Process for the preparation of 1-4-disubstituted-5 (4H)-tetrazolinones

1,4-Disubstituted-5(4H)-tetrazolinones of the formula (I) ##STR1## wherein R.sup.1, R.sup.2 and R.sup.3 have the meanings given in the specification), which are known to be useful as herbicides, can be obtained in very good yields by reacting the corresponding 1-substituted-5(4H)-tetrazolinones with the corresponding carbamoyl chlorides in the presence of 4-dimethylaminopyridine.

The present invention relates to a novel process for the production of 
known 1,4-disubstituted-5(4H)-tetrazolinones which can be utilized, for 
example, as agricultural chemicals. 
Regarding the synthesis of tetrazolinones of the type of general formula 
(I) below, U.S. Pat. No. 4,618,365 discloses a process wherein a 
tetrazolinone of the general formula: 
##STR2## 
wherein M represents hydrogen or an alkali metal such as Li, Na or K is 
reacted with a carbomyl chloride. 
Concerning the above-mentioned reaction, when use is made, as M, of a 
hydrogen atom, it is preferably carried out in the presence of a suitable 
acid-acceptor such as pyridine, a trialkylamine, or the like. Further, in 
this reaction, use may be made, as suitable solvents, of acetone, 
acetonitrile, toluene, chloroform, and the like. 
However, such known process produces, in addition to the desired 
tetrazolinones, the isomeric compounds of the general formula (A): 
##STR3## 
(hereinafter referred to as "O-carbamoyl compounds") as by-products and 
the production rate of such by-products sometimes turns out to be as much 
as one third of the production rate of the desired compounds (FIGS. 1 to 
5). 
The O-carbamoyl compound by-products do not exhibit herbicidal activity as 
comparable to the desired N-carbamoyl tetrazolinones. Further, such 
O-carbamoyl compounds are chemically unstable, i.e. they are readily 
hydrolyzable by aqueous acids and alkali so that the separation and 
removal of O-carbamoyl compounds from the desired N-carbamoyl products (I) 
is difficult. 
Thus the known process has serious inherent defects, viz. with regard to 
reaction procedure and reaction efficiency. 
To solve the above-mentioned technical problem, there has now been found a 
process--with two process variants (a) and (b)--for selectively producing 
1,4-disubstituted-5(4H)-tetrazolinones of the general formula (I), 
##STR4## 
wherein R.sup.1 represents optionally substituted C.sub.1-12 alkyl, 
optionally substituted C.sub.3-8 cycloalkyl, optionally substituted 
C.sub.3-8 alkenyl, optionally substituted C.sub.3-8 alkynyl, or a group of 
the general formula 
##STR5## 
wherein Ar represents optionally substituted phenyl, optionally 
substituted naphthyl or an optionally substituted five- to seven-membered 
heterocyclic ring, 
R.sup.4 represents hydrogen or C.sub.1-4 alkyl, and 
n is 0, 1, 2, 3 or 4, 
R.sup.2 and R.sup.3 each represents, independently, C.sub.1-8 alkyl, 
C.sub.1-6 haloalkyl, C.sub.2-6 alkoxyalkyl, C.sub.2-6 alkylthioalkyl, 
C.sub.2-6 alkenyl, C.sub.2-6 haloalkenyl, C.sub.3-6 alkynyl, C.sub.1-4 
alkoxy, C.sub.1-4 haloalkoxy, C.sub.3-8 cycloalkyl, optionally substituted 
phenyl or optionally substituted aralkyl, or 
R.sup.2 and R.sup.3 together with the adjacent N atom may form a ring, 
which process comprises 
(a) reacting a compound of the general formula (II), 
##STR6## 
wherein R.sup.1 has the same meaning as mentioned above, with a compound 
of the general formula (III) 
##STR7## 
wherein R.sup.2 and R.sup.3 have the same meaning as mentioned above, in 
the presence of 4-dimethylamino-pyridine and optionally in the presence of 
a diluent and of an additional acid-binder, or 
(b) reacting a compound of the above-mentioned general formula (II) with a 
compound of the above-mentioned general formula (III), optionally in the 
presence of a diluent and of an acid-binder other than 
4-dimethylamino-pyridine, to obtain a mixture consisting of a 
tetrazolinone of the above-mentioned general formula (I) and a compound of 
the general formula (IV), 
##STR8## 
wherein R.sup.1, R.sup.2 and R.sup.3 have the same meanings as mentioned 
above, (first step), followed by reacting said obtained mixture with 
4-dimethyl-amino-pyridine, optionally in the presence of a diluent, 
thereby effecting conversion of the compound(s) of formula (IV) to the 
desired isomeric compound(s) of the formula (I) by a "carbamoyl-migration" 
(i.e. 1,3-shift of the carbamoyl group, from O to N) (second step). 
