% based on MMT hydrate. The purity (water free) was about 98.0%. Example 4A The procedure described in Example 4 was carried out with the exception that the 50% aqueous NaOH was added in an amount such that the pH of the reaction mixture was between about 10.2 and about 10.5. The purity of the Flucarbazone-sodium hydrate decreased to about 96.5%. Example 4B The procedure described in Example 4 was carried out with the exception that the 50% aqueous NaOH was added in an amount such that the pH of the reaction mixture was between about 11.0 and about 11.5. The purity of the Flucarbazone-sodium hydrate decreased to about 95.6%. Example 4C The procedure described in Example 4 was carried out with the exception that the 50% aqueous NaOH was added in an amount such that the pH of the reaction mixture attained was between about 12.0 and about 12.5. The purity of the Flucarbazone-sodium hydrate decreased to about 95.1%. In Examples 4A, 4B, and 4C, concentrated H 2 SO 4 was added to the reaction mixture in an amount such that the pH was about 7.0. The purity of the MKH then increased to about 98.0%.

Claims: A process for preparing a salt of a sulfonylaminocarbonyl triazolinone comprising the step of reacting an intermediate product of general formula (III) wherein R 1 represents alkyl, alkenyl or alkynyl having in each case up to 6 carbon atoms, and each of which is unsubstituted or substituted by cyano, halogen, or C 1 -C 4 -alkoxy, or represents cycloalkyl group having 3 to 6 carbon atoms or cycloalkylalkyl group having 3 to 6 carbon atoms in the cycloalkyl moiety and 1 to 4 carbon atoms in the alkyl moiety, each of which is unsubstituted or substituted by halogen or C 1 -C 4 -alkyl, or represents aryl group having 6 or 10 carbon atoms or arylalkyl group having 6 or 10 carbon atoms in the aryl moiety and 1 to 4 carbon atoms in the alkyl moiety, each of which is unsubstituted or substituted by carboxyl, nitro, cyano, halogen, C 1 -C 4 -alkyl, C 1 -C 4 -halogenoalkyl, C 1 -C 4 -alkoxy, C 1 -C 4 -halogenoalkoxy or C 1 -C 4 -alkoxycarbonyl, R 2 represents alkyl, alkenyl or alkynyl, each of which has up to 6 carbon atoms, and each of which is unsubstituted or substituted by cyano, halogen or C 1 -C 4 -alkoxy, or represents cycloalkyl having 3 to 6 carbon atoms or cycloalkylalkyl having 3 to 6 carbon atoms in the cycloalkyl moiety and 1 to 4 carbon atoms in the alkyl moiety, each of which is unsubstituted or substituted by halogen or C 1 -C 4 -alkyle, or represents aryl having 6 to 10 carbon atoms or arylalkyl having 6 or 10 carbon atoms in the aryl moiety and 1 to 4 carbon atoms in the alkyl moiety, each of which is unsubstituted or substituted by carboxyl, cyano, nitro, halogen, C 1 -C 4 -alkyl, C 1 -C 4 -halogenoalkyl, C 1 -C 4 -alkoxy, C 1 -C 4 -halogenoalkoxy or C 1 -C 4 -alkoxy-carbonyl, and R 3 represents the group wherein R 4 and R 5 are identical or different and represent hydrogen, fluorine, chlorine, bromine, iodine, nitro, C 1 -C 6 -alkyl, which is unsubstituted or substtuted by fluorine, chlorine, bromine, cyano, carboxyl, C 1 -C 4 -alkoxycarbonyl, C 1 -C 4 -alkylaminocarbonyl, di-(C 1 -C 4 -alkyl)aminocarbonyl, hydroxyl, C 1 -C 4 -alkoxy, fonnyloxy, C 1 -C 4 -alkylcarbonyloxy, C 1 -C 4 -alkoxycarbonyloxy, C 1 -C 4 -alkylaminocarbonyloxy, C 1 -C 4 -alkylthio, C 1 -C 4 -alkylsulfinyl, C 1 -C 4 -alkylsulfonyl, di-(C 1 -C 4 -alkyl)-aminosulfonyl, C 3 -C 6 -cycloalkyl or phenyl, or represent C 2 -C 6 -alkenyl which is unsubstituted or substituted by fluorine, chlorine, bromine, cyano, C 1 -C 4 -alkoxycarbonyl, carboxyl or phenyl, or represent C 2 -C 6 -alkynyl which is unsubstituted or substituted by fluorine, chlorine, bromine, cyano, C 1 -C 4 -alkoxycarbonyl, carboxyl or phenyl, or represent C 1 -C 4 -alkoxy which is unsubstituted or substituted by fluorine, chlorine, bromine, cyano, carboxyl, C 1 -C 4 -alkoxycarbonyl, C 1 -C 4 -alkoxy, C 1 -C 4 -alkylthio, C 1 -C 4 - alkylsulfinyl or C 1 -C 4 -alkylsulfonyl, or represent C 1 -C 4 -alkylthio which is unsubstituted or substituted by fluorine, chlorine, bromine, cyano, carboxyl, C 1 -C 4 -alkoxycarbonyl, C 1 -C 4 -alkylthio, C 1 -C 4 -alkylsulfinyl or C 1 -C 4 -alkylsulfonyl, or represent C 3 -C 6 alkenyloxy which is unsubstituted or substituted by fluorine, chlorine, bromine, cyano or C 1 -C 4 -alkoxycarbonyl, or represent C 2 -C 6 -alkenylthio which is unsubstituted or substituted by fluorine, chlorine, bromine, cyano, nitro, C 1 -C 3 -aklylthio or C 1 -C 4 -alkoxycarbonyl, C 3 -C 6 -alkynyloxy, C 3 -C 6 -alkynylthio or the radical -S(O) p -R 6 where p represents the numbers 1 or 2, and R 6 represents C 1 -C 4 -alkyl which is unsubstituted or substituted by fluorine, chlorine, bromine, cyano or C 1 -C 4 -alkoxy-carbonyl, C 3 -C 6 -alkenyl, C 3 -C 6 -alkynyl, C 1 -C 4 -alkoxy, C 1 -C 4 -alkoxy-C 1 -C 4 -alkylamino, C 1 -C 4 -alkylamino, di-(C 1 -C 4 -alkyl)amino, phenyl or the radical -NHOR 7 wherein R 7 represents C 1 -C 12 -alkyl which is unsubstituted or substituted by fluorine, chlorine, cyano, C 1 -C 4 -alkoxy, C 1 -C 4 -alkylthio, C 1 -C 4 -alkylsulfinyl, C 1 -C 4 -alkylsulfonyl, C 1 -C 4 -alkylcarbonyl, C 1 -C 4 -alkoxy-carbonyl, C 1 -C 4 -alkylamino-carbonyl or di-(C 1 -C 4 -alkyl)-amino-carbonyl), or represents C 3 -C 6 -alkenyl which is unsubstituted or substituted by fluorine, chlorine or bromine, C 3 -C 6 -alkynyl, C 3 -C 6 -cycloalkyl, C 3 -C 6 -cycloalkyl-C 1 -C 2 -alkyl, phenyl-C 1 -C 2 -alkyl which is unsubstituted or substituted by fluorine, chlorine, nitro, cyano, C 1 -C 4 -alkyl, C 1 -C 4 -alkoxy or C 1 -C 4 -alkoxy-carbonyl), or represents benzhydryl, or represents phenyl which is unsubstituted or substituted by fluorine, chlorine, nitro, cyano, C 1 -C 4 -alkyl, trifluoromethyl, C 1 -C 4 -alkoxy, C 1 -C 2 -fluoroalkoxy, C 1 -C 4 -alkylthio, trifluoromethylthio or C 1 -C 4 -alkoxy-carbonyl, R 4 and/or R 5 furthermore represent phenyl or phenoxy, or represent C 1 -C 4 -alkylcarbonylamino, C 1 -C 4 -alkoxycarbonyl-amino, C 1 -C 4 -alkylamino-carbonyl-amino, di-(C 1 -C 4 -alkyl)-amino-carbonylamino, or the radical -CO-R 8 wherein R 8 represents C 1 -C 6 -alkyl, C 1 -C 6 -alkoxy, C 3 -C 6 -cycloalkoxy, C 3 -C 6 -alkenyloxy, C 1 -C 4 -alkylthio, C 1 -C 4 -alkylamino, C 1 -C 4 -alkoxyamino, C 1 -C 4 -alkoxy-C 1 -C 4 -alkyl-amino or di-(C 1 -C 4 -alkyl)-amino which are unsubstituted or substituted by halogen selected from the group consisting of fluorine and chlorine, R 4 and/or R 5 furthermore represent trimethylsilyl, thiazolinyl, C 1 -C 4 -alkylsulfonyloxy, di-(C 1 -C 4 -alkyl)-aminosulfonylamino or the radical -CH=N-R 9 wherein R 9 represents C 1 -C 6 -alkyl which is unsubstituted or substituted by fluorine, chlorine, cyano, carboxyl, C 1 -C 4 -alkoxy, C 1 -C 4 -alkylthio, C 1 -C 4 -alkylsulfinyl or