Herbicidal 1-pyridyltetrazolinones

Abstract

Herbicidal tetrazolinone derivatives of the formula: ##STR1## in which R.sup.1 is alkyl, haloalkyl, cycloalkyl, alkenyl, haloalkenyl, alkynyl or phenyl, andR.sup.2 is alkyl, haloalkyl, cycloalkyl, alkenyl, haloalkenyl, alkynyl or phenyl, orR.sup.1 and R.sup.2 together with the nitrogen atom to which they are bonded form an optionally benzofused heterocyclic ring, which is optionally substituted by C.sub.1-4 alkyl,n is 0, 1, 2 or 3, andR.sup.3 each independently is nitro, halogen, alkyl, haloalkyl, alkylthio or phenoxy.

Description

The present invention relates to tetrazolinone derivatives, to processes for their preparation and to their use as herbicides, as well as to intermediates therefor.

It has already been known that tetrazolinone derivatives are useful as herbicides (see U.S. Pat. Nos. 4,618,365; 4,826,529; 4,830,661; 4,956,469; 5,003,075; 5,019,152; 5,342,954; 5,344,814; 5,347,009; 5,347,010 and 5,362,704).

There have been found novel tetrazolinone derivatives of the formula (I) ##STR2## wherein

R.sup.1 is alkyl, haloalkyl, cycloalkyl, alkenyl, haloalkenyl, alkynyl or phenyl which may be substituted, and

R.sup.2 is alkyl, haloalkyl, cycloalkyl, alkenyl, haloalkenyl, alkynyl or phenyl which may be substituted, or

R.sup.1 and R.sup.2 may form, together with the nitrogen atom to which R.sup.1 and R.sup.2 are bonded, a 5- or 6-membered heterocyclic ring, said heterocyclic ring may be benzofused and may be substituted by one or more C.sub.1-4 alkyl radicals,

R.sup.3 is nitro, halogen, alkyl, haloalkyl, alkoxy, haloalkoxy, alkylthio or phenoxy, and

n is 0, 1, 2 or 3, and when n is 2 or 3, then R.sup.3 may be same or different.

The novel tetrazolinone derivatives of the formula (I) are obtained when

(a) compounds of the following formula (II) ##STR3## wherein R.sup.3 and n have the above mentioned meanings, are reacted with compounds of the following formula (III) ##STR4## wherein R.sup.1 and R.sup.2 have the above mentioned meanings, and hal represents a releasable group such as chlorine or bromine, in the presence of acid-binder, in the presence of inert solvents.

The novel tetrazolinone derivatives of the formula (I) exhibit powerful herbicidal properties.

Surprisingly, the tetrazolinone derivatives of the formula (I) according to the present invention exhibit a substantially higher herbicidal activity than those known from the prior art, for instance, the aforementioned U.S. Pat. Nos. 4,618,365; 4,826,529; 4,830,661; 4,956,469; 5,003,075; 5,019,152; 5,342,954; 5,344,814; 5,347,009; 5,347,010 and 5,362,704.

In the compounds of the formula (I) according to the invention, and the respective general formulae representing their intermediates employed for the production of the compounds formula (1), each of the halogen as well as the halogen parts of the haloalkyl, haloalkenyl and haloalkoxy represent fluorine, chlorine, bromine or iodine, preferably chlorine or fluorine.

Alkyl is, for example, methyl, ethyl, propyl, isopropyl, n-(iso-, sec-, tert-)butyl, n-(iso-, sec-, tert-, neo-)pentyl or n-(iso-, see-, tert-, neo-)hexyl.

Haloalkyl is the above mentioned alkyl groups substituted with the same or different halogen atoms, such as for example, trifluoromethyl, 2-chloroethyl and 2,2,2-trifluoroethyl.

Cycloalkyl is, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl.

Alkenyl is, for example, vinyl, allyl, isopropenyl, 1-methyl-2-propenyl, 2-methyl-2-propenyl, 2-(or 3-)butenyl or 2-(3- or 4-)pentenyl.

Haloalkenyl is the above mentioned alkenyl groups substituted with the same or different halogen atoms, such as for example, 2-chloro-2-propenyl.

The alkynyl represents, for example, propargyl.

The 5- or 6-membered heterocyclic ring contains, as a hetero-atom, at least one nitrogen and may contain further hetero-atoms selected from the group consisting of nitrogen, oxygen and sulfur. Said heterocyclic group may be benzofused, and for example, pyrrolidinyl, 2,5-dimethylpyrrolidinyl, pyrrolinyl, 2,5-dimethyl-3-pyrrolinyl, imidazolidinyl, pyrazolidinyl, pyrrolinyl, piperidyl, 2-methylpiperidyl, 2,6-dimethylpiperidyl, piperazinyl, indolinyl, morpholinyl, 1,2,3,4-tetrahydroquinolyl or 2-methyl-1,2,3,4-tetrahydroquinolyl can be exemplified.

Phenyl and phenoxy may optionally be substituted. The substitutent(s) are selected from the group consisting of halogen, cyano, nitro, alkyl, haloalkyl, alkoxy, haloalkoxy and alkylthio.

Alkoxy is for example, methoxy, ethoxy, propoxy, isopropoxy, n-(iso-, sec-, tert-)butoxy, n-(iso-, sec-, tert-, neo-)pentoxy or n-(iso-, sec-, tert-, neo-)hextoxy.