The process according to the present invention has surprisingly been found 
to be able selectively to prepare the desired tetrazolinones of general 
formula (I) in high yield, either by reacting a compound of general 
formula (II) with a compound of general formula (III) in the presence of 
4-dimethylamino-pyridine (that has not been employed in the prior art 
processes), or by reacting the above-mentioned starting materials (II) and 
(III) according to a conventional procedure, followed by reacting the 
resulting mixture of isomeric compounds of formulas (I) and (IV) with 
4-dimethylamino-pyridine, thereby effecting a 1,3-migration of the 
carbamoyl substituent. 
The 4-dimethylamino-pyridine to be employed in the process according to the 
present invention can be used as acid-acceptor and catalyst, or as 
catalyst together with another acid-acceptor, as discussed hereinbelow. 
The process according to the present invention can be utilized for the 
prepartion of the many tetrazolinones of general formula (I) and has been 
found to be most suitable for their production on an industrial scale. 
A preferred group of 1,4-disubstituted-5(4H)-tetrazolinones, to be produced 
according to the present invention, are those compounds of formula (I), 
wherein 
R.sup.1 represents C.sub.1-12 alkyl, C.sub.1-6 haloalkyl, C.sub.2-8 
alkoxyalkyl, C.sub.2-8 alkylthioalkyl, C.sub.3-8 cycloalkyl, C.sub.3-8 
alkenyl, C.sub.3-8 haloalkenyl, C.sub.3-8 alkynyl, or a group of the 
general formula 
##STR9## 
wherein Ar represents unsubstituted phenyl, or a phenyl group having a 
substituent or substituents optionally selected from the group consisting 
of halogen, C.sub.1-4 alkyl, C.sub.1-4 haloalkyl, C.sub.1-4 alkoxy, 
C.sub.1-4 haloalkoxy, C.sub.1-4 alkylthio, C.sub.1-4 haloalkylthio, 
C.sub.1-4 alkoxy-carbonyl, carboxy, optionally substituted phenoxy, 
optionally substituted heterocyclyl-oxy, methylene dioxy, halomethylene 
dioxy, ethylene dioxy, haloethylene dioxy, cyano, nitro and --NR.sup.5 
R.sup.6 ; or 
Ar represents unsubstituted naphthyl, or a substituted naphthyl group 
having a substituent or substituents optionally selected from the group 
consisting of halogen, C.sub.1-4 alkyl, C.sub.1-4 haloalkyl, C.sub.1-4 
alkoxy, C.sub.1-4 4 haloalkoxy, C.sub.1-4 alkylthio, C.sub.1-4 
haloalkylthio, C.sub.1-4 alkoxy-carbonyl, carboxyl, optionally substituted 
phenoxy, optionally substituted heterocyclyl-oxy, methylene dioxy, 
halomethylene dioxy, ethylene dioxy, haloethylene dioxy, cyano, nitro and 
--NR.sup.5 R.sup.6 ; or 
Ar represents a five- to seven-membered heterocyclic ring or their 
benzologues or their substituted derivatives having a substituent or 
substituents optionally selected from the group consisting of halogen, 
C.sub.1-4 alkyl, C.sub.1-4 haloalkyl, C.sub.1-4 alkoxy, C.sub.1-4 
haloalkoxy, C.sub.1-4 alkylthio, C.sub.1-4 haloalkylthio C.sub.1-4 
alkoxy-carbonyl, carboxy, optionally substituted phenoxy, optionally 
substituted heterocyclyl-oxy, methylene dioxy, halomethylene dioxy, 
ethylene dioxy, haloethylene dioxy, cyano, nitro and --NR.sup.5 R.sup.6 ; 
R.sup.4 represents hydrogen or C.sub.1-4 alkyl, 
R.sup.5 and R6 may be the same or different and represent hydrogen or 
C.sub.1-4 alkyl, and 
n is 0, 1, 2 or 3; and 
R.sup.2 and R.sup.3 each independently represents methyl, ethyl, n-propyl, 
