Process for preparing substituted N-carbamoyl-Tetrazolinones

A process for preparing a substituted N-carbamoyl-tetrazolinone of the formula ##STR23## in which R.sup.1 represents alkyl which is optionally substituted by carboxyl, cyano, carbamoyl, halogen, C.sub.1 -C.sub.6 -alkoxy, C.sub.1 -C.sub.6 -alkylthio, C.sub.1 -C.sub.6 -alkylsulphinyl or C.sub.1 -C.sub.6 -alkylsulphonyl and which has from 1 to 10 carbon atoms, represents alkenyl or alkinyl which are in each case optionally substituted by carboxyl, cyano, carbamoyl or halogen and which in each case have from 2 to 10 carbon atoms, represents cycloalkyl or cycloalkylalkyl which are in each case optionally substituted by carboxyl, cyano, carbamoyl, halogen, C.sub.1 -C.sub.4 -alkyl or C.sub.1 -C.sub.4 -alkoxy-carbonyl and which in each case have from 3 to 8 carbon atoms in the cycloalkyl moiety and optionally from 1 to 4 carbon atoms in the alkyl moiety, or represents phenyl, naphthyl, phenyl-C.sub.1 -C.sub.4 -alkyl, naphthyl-C.sub.1 -C.sub.4 -alkyl, furyl, benzofuryl, tetrahydrofuryl, furylmethyl, tetrahydrofurylmethyl, thienyl, benzothienyl, tetrahydrothienyl, thienylmethyl, tetrahydrothienylmethyl, pyrrolyl, indolyl, oxazolyl, benzoxazolyl, oxazolylmethyl, isoxazolyl, isoxazolylmethyl, thiazolyl, benzothiazolyl, thiazolylmethyl, pyrazolyl, oxadiazolyl, oxadiazolylmethyl, thiadiazolyl, thiadiazolylmethyl, triazolyl, pyridyl, quinolinyl, isoquinolinyl, pyridylmethyl, pyrazinyl, pyridazinyl, pyrimidinyl, quinazolinyl, quinoxalinyl, pyrimidinylmethyl, triazinyl or triazinylmethyl which are in each case optionally substituted by carboxyl, cyano, carbamoyl, nitro, amino, hydroxyl or halogen, or by C.sub.1 -C.sub.4 -alkyl, C.sub.1 -C.sub.4 -alkoxy, C.sub.1 -C.sub.4 -alkylthio, C.sub.1 -C.sub.4 -alkylsulphinyl, C.sub.1 -C.sub.4 -alkylsulphonyl, di-(C.sub.1 -C.sub.4 -alkyl)amino, C.sub.1 -C.sub.4 -alkylsulphonylamino, di-(C.sub.1 -C.sub.4 -alkyl)aminosulphonyl, C.sub.1 -C.sub.4 -alkyl-carbonyl, C.sub.1 -C.sub.4 -alkyl-carbonylamino, C.sub.1 -C.sub.4 -alkoxy-carbonyl, di-(C.sub.1 -C.sub.4 -alkylamino)-carbonyl, C.sub.1 -C.sub.4 -alkylenedioxy, phenyl or phenoxy (which are in each case optionally substituted by fluorine and/or chlorine),

• R.sup.2 represents alkyl, alkenyl, alkinyl or alkoxy which are in each case optionally substituted by cyano or halogen and which in each case have up to 6 carbon atoms, and
• R.sup.3 represents alkyl which is optionally substituted by cyano or halogen and which has from 1 to 6 carbon atoms, represents alkenyl or alkinyl which are in each case optionally substituted by cyano or halogen and which in each case have from 2 to 6 carbon atoms, represents cycloalkyl or cycloalkylalkyl which are in each case optionally substituted by cyano, halogen or C.sub.1 -C.sub.4 -alkyl and which in each case have from 3 to 6 carbon atoms in the cycloalkyl moiety and optionally from 1 to 2 carbon atoms in the alkyl moiety, or represents phenyl or phenyl-C.sub.1 -C.sub.2 -alkyl which are in each case optionally substituted by cyano, nitro or halogen, or by C.sub.1 -C.sub.4 -alkyl, C.sub.1 -C.sub.4 -alkoxy, C.sub.1 -C.sub.4 -alkylthio, C.sub.1 -C.sub.4 -alkylsulphinyl, C.sub.1 -C.sub.4 -alkylsulphonyl, di-(C.sub.1 -C.sub.4 -alkyl)amino, C.sub.1 -C.sub.4 -alkylsulphonylamino, di-(C.sub.1 -C.sub.4 -alkyl)aminosulphonyl, C.sub.1 -C.sub.4 -alkyl-carbonyl or C.sub.1 -C.sub.4 -alkoxy-carbonyl (which are in each case optionally substituted by fluorine and/or chlorine),