Alkylthio is, for example, methylthio, ethylthio, propylthio, isopropylthio, n-(iso-, sec-, tert-)butylthio, n-(iso-, sec-, tert-, neo-)pentylthio or n-(iso-, sec-, ten-, neo-)hexylthio.

Haloalkoxy is the above mentioned alkoxy substituted with the same or different halogen atoms, for example, trifluoromethoxy.

Among the tetrazolinone derivatives according to the invention, of the formula (I), preferred compounds are those in which

R.sup.1 is C.sub.1-6 alkyl, C.sub.1-6 haloalkyl, C.sub.3-8 cycloalkyl, C.sub.2-6 alkenyl, C.sub.2-6 haloalkenyl, C.sub.3-6 alkynyl or phenyl, and

R.sup.2 is C.sub.1-6 alkyl, C.sub.1-6 haloalkyl, C.sub.3-8 cycloalkyl, C.sup.2-6 alkenyl, C.sub.2-6 haloalkenyl, C.sup.3-6 alkynyl or phenyl, or

R.sup.1 and R.sup.2 may form, together with the nitrogen atom to which R.sup.1 and R.sup.2 are bonded, a 5- or 6-membered heterocyclic ring, the hetero atoms of which are selected from the group consisting of nitrogen atom, oxygen and sulfur and said heterocyclic ring may be benzofused and may be substituted by one or more methyl radicals,

R.sup.3 is nitro, fluoro, chloro, bromo, 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 or phenoxy, and

n is 0, 1, 2 or 3, and when n is 2 or 3, R.sup.3 may be same or different.

Particularly preferred tetrazolinone derivatives of the formula (I) are those in which

R.sup.1 is C.sub.1-4 alkyl, C.sub.1-4 haloalkyl, cyclopropyl, cyclopentyl, cyclohexyl, C.sub.2-4 alkenyl, C.sub.2-4 haloalkenyl, C.sub.3-4 alkynyl or phenyl, and

R.sup.2 is C.sub.1-4 alkyl, C.sub.1-4 haloalkyl, cyclopropyl, cyclopentyl, cyclohexyl, C.sub.2-4 alkenyl, C.sub.2-4 haloalkenyl, C.sub.3-4 alkynyl or phenyl, or

R.sup.1 and R.sup.2 may form, together with the nitrogen atom to which R.sup.1 and R.sup.2 are bonded, pyrrolidinyl, 2,5-dimethylpyrrolidinyl, pyrrolinyl, 2,5-dimethyl-3-pyrrolinyl, piperidyl, 2-methylpiperidyl, 2,6-dimethylpiperidyl, piperazinyl, morpholinyl, 1,2,3,4-tetrahydroquinolyl or 2-methyl- 1,2,3,4-tetrahydroquinolyl.

R.sup.3 is nitro, fluoro, chloro, bromo, 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 or phenoxy, and

n is 0, 1 or 2, and when n is 2, R.sup.3 may be same or different.

Specifically, compounds according to the invention wherein R.sup.1 and R.sup.2 represent each an independent group are shown in the Table 1, and those wherein R.sup.1 and R.sup.2 together with the nitrogen to which they are bonded form a heterocyclic ring are shown in the Table 2. ##STR5##