isopropyl, n-(sec-,iso-, or tert-)butyl, n-pentyl, n-hexyl, 
trifluoromethyl, difluoromethyl, 2-chloroethyl, 2-fluoroethyl, 
2,2,2-trifluoroethyl, 3-fluoropropyl, perfluoropropyl, perfluorohexyl, 
2-methoxyethyl, ethoxymethyl, 2-ethoxyethyl, 2-propoxyethyl, 
2-methylthioethyl, 3-methylthiopropyl, 2-ethylthioethyl, allyl, 2-(3-, 
4-)butenyl, hexenyl, 3-chloroallyl, propargyl, methoxy, ethoxy, n-propoxy, 
isopropoxy, 3-chloroallyloxy, cyclopropyl, cyclopentyl, cyclohexyl, 
optionally substituted phenyl or benzyl, (wherein said substituents may be 
optionally selected from the group consisting of fluorine, chlorine, 
bromine, methyl, ethyl, n-propyl, isopropyl, tert-butyl, trifluoromethyl, 
methoxy, ethoxy, isopropoxy, difluoromethoxy, trifluoromethoxy, 
methylthio, ethoxy, isopropoxy, difluoromethoxy, trifluoromethoxy, 
methylthio, ethylthio, trifluoromethylthio, 2,2,2-trifluoroethylthio, 
cyano and nitro), or 
R.sup.2 and R.sup.3 together with the adjacent nitrogen atom may form 
piperidino, 2,6-dimethylpiperidino, morpholino, 2,6-dimethylmorpholino, 
thiomorpholino, 2,3-dihydroindolyl or perhydroindolyl. 
A particularly preferred group of 1,4-disubstituted-5(4H)-tetrazolinones, 
to be produced according to the present invention, are those compounds of 
formula (I), wherein 
R.sup.1 represents methyl, ethyl, n-propyl, isopropyl, n-(sec-, iso-, or 
tert-)butyl, n-hexyl, trifluoromethyl, difluoromethyl, 
chlorodifluoromethyl, 2,2,2-trifluoroethyl, perfluoropropyl, 
perfluorohexyl, methoxyethyl, ethoxymethyl, ethoxyethyl, propoxyethyl, 
butoxyethyl, methylthioethyl, methylthiomethyl, methylthiopropyl, 
ethylthiomethyl, ethylthioethyl, propylthioethyl, butylthioethyl, 
cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, allyl, chloroallyl, 
butenyl, hexenyl, propargyl, or a group of the general formula 
##STR10## 
wherein Ar represents unsubstituted phenyl or a phenyl group having a 
substituent or substituents optionally selected from the group consisting 
of fluorine, chlorine, bromine, methyl, ethyl, propyl, butyl, 
difluoromethyl, chlorodifluoromethyl, trifluoromethyl, 
2,2,2-trifluoroethyl, methoxy, ethoxy, propoxy, butoxy, difluoromethoxy, 
chlorodifluoromethoxy, trifluoromethoxy, 2,2,2-trifluoroethoxy, 
methylthio, ethylthio, propylthio, difluoromethylthio, 
trifluoromethylthio, 2,2,2-trifluoroethylthio, dimethylamino, 
diethylamino, methoxycarbonyl, ethoxycarbonyl, butoxycarbonyl, carboxy, 
phenoxy, optionally substituted heterocyclyl-oxy, (wherein the hetero ring 
of said heterocyclyl-oxy is selected from the group consisting of 
imidazole, pyrazole, triazole, oxazole, isoxazole, benzoxazole, thiazole, 
isothiazole, benzothiazole, oxadiazole, thiadiazole, tetrazole, pyridine, 
quinoline, isoquinoline, pyrimidine, pyridazine, pyrazine, quinazoline, 
quinoxaline, triazine, thiophene, benzothiophene, furan and benzofuran), 
methylenedioxy, difluoromethylenedioxy, ethylenedioxy, 
chlorodifluoroethylenedioxy, difluoroethylenedioxy, 
trifluoroethylenedioxy, tetrafluoroethylenedioxy, cyano and nitro; or 
Ar represents unsubstituted naphthyl or a substituted naphthyl group having 
a substituent or substituents optionally selected from the group 
consisting of fluorine, chlorine, bromine, methyl, ethyl, propyl, butyl, 
difluoromethyl, chlorodifluoromethyl, trifluoromethyl, 