C 1 -C 4 -alkylsulfonyl, or represents benzyl which is unsubstituted or substituted by fluorine or chlorine, or represents C 3 -C 6 -alkenyl or C 3 -C 6 -alkynyl, each of which is unsubstituted or substituted by fluorine or chlorine, or represents phenyl which is unsubstituted or substituted by fluorine, chlorine, bromine, C 1 -C 4 -alkyl, C 1 -C 4 -alkoxy, trifluoromethyl, trifluoromethoxy or trifluoromethylthio, or represents unsubstituted or halogen substituted C 1 -C 6 -alkoxy, C 3 -C 6 -alkenoxy, C 3 -C 6 -alkynoxy or benzyloxy, wherein the halogen is selected from the group consisting of fluorine and chlorine, or represents amino, C 1 -C 4 -alkylamino, di-(C 1 -C 4 -alkyl)-amino, phenylamino, C 1 -C 4 -alkyl-carbonylamino, C 1 -C 4 -alkoxy-carbonyl amino or C 1 -C 4 -alkyl-sulfonyl amino, or represents phenylsulfonylamino which is unsubstituted or substituted by fluorine, chlorine, bromine or methyl, furthermore R 3 represents the radical wherein R 10 represents hydrogen or C 1 -C 4 -alkyl, wherein R 11 and R 12 are identical or different and represent hydrogen, fluorine, chlorine, bromine, nitro, cyano, C 1 -C 4 -alkyl which is unsubstituted or substituted by halogen selected from the group consisting of fluorine and chlorine, C 1 -C 4 -alkoxy which is unsubstituted or substituted by halogen selected from the group consisting of fluorine and chlorine, carboxyl, C 1 -C 4 -alkoxycarbonyl, dimethylaminocarbonyl, C 1 -C 4 -alkylsulfonyl or di-(C 1 -C 4 -alkyl)-aminosulfonyl; furthermore R 3 represents the radical wherein R 13 and R 14 are identical or different and represent hydrogen, fluorine, chlorine, bromine, nitro, cyano, C 1 -C 4 -alkyl which is unsubstituted or substituted by halogen selected from the group consisting of fluorine and chlorine, or C 1 -C 4 -alkoxy which is unsubstituted or substituted by halogen selected from the group consisting of fluorine and chlorine; furthermore R 3 represents the radical wherein R 15 and R 16 are identical or different and represent hydrogen, fluorine, chlorine, bromine, nitro, cyano, C 1 -C 4 -alkyl which is unsubstituted or substituted by halogen selected from the group consisting of fluorine and chlorine, C 1 -C 4 -alkoxy which is unsubstituted or substituted by halogen selected from the group consisting of fluorine and chlorine, or represent C 1 -C 4 -alkylthio, C 1 -C 4 -alkylsulfinyl or C 1 -C 4 -alkylsulfonyl which are unsubstituted or substituted by halogen selected from the group consisting of fluorine and chlorine, or represent aminosalfonyl, mono-(C 1 -C 4 -alkyl)-aminosulfonyl, di-(C 1 -C 4 -alkyl)-aminosulfonyl or C 1 -C 4 -alkoxycarbonyl or dimethylaminocarbonyl; furthermore R 3 represents the radical wherein R 17 and R 18 are identical or different and represent hydrogen, fluorine, chlorine, bromine, C 1 -C 4 -alkyl which is unsubstituted or substituted by halogen selected from the group consisting of fluorine and bromine, C 1 -C 4 -alkoxy which is unsubstituted or substituted by halogen selected from the group consisting of fluorine and chlorine, C 1 -C 4 -alkylthio, C 1 -C 4 -alkylsulfinyl or C 1 -C 4 -alkylsulfonyl which are unsubstituted or substituted by halogen selected from the group consisting of fluorine and chlorine, or represent di-(C 1 -C 4 -alkyl)-aminosulphonyl; furthermore R 3 represents the radical wherein R 19 and R 20 are identical or different and