• or, together with R.sup.2, represents alkanediyl having 2 to 6 carbon atoms,
• which comprises reacting an optionally isolated metal salt of the formula ##STR24## in which R.sup.1 has the abovementioned meaning, and
• M represents an alkali metal equivalent, an alkaline earth metal equivalent or an earth metal equivalent, with a carbamoyl halide of the formula ##STR25## in which R.sup.2 and R.sup.3 have the abovementioned meaning, and
• X represents halogen,
• in the presence of a diluent, at temperatures of between 0.degree. C. and 200.degree. C., and the O-carbamoylation product of the formula (Ia) ##STR26## which is formed under these circumstances as a byproduct is either isomerized by heating at the upper range of the above mentioned temperature interval to form the desired product of the formula (I) or is converted by hydrolysis into water-soluble, and thus readily separable, components.

A process for preparing a substituted N-carbamoyl-tetrazolinone of the formula ##STR27## in which R.sup.1 represents alkyl which is optionally substituted by carboxyl, cyano, carbamoyl, halogen, C.sub.1 -C.sub.6 -alkoxy, C.sub.1 -C.sub.6 -alkylthio, C.sub.1 -C.sub.6 -alkylsulphinyl or C.sub.1 -C.sub.6 -alkylsulphonyl and which has from 1 to 10 carbon atoms, represents alkenyl or alkinyl which are in each case optionally substituted by carboxyl, cyano, carbamoyl or halogen and which in each case have from 2 to 10 carbon atoms, represents cycloalkyl or cycloalkylalkyl which are in each case optionally substituted by carboxyl, cyano, carbamoyl, halogen, C.sub.1 -C.sub.4 -alkyl or C.sub.1 -C.sub.4 -alkoxy-carbonyl and which in each case have from 3 to 8 carbon atoms in the cycloalkyl moiety and optionally from 1 to 4 carbon atoms in the alkyl moiety, or represents phenyl, naphthyl, phenyl-C.sub.1 -C.sub.4 -alkyl, naphthyl-C.sub.1 -C.sub.4 -alkyl, furyl, benzofuryl, tetrahydrofuryl, furylmethyl, tetrahydrofurylmethyl, thienyl, benzothienyl, tetrahydrothienyl, thienylmethyl, tetrahydrothienylmethyl, pyrrolyl, indolyl, oxazolyl, benzoxazolyl, oxazolylmethyl, isoxazolyl, isoxazolylmethyl, thiazolyl, benzothiazolyl, thiazolylmethyl, pyrazolyl, oxadiazolyl, oxadiazolylmethyl, thiadiazolyl, thiadiazolylmethyl, triazolyl, pyridyl, quinolinyl, isoquinolinyl, pyridylmethyl, pyrazinyl, pyridazinyl, pyrimidinyl, quinazolinyl, quinoxalinyl, pyrimidinylmethyl, triazinyl or triazinylmethyl which are in each case optionally substituted by carboxyl, cyano, carbamoyl, nitro, amino, hydroxyl or halogen, or by C.sub.1 -C.sub.4 -alkyl, C.sub.1 -C.sub.4 -alkoxy, C.sub.1 -C.sub.4 -alkylthio, C.sub.1 -C.sub.4 -alkylsulphinyl, C.sub.1 -C.sub.4 -alkylsulphonyl, di-(C.sub.1 -C.sub.4 -alkyl)amino, C.sub.1 -C.sub.4 -alkylsulphonylamino, di-(C.sub.1 -C.sub.4 -alkyl)aminosulphonyl, C.sub.1 -C.sub.4 -alkyl-carbonyl, C.sub.1 -C.sub.4 -alkyl-carbonylamino, C.sub.1 -C.sub.4 -alkoxy-carbonyl, di-(C.sub.1 -C.sub.4 -alkylamino)-carbonyl, C.sub.1 -C.sub.4 -alkylenedioxy, phenyl or phenoxy (which are in each case optionally substituted by fluorine and/or chlorine),