TABLE 1______________________________________Q R.sup.1 R.sup.2______________________________________Q1 methyl isopropylQ1 methyl cyclopropylQ1 ethyl ethylQ1 ethyl isopropylQ1 ethyl cyclopropylQ1 ethyl cyclohexylQ1 n-propyl isopropylQ1 isopropyl isopropylQ1 isopropyl phenylQ2 methyl ethylQ2 methyl isopropylQ2 methyl cyclopropylQ2 ethyl ethylQ2 ethyl isopropylQ2 ethyl cyclopropylQ2 n-propyl cyclopropylQ2 isopropyl isopropylQ2 isopropyl cyclohexylQ3 methyl methylQ3 methyl isopropylQ3 methyl cyclopropylQ3 ethyl ethylQ3 ethyl n-propylQ3 ethyl isopropylQ3 ethyl cyclohexylQ3 n-propyl isopropylQ3 isopropyl isopropylQ3 isopropyl phenylQ4 methyl n-propylQ4 methyl isopropylQ4 methyl cyclopropylQ4 methyl cyclohexylQ4 methyl 1-methyl-2-propenylQ4 ethyl ethylQ4 ethyl isopropylQ4 ethyl cyclopropylQ4 ethyl cyclohexylQ4 2-chloroethyl isopropylQ4 2-chloroethyl 2-chloroethylQ4 isopropyl 2,2,2-trifluoroethylQ4 n-propyl isopropylQ4 n-propyl cyclopropylQ4 n-propyl cyclohexylQ4 isopropyl isopropylQ4 isopropyl phenylQ4 isopropyl propargylQ4 allyl allylQ4 propargyl propargylQ4 isopropyl allylQ5 methyl methylQ5 methyl ethylQ5 methyl n-propylQ5 methyl isopropylQ5 methyl cyclopropylQ5 methyl 1-methyl-2-propenylQ5 methyl cyclopentylQ5 ethyl ethylQ5 ethyl n-propylQ5 ethyl isopropylQ5 ethyl sec-butylQ5 ethyl cyclopropylQ5 ethyl cyclohexylQ5 ethyl 2,2,2-trifluoroethylQ5 n-propyl 2,2,2-trifluoroethylQ5 isopropyl 2,2,2-trifluoroethylQ5 2-chloroethyl ethylQ5 2-chloroethyl n-propylQ5 2-chloroethyl isopropylQ5 2-chloroethyl 2-chloroethylQ5 n-propyl isopropylQ5 n-propyl cyclopropylQ5 n-propyl cyclohexylQ5 isopropyl isopropylQ5 isopropyl phenylQ5 isopropyl allylQ5 isopropyl 2-chloro-2-propenylQ5 isopropyl 2-methyl-2-propenylQ5 isopropyl propargylQ5 allyl allylQ5 propargyl propargylQ6 methyl methylQ6 methyl isopropylQ6 methyl cyclopropylQ6 methyl cyclopentylQ6 methyl 1-methyl-2-propenylQ6 ethyl ethylQ6 ethyl isopropylQ6 ethyl cyclopropylQ6 ethyl cyclohexylQ6 isopropyl 2,2,2-trifluoroethylQ6 2-chloroethyl isopropylQ6 2-chloroethyl 2-chloroethylQ6 n-propyl isopropylQ6 n-propyl cyclopropylQ6 n-propyl cyclopentylQ6 isopropyl isopropylQ6 isopropyl cyclohexylQ6 isopropyl phenylQ6 isopropyl allylQ6 isopropyl propargylQ6 allyl allylQ6 propargyl propargylQ7 methyl isopropylQ7 methyl cyclopropylQ7 ethyl ethylQ7 ethyl isopropylQ7 ethyl cyclopropylQ7 n-propyl isopropylQ7 isopropyl isopropylQ7 isopropyl phenylQ8 methyl methylQ8 methyl isopropylQ8 methyl cyclopropylQ8 methyl cyclohexylQ8 methyl 1-methyl-2-propenylQ8 ethyl ethylQ8 ethyl isopropylQ8 ethyl cyclopropylQ8 ethyl cyclopentylQ8 ethyl 2,2,2-trifluoroethylQ8 n-propyl 2,2,2-trifluoroethylQ8 iso-propyl 2,2,2-trifluoroethylQ8 2-chloroethyl ethylQ8 2-chloroethyl n-propylQ8 2-chloroethyl isopropylQ8 2-chloroethyl 2-chloroethylQ8 n-propyl isopropylQ8 n-propyl cyclopropylQ8 n-propyl cyclohexylQ8 isopropyl isopropylQ8 isopropyl phenylQ8 isopropyl allylQ8 isopropyl 2-chloro-2-propenylQ8 isopropyl 2-methyl-2-propenylQ8 isopropyl propargylQ8 allyl allylQ8 propargyl propargylQ9 methyl ethylQ9 methyl isopropylQ9 methyl cyclopropylQ9 methyl s-butylQ9 methyl 1-methyl-2-propenylQ9 ethyl ethylQ9 ethyl n-propylQ9 ethyl isopropylQ9 ethyl cyclopropylQ9 isopropyl 2,2,2-trifluoroethylQ9 2-chloroethyl isopropylQ9 2-chloroethyl 2-chloroethylQ9 n-propyl isopropylQ9 n-propyl cyclopropylQ9 n-propyl s-butylQ9 isopropyl isopropylQ9 isopropyl cyclohexylQ9 isopropyl phenylQ9 isopropyl allylQ9 isopropyl propargylQ9 allyl allylQ9 propargyl propargylQ10 methyl n-propylQ10 methyl isopropylQ10 methyl cyclopropylQ10 methyl s-butylQ10 