2,2,2-trifluoroethyl, methoxy, ethoxy, propoxy, butoxy, difluoromethoxy, 
chlorodifluoromethoxy, trifluoromethoxy, 2,2,2-trifluoroethoxy, 
methylthio, ethylthio, propylthio, difluoromethylthio, 
trifluoromethylthio, 2,2,2-trifluoroethylthio, dimethylamino, 
diethylamino, methoxycarbonyl, ethoxycarbonyl, butoxycarbonyl, carboxy, 
phenoxy, optionally substituted heterocyclyl-oxy, (wherein the hetero ring 
of said heterocyclyl-oxy is selected from the group consisting of 
imidazole, pyrazole, triazole, oxazole, isoxazole, benzoxazole, thiazole, 
isothiazole, benzothiazole, oxadiazole, thiadiazole, tetrazole, pyridine, 
quinoline, isoquinoline, pyrimidine, pyridazine, pyrazine, quinazoline, 
quinoxaline, triazine, thiophene, benzothiophene, furan and benzofuran), 
methylenedioxy, difluoromethylenedioxy, ethylenedioxy, 
chlorodifluoroethylenedioxy, difluoroethylenedioxy, 
trifluoroethylenedioxy, tetrafluoroethylenedioxy, cyano and nitro; or 
Ar represents an unsubstituted or substituted five- or six-membered 
heterocyclic ring and their benzologues, wherein said hetero ring is 
selected from the group consisting of imidazole, pyrazole, triazole, 
oxazole, isoxazole, benzoxazole, thiazole, isothiazole, benzothiazole, 
oxadiazole, thiadiazole, tetrazole, pyridine, quinoline, isoquinoline, 
pyrimidine, pyridazine, pyrazine, quinazoline, quinoxaline, triazine, 
thiophene, and furan), having a substituent or substituents optionally 
selected from the group consisting of fluorine, chlorine, bromine, methyl, 
ethyl, propyl, butyl, difluoromethyl, chlorodifluoromethyl, 
trifluoromethyl, 2,2,2-trifluoroethyl, methoxy, ethoxy, propoxy, butoxy, 
difluoromethoxy, chlorodifluoromethoxy, trifluoromethoxy, 
2,2,2-trifluoroethoxy, methylthio, ethylthio, propylthio, 
difluoromethylthio, trifluoromethylthio, 2,2,2-trifluoroethylthio, 
dimethylamino, diethylamino, methoxycarbonyl, ethoxycarbonyl, 
butoxycarbonyl, carboxy, phenoxy, optionally substituted heterocyclyl-oxy, 
(wherein the hetero ring of said heterocyclyl-oxy is selected from the 
group consisting of imidazole, pyrazole, triazole, oxazole, isoxazole, 
benzoxazole, thiazole, isothiazole, benzothiazole, oxadiazole, 
thiadiazole, tetrazole, pyridine, quinoline, isoquinoline, pyrimidine, 
pyridazine, pyrazine, quinazoline, quinoxaline, triazine, thiophene, 
benzothiophene, furan and benzofuran), methylenedioxy, 
difluoromethylenedioxy, ethylenedioxy, chlorodifluoroethylenedioxy, 
difluoroethylenedioxy, trifluoroethylenedioxy, tetrafluoroethylenedioxy, 
cyano and nitro, 
R.sup.4 represents hydrogen or methyl, 
n is 0, 1 or 2, and 
R.sup.2 and R.sup.3 each independently represents methyl, ethyl, n-propyl, 
isopropyl, n-(iso-, sec-, tert-)butyl, trifluoromethyl, difluoromethyl, 
2-methoxyethyl, ethoxymethyl, 2-ethoxyethyl, 2-methylthioethyl, allyl, 
2-butenyl, 3-chloroallyl, propargyl, methoxy, ethoxy, n-propoxy, 
cyclopropyl, cyclopentyl, cyclohexyl, or optionally substituted phenyl or 
benzyl, having a substituent or substituents selected from the group 
consisting of fluorine, chlorine, bromine, methyl, ethyl, n-propyl, 
isopropyl, tert-butyl, trifluoromethyl, methoxy, ethoxy, trifluoromethoxy, 
methylthio, cyano and nitro, or 
R.sup.2 and R.sup.3 together with the adjacent nitrogen atom may form 
piperidino, morpholino, thiomorpholino, 2,3-dihydroindolyl or 
perhydroindolyl. 