represent hydrogen, fluorine, chlorine, bromine, cyano, nitro, C 1 -C 4 -alkyl which is unsubstituted or substituted by halogen selected from the group consisting of fluorine and chlorine, C 1 -C 4 -alkoxy which is unsubstituted or substituted by halogen selected from the group consisting of fluorine and chlorine, C 1 -C 4 -alkylthio, C 1 -C 4 -alkylsulfinyl or C 1 -C 4 -alkysulfonyl which is unsubstituted or substituted by halogen selected from the group consisting of fluorine and chlorine, di-(C 1 -C 4 -alkylyaminosulfonyl, C 1 -C 4 -alkoxy-carbonyl or dimethylaminocarbonyl, and A represents oxygen, sulfur or the group N-Z 1 , wherein Z 1 represents hydrogen, C 1 -C 4 -alkyl which is unsubstituted or substituted by fluorine, chlorine, bromine, or cyano, C 3 -C 6 -cycloalkyl, benzyl, phenyl which is unsubstituted or substituted by fluorine, chlorine, bromine or nitro, C 1 -C 4 -alkylcarbonyl, C 1 -C 4 -alkoxy-carbonyl or di-(C 1 -C 4 -alkyl)-amino-carbonyl; furthermore R 3 represents the radical wherein R 21 and R 22 are identical or different and represent hydrogen, C 1 -C 4 -alkyl, halogen, C 1 -C 4 -alkoxycarbonyl, C 1 -C 4 -alkoxy or C 1 -C 4 -halogenoalkoxy, Y 1 represents sulfur or the group N-R 23 , wherein R 23 represents hydrogen or C 1 -C 4 -alkyl; furthermore R 3 represents the radical wherein : R 24 represents hydrogen, C 1 -C 4 -alkyl, benzyl, pyridyl, quinolinyl or phenyl, R 25 represents hydrogen, halogen, cyano, nitro, C 1 -C 4 -alkyl which is unsubstituted or substituted by halogen selected from the group consisting of fluorine and chlorine, C 1 -C 4 -alkoxy which is unsubstituted or substituted by halogen selected from the group consisting of fluorine and chlorine, dioxolanyl or C 1 -C 4 -alkoxy-carbonyl, and R 26 represents hydrogen, halogen or C 1 -C 4 -alkyl; furthermore R 3 represents a compound selected from the group consisting of under pH controlled conditions with a base, in such a way that the base is added to the reaction mixture in an amount such that the pH of the mixture attained from 5 to 9, to produce a salt thereof, a final product of the general formula (IV) wherein R 1 , R 2 , and R 3 are as defined above, and M represents an alkali or alkaline earth metal, or protonated ammonia derivative. The process of Claim 1 which is carried out at a temperature of from about -20°C to about 120°C. The process of Claim 1 which is carried out at a temperature of from about 0°C to about 45°C. The process of Claim 1 wherein the base is selected from the group consisting of sodium hydroxide, potassium hydroxide, ammonia, or aqueous mixtures thereof. The process of Claim 1 wherein 4,5-dihydro-3-methoxy-4-methyl-5-oxo-N-[[2-(trifluoromethoxy)phenyl]sulfonyl]-1 H-1,2,4-triazole-1-carboxamide (MSU) is converted to a salt thereof. The process of Claim 1, wherein 2-[[[(4,5-dihydro-4-methyl-5-oxo-3-propoxy-1H-1,2,4-triazol-1-yl)carbonyl]amino]sulfonyl]benzoic acid methyl ester is converted to a salt thereof. The process of Claim 5 further comprising the step of isolating the MSU salt thereof as a monohydrate.

Inventors: DESAI VIJAY C, JELICH KLAUS DR, KULKARNI SHEKHAR V, PRASAD VIDYANATHA A, RIVADENEIRA ERIC DR, DESAI, VIJAY C., JELICH, KLAUS, DR., KULKARNI, SHEKHAR V., PRASAD, VIDYANATHA A., RIVADENEIRA, ERIC, DR.
Applicants: BAYER AG, BAYER CORPORATION
Application year: 2000
Main classification: C07D249
IPC codes: C07D249