methyl 1-methyl-2-propenylQ10 ethyl ethylQ10 ethyl n-propylQ10 ethyl isopropylQ10 ethyl cyclopropylQ10 ethyl phenylQ10 isopropyl 2,2,2-trifluoroethylQ10 2-chloroethyl isopropylQ10 2-chloroethyl 2-chloroethylQ10 n-propyl isopropylQ10 n-propyl cyclopropylQ10 n-propyl s-butylQ10 isopropyl cyclohexylQ10 isopropyl phenylQ10 isopropyl allylQ10 isopropyl propargylQ10 allyl allylQ10 propargyl propargylQ11 methyl isopropylQ11 ethyl ethylQ11 ethyl isopropylQ11 ethyl s-butylQ11 ethyl phenylQ11 n-propyl isopropylQ11 isopropyl phenylQ12 methyl n-propylQ12 methyl isopropylQ12 methyl cyclopropylQ12 methyl 1-methyl-2-propenylQ12 ethyl ethylQ12 ethyl isopropylQ12 ethyl cyclopropylQ12 ethyl cyclohexylQ12 isopropyl 2,2,2-trifluoroethylQ12 2-chloroethyl isopropylQ12 2-chloroethyl 2-chloroethylQ12 n-propyl isopropylQ12 n-propyl cyclopropylQ12 n-propyl cyclohexylQ12 isopropyl isopropylQ12 isopropyl phenylQ12 isopropyl allylQ12 isopropyl propargylQ12 allyl allylQ12 propargyl propargylQ13 methyl isopropylQ13 methyl cyclopropylQ13 methyl cyclohexylQ13 methyl 1-methyl-2-propenylQ13 ethyl ethylQ13 ethyl isopropylQ13 ethyl cyclopropylQ13 ethyl cyclohexylQ13 isopropyl 2,2,2-trifluoroethylQ13 2-chloroethyl isopropylQ13 2-chloroethyl 2-chloroethylQ13 n-propyl isopropylQ13 n-propyl cyclopropylQ13 isopropyl isopropylQ13 isopropyl phenylQ13 isopropyl allylQ13 isopropyl propargylQ13 allyl allylQ13 propargyl propargylQ14 methyl methylQ14 methyl ethylQ14 methyl n-propylQ14 methyl isopropylQ14 methyl cyclopropylQ14 methyl cyclopentylQ14 methyl 1-methyl-2-propenylQ14 ethyl ethylQ14 ethyl n-propylQ14 ethyl sec-butylQ14 ethyl isopropylQ14 ethyl cyclopropylQ14 ethyl cyclohexylQ14 ethyl 2,2,2-trifluoroethylQ14 n-propyl 2,2,2-trifluoroethylQ14 isopropyl 2,2,2-trifluoroethylQ14 2-chloroethyl ethylQ14 2-chloroethyl n-propylQ14 2-chloroethyl isopropylQ14 2-chloroethyl 2-chloroethylQ14 n-propyl isopropylQ14 n-propyl cyclopropylQ14 isopropyl isopropylQ14 isopropyl 2-chloro-2-propenylQ14 isopropyl 2-methyl-2-propenylQ14 isopropyl propargylQ14 isopropyl phenylQ14 isopropyl allylQ14 allyl allylQ14 propargyl propargylQ15 methyl isopropylQ15 methyl cyclopropylQ15 methyl 1-methyl-2-propenylQ15 ethyl ethylQ15 ethyl isopropylQ15 ethyl cyclopropylQ15 ethyl cyclohexylQ15 isopropyl 2,2,2-trifluoroethylQ15 2-chloroethyl isopropylQ15 2-chloroethyl 2-chloroethylQ15 n-propyl isopropylQ15 n-propyl cyclopropylQ15 isopropyl isopropylQ15 isopropyl phenylQ15 isopropyl allylQ15 isopropyl propargylQ15 allyl allylQ15 propargyl propargylQ16 methyl isopropylQ16 methyl cyclopropylQ16 methyl 1-methyl-2-propenylQ16 ethyl ethylQ16 ethyl isopropylQ16 ethyl cyclopropylQ16 ethyl cyclohexylQ16 isopropyl 2,2,2-trifluoroethylQ16 2-chloroethyl isopropylQ16 2-chloroethyl 2-chloroethylQ16 n-propyl isopropylQ16 n-propyl cyclopropylQ16 isopropyl isopropylQ16 isopropyl phenylQ16 isopropyl allylQ16 isopropyl propargylQ16 allyl allylQ16 propargyl propargylQ17 methyl isopropylQ17 methyl cyclopropylQ17 n-propyl isopropylQ17 methyl 1-methyl-2-propenylQ17 ethyl ethylQ17 ethyl isopropylQ17 ethyl cyclopropylQ17 isopropyl 2,2,2-trifluoroethylQ17 2-chloroethyl isopropylQ17 2-chloroethyl 2-chloroethylQ17 n-propyl cyclopropylQ17 isopropyl isopropylQ17 isopropyl phenylQ17 isopropyl allylQ17 isopropyl propargylQ17 allyl allylQ17 propargyl propargylQ18 methyl isopropylQ18 methyl cyclopropylQ18 methyl phenylQ18 methyl 1-methyl-2-propenylQ18 ethyl ethylQ18 ethyl n-propylQ18 ethyl isopropylQ18 ethyl cyclopropylQ18 isopropyl 2,2,2-trifluoroethylQ18 2-chloroethyl isopropylQ18 2-chloroethyl 2-chloroethylQ18 n-propyl