The compounds represented by the general formula (II) and employed as 
starting materials in the processes according to the present invention can 
be obtained by the processes disclosed in J. Am. Chem. Soc., vol. 81, pp. 
3076-3079 (1959); J. Org. Chem. vol. 45, pp. 5130-5136 (1980) and Japanese 
Patent Application No. Hei 5-212153. 
The compounds represented by the general formula (III) are well known. 
The above-mentioned general definitions of radicals or explanations, or 
those mentioned as preferred, are applicable in a corresponding manner to 
the end products (I) and to the starting materials (II) and (III) and 
"intermediates" (IV). These definitions of radicals may be combined with 
one another, as desired. 
Representative 1-substituted-5(4H)-tetrazolinones of the formula (II) 
include the following compounds: 
1-phenyl-5(4H)-tetrazolinone, 
1-(3,5-dimethylphenyl)-5(4H)-tetrazolinone, 
1-(2-chlorophenyl)-5(4H)-tetrazolinone, 
1-(2-chloro-3-methylphenyl)-5(4H)-tetrazolinone, 
1-(2-chloro-4-trifluoromethylphenyl)-5(4H)-tetrazolinone, 
1-methyl-5(4H)-tetrazolinone, 
1-benzyl-5(4H)-tetrazolinone, 
1-(3,4-tetrafluoroethylenedioxyphenyl)-5(4H)-tetrazolinone, 
1-(2-chloro-5-pyridylmethyl)-5(4H)-tetrazolinone, 
1-ethyl-5(4H)-tetrazolinone, 
1-n-propyl-5(4H)-tetrazolinone, 
1-isopropyl-5(4H)-tetrazolinone, 
1-tert-butyl-5(4H)-tetrazolinone, 
1-cyclopropyl-5(4H)-tetrazolinone, 
1-cyclopentyl-5(4H)-tetrazolinone, 
1-cyclohexyl-5(4H)-tetrazolinone, 
1-(2,2,2-trifluoroethyl)-5(4H)-tetrazolinone, 
1-(2-methoxyethyl)-5(4H)-tetrazolinone, 
1-(2-ethylthioethyl)-5(4H)-tetrazolinone, 
1-(2-methylthioethyl)-5(4H)-tetrazolinone, 
1-allyl-5(4H)-tetrazolinone, 
1-(3-chloroallyl)-5(4H)-tetrazolinone, 
1-propargyl-5(4H)-tetrazolinone, 
1-(2-fluorophenyl)-5(4H)-tetrazolinone, 
1-(3-chlorophenyl)-5(4H)-tetrazolinone, 
1-(3-trifluoromethylphenyl)-5(4H)-tetrazolinone, 
1-(4-trifluoromethylphenyl)-5(4H)-tetrazolinone, 
1-(4-chlorophenyl)-5(4H)-tetrazolinone, 
1-(2-methylphenyl)-5(4H)-tetrazolinone, 
1-(3-methylphenyl)-5(4H)-tetrazolinone, 
1-(4-methylphenyl)-5(4H)-tetrazolinone, 
1-(2-methoxyphenyl)-5(4H)-tetrazolinone, 
1-(4-methoxyphenyl)-5(4H)-tetrazolinone, 
1-(4-trifluoromethoxyphenyl)-5(4H)-tetrazolinone, 
1-(4-trifluoromethylthiophenyl)-5(4H)-tetrazolinone, 
1-(3-propylphenyl)-5(4H)-tetrazolinone, 
1-(4-tert-butylphenyl)-5(4H)-tetrazolinone, 
1-(2,4-dichlorophenyl)-5(4H)-tetrazolinone, 
1-(2,6-dichlorophenyl)-5(4H)-tetrazolinone, 
1-(2-chloro-6-methylphenyl)-5(4H)-tetrazolinone, 
1-(3-chloro-4-trifluoromethylphenyl)-5(4H)-tetrazolinone, 
1-4-(2,4-dichlorophenoxy)phenyl!-5(4H)-tetrazolinone, 
1-4-(2-chloro-4-trifluoromethylphenoxy)phenyl!-5(4H)-tetrazolinone, 
1-4-(2,6-dichloro-4-trifluoromethylphenoxy)phenyl!-5(4H)-tetrazolinone, 
1-(3-phenoxyphenyl)-5(4H)-tetrazolinone, 
1-(3,4-difluoromethylenedioxyphenyl)-5(4H)-tetrazolinone, 
1-4-(3,5-dichloropyridin-2-yloxy)-phenyl!-5(4H)-tetrazolinone, 