• R.sup.2 represents alkyl, alkenyl, alkinyl or alkoxy which are in each case optionally substituted by cyano or halogen and which in each case have up to 6 carbon atoms, and
• R.sup.3 represents alkyl which is optionally substituted by cyano or halogen and which has from 1 to 6 carbon atoms, represents alkenyl or alkinyl which are in each case optionally substituted by cyano or halogen and which in each case have from 2 to 6 carbon atoms, represents cycloalkyl or cycloalkylalkyl which are in each case optionally substituted by cyano, halogen or C.sub.1 -C.sub.4 -alkyl and which in each case have from 3 to 6 carbon atoms in the cycloalkyl moiety and optionally from 1 to 2 carbon atoms in the alkyl moiety, or represents phenyl or phenyl-C.sub.1 -C.sub.2 -alkyl which are in each case optionally substituted by cyano, nitro or halogen, or by C.sub.1 -C.sub.4 -alkyl, C.sub.1 -C.sub.4 -alkoxy, C.sub.1 -C.sub.4 -alkylthio, C.sub.1 -C.sub.4 -alkylsulphinyl, C.sub.1 -C.sub.4 -alkylsulphonyl, di-(C.sub.1 -C.sub.4 -alkyl)amino, C.sub.1 -C.sub.4 -alkylsulphonylamino, di-(C.sub.1 -C.sub.4 -alkyl)aminosulphonyl, C.sub.1 -C.sub.4 -alkyl-carbonyl or C.sub.1 -C.sub.4 -alkoxy-carbonyl (which are in each case optionally substituted by fluorine and/or chlorine),
• or, together with R.sup.2, represents alkanediyl having 2 to 6 carbon atoms,
• which comprises isomerizing a substituted carbamoyloxytetrazole of the formula ##STR28## in which R.sup.1, R.sup.2 and R.sup.3 have the abovementioned meanings,
• wherein compounds of the formula I are optionally present, to form the corresponding N-carbamoyl-tetrazolinones of the formula (I), where appropriate in the presence of a diluent and where appropriate in the presence of a reaction auxiliary wherein said reaction auxiliary is a basic organic nitrogen compound, iodine or an alkali metal iodide, at temperatures of between 50.degree. C. and 200.degree. C.

A process for preparing a substituted N-carbamoyl-tetrazolinone of the formula ##STR29## in which R.sup.1 represents alkyl which is optionally substituted by carboxyl, cyano, carbamoyl, halogen, C.sub.1 -C.sub.6 -alkoxy, C.sub.1 -C.sub.6 -alkylthio, C.sub.1 -C.sub.6 -alkylsulphinyl or C.sub.1 -C.sub.6 -alkylsulphonyl and which has from 1 to 10 carbon atoms, represents alkenyl or alkinyl which are in each case optionally substituted by carboxyl, cyano, carbamoyl or halogen and which in each case have from 2 to 10 carbon atoms, represents cycloalkyl or cycloalkylalkyl which are in each case optionally substituted by carboxyl, cyano, carbamoyl, halogen, C.sub.1 -C.sub.4 -alkyl or C.sub.1 -C.sub.4 -alkoxy-carbonyl and which in each case have from 3 to 8 carbon atoms in the cycloalkyl moiety and optionally from 1 to 4 carbon atoms in the alkyl moiety, or represents phenyl, naphthyl, phenyl-C.sub.1 -C.sub.4 -alkyl, naphthyl-C.sub.1 -C.sub.4 -alkyl, furyl, benzofuryl, tetrahydrofuryl, furylmethyl, tetrahydrofurylmethyl, thienyl, benzothienyl, tetrahydrothienyl, thienylmethyl, tetrahydrothienylmethyl, pyrrolyl, indolyl, oxazolyl, benzoxazolyl, oxazolylmethyl, isoxazolyl, isoxazolylmethyl, thiazolyl, benzothiazolyl, thiazolylmethyl, pyrazolyl, oxadiazolyl, oxadiazolylmethyl, thiadiazolyl, thiadiazolylmethyl, triazolyl, pyridyl, quinolinyl, isoquinolinyl, pyridylmethyl, pyrazinyl, pyridazinyl, pyrimidinyl, quinazolinyl, quinoxalinyl, pyrimidinylmethyl, triazinyl or triazinylmethyl which are in each case optionally substituted by carboxyl, cyano, carbamoyl, nitro, amino, hydroxyl or halogen, or by C.sub.1 -C.sub.4 -alkyl, C.sub.1 -C.sub.4 -alkoxy, C.sub.1 -C.sub.4 -alkylthio, C.sub.1 -C.sub.4 -alkylsulphinyl, C.sub.1 -C.sub.4 -alkylsulphonyl, di-(C.sub.1 -C.sub.4 -alkyl)amino, C.sub.1 -C.sub.4 -alkylsulphonylamino, di-(C.sub.1 -C.sub.4 -alkyl)aminosulphonyl, C.sub.1 -C.sub.4 -alkyl-carbonyl, C.sub.1 -C.sub.4 -alkyl-carbonylamino, C.sub.1 -C.sub.4 -alkoxy-carbonyl, di-(C.sub.1 -C.sub.4 -alkylamino)-carbonyl, C.sub.1 -C.sub.4 -alkylenedioxy, phenyl or phenoxy (which are in each case optionally substituted by fluorine and/or chlorine),

• R.sup.2 represents alkyl, alkenyl, alkinyl or alkoxy which are in each case optionally substituted by cyano or halogen and which in each case have up to 6 carbon atoms, and
• R.sup.3 represents alkyl which is optionally substituted by cyano or halogen and which has from 1 to 6 carbon atoms, represents alkenyl or alkinyl which are in each case optionally substituted by cyano or halogen and which in each case have from 2 to 6 carbon atoms, represents cycloalkyl or cycloalkylalkyl which are in each case optionally substituted by cyano, halogen or C.sub.1 -C.sub.4 -alkyl and which in each case have from 3 to 6 carbon atoms in the cycloalkyl moiety and optionally from 1 to 2 carbon atoms in the alkyl moiety, or represents phenyl or phenyl-C.sub.1 -C.sub.4 -alkyl which are in each case optionally substituted by cyano, nitro or halogen, or by C.sub.1 -C.sub.4 -alkyl, C.sub.1 -C.sub.4 -alkoxy, C.sub.1 -C.sub.4 -alkylthio, C.sub.1 -C.sub.4 -alkylsulphinyl, C.sub.1 -C.sub.4 -alkylsulphonyl, di-(C.sub.1 -C.sub.4 -alkyl)amino, C.sub.1 -C.sub.4 -alkylsulphonylamino, di-(C.sub.1 -C.sub.4 -alkyl)aminosulphonyl, C.sub.1 -C.sub.4 -alkyl-carbonyl or C.sub.1 -C.sub.4 -alkoxy-carbonyl (which are in each case optionally substituted by fluorine and/or chlorine),
• or, together with R.sup.2, represents alkanediyl having 2 to 6 carbon atoms,
• which comprises reacting a substituted carbamoyloxytetrazole of the formula ##STR30## in which R.sup.1, R.sup.2 and R.sup.3 have the abovementioned meanings,
• with water and/or an alcohol, optionally in the presence of an inert organic solvent and where appropriate in the presence of a reaction auxiliary wherein said reaction auxiliary is a basic organic nitrogen compound, iodine, or an alkali metal iodide at temperatures of between 10.degree. C. and 150.degree. C., and the products of the hydrolysis or the alcoholysis of the compounds of the formula (Ia) are separated off.