isopropylQ18 isopropyl isopropylQ18 isopropyl phenylQ18 isopropyl allylQ18 isopropyl propargylQ18 allyl allylQ18 propargyl propargylQ19 methyl methylQ19 methyl ethylQ19 methyl isopropylQ19 methyl cyclopropylQ19 methyl 1-methyl-2-propenylQ19 ethyl ethylQ19 ethyl isopropylQ19 ethyl cyclopropylQ19 ethyl 2,2,2-trifluoroethylQ19 n-propyl 2,2,2-trifluoroethylQ19 isopropyl 2,2,2-trifluoroethylQ19 2-chloroethyl ethylQ19 2-chloroethyl n-propylQ19 2-chloroethyl isopropylQ19 2-chloroethyl 2-chloroethylQ19 n-propyl isopropylQ19 isopropyl isopropylQ19 isopropyl phenylQ19 isopropyl allylQ19 isopropyl 2-chloro-propenylQ19 isopropyl 2-methyl-propenylQ19 isopropyl propargylQ19 allyl allylQ19 propargyl propargylQ20 methyl isopropylQ20 methyl 1-methyl-2-propenylQ20 ethyl ethylQ20 ethyl isopropylQ20 ethyl cyclopropylQ20 2-chloroethyl isopropylQ20 2-chloroethyl 2-chloroethylQ20 isopropyl 2,2,2-trifluoroethylQ20 n-propyl isopropylQ20 n-propyl cyclopropylQ20 isopropyl isopropylQ20 isopropyl phenylQ20 isopropyl allylQ20 isopropyl propargylQ20 allyl allylQ20 propargyl propargylQ21 methyl isopropylQ21 methyl cyclopropylQ21 methyl cyclohexylQ21 methyl 1-methyl-2-propenylQ21 ethyl ethylQ21 ethyl isopropylQ21 ethyl cyclopropylQ21 ethyl cyclohexylQ21 2-chloroethyl isopropylQ21 2-chloroethyl 2-chloroethylQ21 isopropyl 2,2,2-trifluoroethylQ21 n-propyl isopropylQ21 n-propyl cyclopropylQ21 n-propyl cyclohexylQ21 isopropyl isopropylQ21 isopropyl phenylQ21 isopropyl allylQ21 isopropyl propargylQ21 allyl allylQ21 propargyl propargylQ22 methyl isopropylQ22 ethyl ethylQ22 ethyl isopropylQ22 n-propyl isopropylQ22 isopropyl isopropylQ23 methyl n-propylQ23 methyl isopropylQ23 methyl cyclopropylQ23 methyl cyclopentylQ23 methyl cyclohexylQ23 methyl 1-methyl-2-propenylQ23 ethyl ethylQ23 ethyl n-propylQ23 ethyl isopropylQ23 ethyl s-butylQ23 ethyl phenylQ23 2-chloroethyl isopropylQ23 2-chloroethyl 2-chloroethylQ23 isopropyl 2,2,2-trifluoroethylQ23 n-propyl isopropylQ23 n-propyl cyclopropylQ23 n-propyl cyclopentylQ23 isopropyl isopropylQ23 isopropyl cyclohexylQ23 isopropyl phenylQ23 isopropyl allylQ23 isopropyl propargylQ23 allyl allylQ23 propargyl propargylQ24 methyl ethylQ24 methyl isopropylQ24 methyl cyclopropylQ24 methyl s-butylQ24 methyl phenylQ24 methyl 1-methyl-2-propenylQ24 ethyl ethylQ24 ethyl isopropylQ24 ethyl cyclopropylQ24 ethyl cyclohexylQ24 ethyl 2,2,2-trifluoroethylQ24 n-propyl 2,2,2-trifluoroethylQ24 isopropyl 2,2,2-trifluoroethylQ24 2-chloroethyl ethylQ24 2-chloroethyl n-propylQ24 2-chloroethyl isopropylQ24 2-chloroethyl 2-chloroethylQ24 n-propyl isopropylQ24 n-propyl s-butylQ24 n-propyl cyclohexylQ24 isopropyl isopropylQ24 isopropyl cyclohexylQ24 isopropyl phenylQ24 isopropyl allylQ24 isopropyl 2-chloro-2-propenylQ24 isopropyl 2-methyl-2-propenylQ24 isopropyl propargylQ24 allyl allylQ24 propargyl propargylQ25 methyl ethylQ25 methyl isopropylQ25 methyl cyclopropylQ25 methyl cyclohexylQ25 methyl 1-methyl-2-propenylQ25 ethyl ethylQ25 ethyl isopropylQ25 ethyl cyclopropylQ25 ethyl cyclohexylQ25 2-chloroethyl isopropylQ25 2-chloroethyl 2-chloroethylQ25 isopropyl 2,2,2-trifluoroethylQ25 n-propyl isopropylQ25 n-propyl cyclopropylQ25 isopropyl isopropylQ25 isopropyl phenylQ25 isopropyl allylQ25 isopropyl propargylQ25 allyl allylQ25 propargyl propargylQ26 methyl methylQ26 methyl ethylQ26 methyl n-propylQ26 methyl isopropylQ26 methyl cyclopropylQ26 methyl cyclopentylQ26 methyl cyclohexylQ26 methyl 1-methyl-2-propenylQ26 ethyl ethylQ26 ethyl isopropylQ26 ethyl cyclopropylQ26 ethyl cyclohexylQ26 ethyl 2,2,2-trifluoroethylQ26 n-propyl 