1-3,5-bis(trifluoromethyl)phenyl!-5(4H)-tetrazolinone, 
1-(2-cyanophenyl)-5(4H)-tetrazolinone, 
1-(4-chloro-2-fluoro-5-isopropoxyphenyl)-5(4H)-tetrazolinone, 
1-4-chloro-2-fluoro-5-(methoxycarbonyl)methoxyphenyl!-5(4H)-tetrazolinone, 
1-4-chloro-2-fluoro-5-(n-pentyloxycarbonyl)methoxyphenyl!-5(4H)-tetrazolin 
one, 
1-(7-fluoro-4-ethoxy-2H-1,4-benzoxazine-3(4H)-one-6-yl)-5(4H)-tetrazolinone 
1-(7-fluoro-4-propargyl-2H-1,4-benzoxazine-3(4H)-one-6-yl)-5(4H)-tetrazolin 
one, 
1-(6-fluoro-4-propargyl-2H-1,3-benzoxazole-2-one-5-yl)-5(4H)-tetrazolinone, 
1-(6-fluoro-4-propargyl-2H-1,3-benzothiazole-2-one-5-yl)-5(4H)-tetrazolinon 
e, 
1-4-chloro-2-fluoro-5-(methanesulfonylamino)phenyl!-5(4H)-tetrazolinone 
1-(3-tert-butylisoxazol-5-yl)-5(4H)-tetrazolinone, 
1-(5-tert-butylisoxazole-3-yl)-5(4H)-tetrazolinone, 
1-(5-tert-butyl-1,3,4-thiazol-2-yl)-5(4H)-tetrazolinone, 
1-(5-trifluoromethyl-pyridin-2-yl)-5(4H)-tetrazolinone, 
1-(3-chloro-5-trifluoromethyl-pyridin-2-yl)-5(4H)-tetrazolinone, 
1-(2-chloroethyl)-5(4H)-tetrazolinone, 
1-(2-fluoroethyl)-5(4H)-tetrazolinone, and 
1-3(fluoropropyl)-5(4H)-tetrazolinone. 
Representative carbamoyl chlorides of the formula (III) include the 
following compounds: 
N,N-dimethyl carbamoylchloride, 
N,N-diethyl carbamoylchloride, 
N-ethyl-N-methyl carbamoylchloride, 
N-ethyl-N-n-propyl carbamoylchloride, 
N-ethyl-N-isopropyl carbamoylchloride, 
N-ethyl-N-iso-butyl carbamoylchloride, 
N-ethyl-N-sec-butyl carbamoylchloride, 
N-ethyl-N-tert-butyl carbamoylchloride, 
N-ethyl-N-cyclopentyl carbamoylchloride, 
N-ethyl-N-cyclohexyl carbamoylchloride, 
N,N-di-n-propyl carbamoylchloride, 
N-n-propyl-N-isopropyl carbamoylchloride, 
N-n-propyl-N-cyclopentyl carbamoylchloride, 
N-n-propyl-N-cyclohexyl carbamoylchloride, 
N,N-di-isopropyl carbamoylchloride, 
N-isopropyl-N-cyclopentyl carbamoylchloride, 
N-isopropyl-N-cyclohexyl carbamoylchloride, 
N,N-di-n-butyl carbamoylchloride, 
N-n-butyl-N-cyclopropyl carbamoylchloride, 
N,N-diallyl carbamoylchloride, 
N,N-dipropargyl carbamoylchloride, 
N-methoxy-N-n-propyl carbamoylchloride, 
N-ethoxy-N-n-propyl carbamoylchloride, 
N-methyl-N-phenyl carbamoylchloride, 
N-ethyl-N-phenyl carbamoylchloride, 
N-n-propyl-N-phenyl carbamoylchloride, 
N-isopropyl-N-phenyl carbamoylchloride, 
N-isopropyl-N-(3-methylphenyl) carbamoylchloride, 
N-isopropyl-N-(4-chlorophenyl) carbamoylchloride, 
N-isopropyl-N-(4-fluorophenyl) carbamoylchloride, 
N-methyl-N-(2-trifluoromethylphenyl) carbamoylchloride, 
N-methyl-N-(3-trifluoromethylphenyl) carbamoylchloride, 
N-isopropyl-(3-trifluoromethylphenyl) carbamoylchloride, 
N-isopropyl-(3-n-propylphenyl) carbamoylchloride, 
4-chlorocarbonyl-morpholine, 
4-chlorocarbonyl-thiomorpholine, 
4-chlorocarbonyl-2,6-dimethylmorpholine, 
1-chlorocarbonyl-piperdine, 
1-chlorocarbonyl-2,6-dimethylpiperidine, 
1-chlorocarbonyl-2,3-dihydroindole, and 
1-chlorocarbonyl-perhydroindole. 