2,2,2-trifluoroethylQ26 isopropyl 2,2,2-trifluoroethylQ26 2-chloroethyl ethylQ26 2-chloroethyl n-propylQ26 2-chloroethyl isopropylQ26 2-chloroethyl 2-chloroethylQ26 n-propyl isopropylQ26 n-propyl cyclopropylQ26 isopropyl isopropylQ26 isopropyl phenylQ26 isopropyl allylQ26 isopropyl 2-chloro-2-propenylQ26 isopropyl 2-methyl-2-propenylQ26 isopropyl propargylQ26 allyl allylQ26 propargyl propargylQ27 methyl isopropylQ27 methyl cyclopropylQ27 methyl cyclohexylQ27 ethyl ethylQ27 ethyl isopropylQ27 ethyl cyclohexylQ27 n-propyl isopropylQ27 isopropyl isopropylQ27 isopropyl phenylQ28 ethyl cyclohexylQ28 ethyl phenylQ28 ethyl 2,2,2-trifluoroethylQ28 n-propyl 2,2,2-trifluoroethylQ28 isopropyl 2,2,2-trifluoroethylQ28 2-chloroethyl ethylQ28 2-chloroethyl n-propylQ28 2-chloroethyl isopropylQ28 2-chloroethyl 2-chloroethylQ28 n-propyl isopropylQ28 n-propyl cyclopropylQ28 n-propyl s-butylQ28 n-propyl cyclopentylQ28 n-propyl cyclohexylQ28 isopropyl isopropylQ28 isopropyl cyclohexylQ28 isopropyl phenylQ28 isopropyl allylQ28 isopropyl 2-chloro-2-propenylQ28 isopropyl 2-methyl-2-propenylQ28 isopropyl propargylQ28 allyl allylQ28 propargyl propargylQ29 methyl methylQ29 methyl ethylQ29 methyl n-propylQ29 methyl isopropylQ29 methyl cyclopropylQ29 methyl cyclopentylQ29 methyl cyclohexylQ29 methyl phenylQ28 methyl methylQ28 methyl ethylQ28 methyl n-propylQ28 methyl isopropylQ28 methyl cyclopropylQ28 methyl s-butylQ28 methyl cyclopentylQ28 methyl cyclohexylQ28 methyl phenylQ28 methyl 1-methyl-2-propenylQ28 ethyl ethylQ28 ethyl n-propylQ28 ethyl isopropylQ28 ethyl cyclopropylQ28 ethyl s-butylQ28 ethyl cyclopentylQ29 methyl 1-methyl-2-propenylQ29 ethyl ethylQ29 ethyl isopropylQ29 ethyl cyclopropylQ29 ethyl phenylQ29 ethyl 2,2,2-trifluoroethylQ29 2-chloroethyl ethylQ29 2-chloroethyl n-propylQ29 2-chloroethyl isopropylQ29 2-chloroethyl 2-chloroethylQ29 n-propyl cyclopropylQ29 n-propyl 2,2,2-trifluoroethylQ29 isopropyl 2,2,2-trifluoroethylQ29 isopropyl isopropylQ29 isopropyl phenylQ29 isopropyl allylQ29 isopropyl 2-chloro-2-propenylQ29 isopropyl 2-methyl-2-propenylQ29 isopropyl propargylQ29 allyl allylQ29 propargyl propargylQ30 methyl methylQ30 methyl ethylQ30 methyl n-propylQ30 methyl isopropylQ30 methyl cyclopropylQ30 methyl s-butylQ30 methyl cyclopentylQ30 methyl cyclohexylQ30 methyl phenylQ30 methyl 1-methyl-2-propenylQ30 ethyl ethylQ30 ethyl n-propylQ30 ethyl isopropylQ30 ethyl cyclopropylQ30 ethyl s-butylQ30 ethyl cyclopentylQ30 ethyl cyclohexylQ30 ethyl phenylQ30 ethyl 2,2,2-trifluoroethylQ30 n-propyl 2,2,2-trifluoroethylQ30 isopropyl 2,2,2-trifluoroethylQ30 2-chloroethyl ethylQ30 2-chloroethyl n-propylQ30 2-chloroethyl isopropylQ30 2-chloroethyl 2-chloroethylQ30 n-propyl isopropylQ30 n-propyl cyclopropylQ30 n-propyl s-butylQ30 n-propyl cyclopentylQ30 n-propyl cyclohexylQ30 isopropyl isopropylQ30 isopropyl 2-chloro-2-propenylQ30 isopropyl 2-methyl-2-propenylQ30 isopropyl propargylQ30 isopropyl cyclohexylQ30 isopropyl phenylQ30 isopropyl allylQ30 allyl allylQ30 propargyl propargylQ31 methyl ethylQ31 methyl n-propylQ31 methyl isopropylQ31 methyl cyclopropylQ31 methyl s-butylQ31 methyl 1-methyl-2-propenylQ31 ethyl ethylQ31 ethyl n-propylQ31 ethyl isopropylQ31 ethyl cyclopropylQ31 ethyl 2,2,2-trifluoroethylQ31 n-propyl 2,2,2-trifluoroethylQ31 isopropyl 2,2,2-trifluoroethylQ31 2-chloroethyl ethylQ31 2-chloroethyl n-propylQ31 2-chloroethyl isopropylQ31 2-chloroethyl 2-chloroethylQ31 n-propyl isopropylQ31 n-propyl cyclopropylQ31 isopropyl isopropylQ31 isopropyl phenylQ31 isopropyl allylQ31 isopropyl 2-chloro-2-propenylQ31 isopropyl 2-methyl-2-propenylQ31 isopropyl propargylQ31 allyl allylQ31 propargyl propargylQ32 methyl methylQ32 methyl ethylQ32 methyl n-propylQ32 methyl isopropylQ32 methyl cyclopropylQ32 methyl s-butylQ32 methyl cyclopentylQ32 methyl cyclohexylQ32 methyl phenylQ32 methyl 1-methyl-2-propenylQ32 ethyl ethylQ32 ethyl n-propylQ32 ethyl isopropylQ32 ethyl cyclopropylQ32 ethyl s-butylQ32 ethyl cyclopentylQ32 ethyl cyclohexylQ32 ethyl phenylQ32 n-propyl isopropylQ32 n-propyl cyclopropylQ32 n-propyl s-butylQ32 n-propyl cyclopentylQ32 n-propyl cyclohexylQ32 isopropyl isopropylQ32 isopropyl cyclohexylQ32 isopropyl phenylQ32 isopropyl allylQ32 isopropyl 2-chloro-2-propenylQ32 isopropyl 2-methyl-2-propenylQ32 isopropyl propargylQ32 allyl allylQ32 propargyl propargylQ33 methyl methylQ33 methyl ethylQ33 methyl n-propylQ33 methyl isopropylQ33 methyl cyclopropylQ33 methyl s-butylQ33 methyl cyclopentylQ33 methyl cyclohexylQ33 methyl phenylQ33 methyl 1-methyl-2-propenylQ33 ethyl ethylQ33 ethyl n-propylQ33 ethyl isopropylQ33 ethyl cyclopropylQ33 ethyl s-butylQ33 ethyl cyclopentylQ33 ethyl cyclohexylQ33 ethyl phenylQ33 ethyl 2,2,2-trifluoroethylQ33 n-propyl 2,2,2-trifluoroethylQ33 isopropyl 2,2,2-trifluoroethylQ33 2-chloroethyl ethylQ33 2-chloroethyl n-propylQ33 2-chloroethyl isopropylQ33 2-chloroethyl 2-chloroethylQ33 n-propyl isopropylQ33 n-propyl cyclopropylQ33 n-propyl s-butylQ33 n-propyl cyclopentylQ33 n-propyl cyclohexylQ33 isopropyl isopropylQ33 isopropyl cyclohexylQ33 isopropyl phenylQ33 isopropyl allylQ33 isopropyl propargylQ33 allyl allylQ33 propargyl propargylQ34 methyl n-propylQ34 methyl isopropylQ34 methyl cyclopropylQ34 methyl cyclopentylQ34 methyl cyclohexylQ34 methyl 1-methyl-2-propenylQ34 ethyl ethylQ34 ethyl isopropylQ34 ethyl cyclopropylQ34 ethyl cyclopentylQ34 ethyl cyclohexylQ34 ethyl 2,2,2-trifluoroethylQ34 n-propyl 2,2,2-trifluoroethylQ34 isopropyl 2,2,2-trifluoroethylQ34 2-chloroethyl ethylQ34 2-chloroethyl n-propylQ34 2-chloroethyl isopropylQ34 2-chloroethyl 2-chloroethylQ34 n-propyl isopropylQ34 n-propyl cyclopropylQ34 n-propyl cyclohexylQ34 isopropyl isopropylQ34 isopropyl cyclohexylQ34 isopropyl phenylQ34 isopropyl allylQ34 isopropyl 2-chloro-2-propenylQ34 isopropyl 2-methyl-2-propenylQ34 isopropyl propargylQ34 allyl allylQ34 propargyl propargylQ35 methyl n-propylQ35 methyl isopropylQ35 methyl cyclopropylQ35 methyl s-butylQ35 methyl cyclopentylQ35 methyl cyclohexylQ35 methyl 1-methyl-2-propenylQ35 ethyl ethylQ35 ethyl isopropylQ35 ethyl cyclopropylQ35 ethyl cyclopentylQ35 ethyl cyclohexylQ35 ethyl 2,2,2-trifluoroethylQ35 n-propyl 2,2,2-trifluoroethylQ35 isopropyl 2,2,2-trifluoroethylQ35 2-chloroethyl ethylQ35 2-chloroethyl n-propylQ35 2-chloroethyl isopropylQ35 2-chloroethyl 2-chloroethylQ35 n-propyl isopropylQ35 n-propyl cyclopropylQ35 n-propyl cyclohexylQ35 isopropyl isopropylQ35 isopropyl cyclohexylQ35 isopropyl phenylQ35 isopropyl allylQ35 isopropyl 2-chloro-2-propenylQ35 isopropyl 2-methyl-2-propenylQ35 isopropyl propargylQ35 allyl allylQ35 propargyl propargylQ36 methyl methylQ36 methyl ethylQ36 methyl n-propylQ36 methyl isopropylQ36 methyl cyclopropylQ36 methyl s-butylQ36 methyl cyclopentylQ36 methyl cyclohexylQ36 methyl phenylQ36 methyl 1-methyl-2-propenylQ36 ethyl ethylQ36 ethyl n-propylQ36 ethyl isopropylQ36 ethyl cyclopropylQ36 ethyl s-butylQ36 ethyl cyclopentylQ36 ethyl cyclohexylQ36 ethyl phenylQ36 ethyl 2,2,2-trifluoroethylQ36 n-propyl 2,2,2-trifluoroethylQ36 isopropyl 2,2,2-trifluoroethylQ36 2-chloroethyl ethylQ36 2-chloroethyl n-propylQ36 2-chloroethyl isopropylQ36 2-chloroethyl 2-chloroethylQ36 n-propyl