Process variant (a) according to the invention for the production of the 
compounds of formula (I) is preferably carried out using diluents. 
Representative suitable diluents include liquid aliphatic, cycloaliphatic 
and aromatic, optionally chlorinated, hydrocarbons such as benzene, 
toluene, xylene, chloroform, chlorobenzene, and the like; ethers such as 
dioxane, dimethoxyethane (DME), tetrahydrofuran (THF), and the like; 
ketones such as, for example, acetone, methyl ethyl ketone, methyl 
isopropyl ketone, methyl iso-butyl ketone, and the like; nitrites such as 
acetonitrile, propionitrile, and the like; esters such as, for example, 
ethyl acetate, and the like; and liquid bases such as, for example, 
pyridine, and the like. 
Process variant (a) according to the invention is carried out in the 
presence of 4-dimethylamino-pyridine, which functions not only as 
acid-binder but also as catalyst. 
If 4-dimethylamino-pyridine is employed in only catalytic 
(sub-stoichiometric) amounts, then process variant (a) is carried out in 
the presence of an additional acid-binder (in at least stoichiometric 
amount). 
Representative additional acid-binders include inorganic bases such as, for 
example, carbonates and bicarbonates of alkali metals such as, for 
example, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium 
carbonate, potassium carbonate, and the like; and, as organic bases there 
may be mentioned tertiary amines, dialkylaminoanilines and pyridines such 
as, for example, triethylamine, 1,1,4,4-tetramethylethylenediamine 
(TMEDA), N,N-dimethylaniline, N,N-diethylaniline, pyridine, 
1,4-diazabicyclo-2,2,2!octane (DABCO), and 
1,8-diazabicyclo-5,4,0!undec-7-ene (DBU). 
In general, the process variant (a) is carried out at a temperature of from 
about 15.degree. C. to about 150.degree. C., preferably from about 
50.degree. C. to about 130.degree. C. 
Further, the reaction is preferably carried out under normal pressure, 
although it is also possible to employ a higher or reduced pressure. 
In carrying out process variant (a) according to the invention, the desired 
compounds of the formula (I) can be obtained in high yields by reacting 
about 0.8 to 1.5 mols of the compound of the formula (III) per mol of the 
compound of the formula (II), in the presence of about 0.01 to about 0.5 
mols of 4-dimethylamino-pyridine as well as 0.3 to 1.5 mols of an 
additional acid binder. 
In carrying out the process variant (a) with the use of 
4-dimethylamino-pyridine as sole acid binder, it may be used in the amount 
of from about 0.8 to about 1.5 mols, including the desired catalytic 
amount. 
Process variant (b) according to the invention is preferably carried out 
using diluents. Solvents which are suitable for this purpose are virtually 
the same organic solvents as have been mentioned above in connection with 
the description of process variant (a) according to the invention. 
The first step of process variant (b) is preferably carried out in the 
presence of an acid acceptor. Acid-binding agents which are suitable for 
this purpose are the same as have been mentioned above in connection with 
the description of process variant (a) according to the invention. 
In the second step of process variant (b), there must be employed 
4-dimethylamino-pyridine as catalyst for the isomerization reaction 
(carbamoyl-migration). 
In general, the process variant (b) is carried out at a temperature of from 
about 15.degree. C. to about 150.degree. C., preferably from about 
50.degree. C. to about 130.degree. C. 
Further, the reaction is preferably carried out under normal pressure, 
although it is also possible to employ a higher or reduced pressure. 
When the above-mentioned process variant (b) according to the present 
invention is carried out, the compounds of the general formulae (II) and 
(III), respectively, are reacted in approximately equimolar amounts, 
followed by reacting the thus prepared mixture of a compound of the 
general formula (I) and its isomer of the general formula (IV) with about 
0.01 to about 0.5 mols of 4-dimethylamino-pyridine as catalyst, so as to 
obtain the desired tetrazolinones of the general formula (I) in high 
yields.