isopropylQ36 n-propyl cyclopropylQ36 n-propyl s-butylQ36 n-propyl cyclopentylQ36 n-propyl cyclohexylQ36 isopropyl isopropylQ36 isopropyl cyclohexylQ36 isopropyl phenylQ36 isopropyl allylQ36 isopropyl 2-chloro-2-propenylQ36 isopropyl 2-chloro-2-propenylQ36 isopropyl propargylQ36 allyl allylQ36 propargyl propargylQ37 methyl methylQ37 methyl ethylQ37 methyl n-propylQ37 methyl isopropylQ37 methyl cyclopropylQ37 methyl s-butylQ37 methyl cyclopentylQ37 methyl cyclohexylQ37 methyl phenylQ37 methyl 1-methyl-2-propenylQ37 ethyl ethylQ37 ethyl n-propylQ37 ethyl isopropylQ37 ethyl cyclopropylQ37 ethyl s-butylQ37 ethyl cyclopentylQ37 ethyl cyclohexylQ37 ethyl phenylQ37 ethyl 2,2,2-trifluoroethylQ37 n-propyl 2,2,2-trifluoroethylQ37 isopropyl 2,2,2-trifluoroethylQ37 2-chloroethyl ethylQ37 2-chloroethyl n-propylQ37 2-chloroethyl isopropylQ37 2-chloroethyl 2-chloroethylQ37 n-propyl isopropylQ37 n-propyl cyclopropylQ37 n-propyl s-butylQ37 n-propyl cyclopentylQ37 n-propyl cyclohexylQ37 isopropyl isopropylQ37 isopropyl cyclohexylQ37 isopropyl phenylQ37 isopropyl allylQ37 isopropyl 2-chloro-2-propenylQ37 isopropyl 2-methyl-2-propenylQ37 isopropyl propargylQ37 allyl allylQ37 propargyl propargylQ38 methyl methylQ38 methyl ethylQ38 methyl n-propylQ38 methyl isopropylQ38 methyl cyclopropylQ38 methyl s-butylQ38 methyl cyclopentylQ38 methyl cyclohexylQ38 methyl phenylQ38 methyl 1-methyl-2-propenylQ38 ethyl ethylQ38 ethyl n-propylQ38 ethyl isopropylQ38 ethyl cyclopropylQ38 ethyl s-butylQ38 ethyl cyclopentylQ38 ethyl cyclohexylQ38 ethyl phenylQ38 ethyl 2,2,2-trifluoroethylQ38 n-propyl 2,2,2-trifluoroethylQ38 isopropyl 2,2,2-trifluoroethylQ38 2-chloroethyl ethylQ38 2-chloroethyl n-propylQ38 2-chloroethyl isopropylQ38 2-chloroethyl 2-chloroethylQ38 n-propyl isopropylQ38 n-propyl cyclopropylQ38 n-propyl s-butylQ38 n-propyl cyclopentylQ38 n-propyl cyclohexylQ38 isopropyl isopropylQ38 isopropyl cyclohexylQ38 isopropyl phenylQ38 isopropyl allylQ38 isopropyl 2-chloro-2-propenylQ38 isopropyl 2-methyl-2-propenylQ38 isopropyl propargylQ38 allyl allylQ38 propargyl propargylQ39 methyl isopropylQ39 methyl cyclopropylQ39 ethyl ethylQ39 ethyl isopropylQ39 ethyl cyclopropylQ39 n-propyl isopropylQ39 isopropyl isopropylQ39 isopropyl phenylQ40 methyl ethylQ40 methyl isopropylQ40 methyl cyclopropylQ40 methyl 1-methyl-2-propenylQ40 ethyl ethylQ40 ethyl isopropylQ40 ethyl cyclopropylQ40 ethyl cyclohexylQ40 n-propyl isopropylQ40 n-propyl cyclopropylQ40 n-propyl cyclohexylQ40 isopropyl isopropylQ40 isopropyl phenylQ40 isopropyl allylQ41 methyl methylQ41 methyl ethylQ41 methyl n-propylQ41 methyl isopropylQ41 methyl cyclopropylQ41 methyl s-butylQ41 methyl cyclopentylQ41 methyl cyclohexylQ41 methyl phenylQ41 methyl 1-methyl-2-propenylQ41 ethyl ethylQ41 ethyl n-propylQ41 ethyl isopropylQ41 ethyl cyclopropylQ41 ethyl s-butylQ41 ethyl cyclopentylQ41 ethyl cyclohexylQ41 ethyl phenylQ41 n-propyl isopropylQ41 n-propyl cyclopropylQ41 n-propyl s-butylQ41 n-propyl cyclopentylQ41 n-propyl cyclohexylQ41 isopropyl isopropylQ41 isopropyl cyclohexylQ41 isopropyl phenylQ41 isopropyl allylQ41 isopropyl 2-chloro-2-propenylQ41 isopropyl 2-methyl-2-propenylQ41 isopropyl propargylQ41 allyl allylQ41 propargyl propargyl______________________________________ TABLE 2______________________________________ ##STR6## ##STR7##______________________________________Q1 pyrrolidinylQ1 piperidylQ2 piperidylQ2 morpholinylQ3 pyrrolidinylQ3 morpholinylQ4 pyrrolidinylQ4 piperidylQ4 morpholinylQ4 2-methylpiperidylQ5 pyrrolidinylQ5 piperidylQ5 morpholinylQ5 2-methyl-1,2,3,4-tetrahydroquinolylQ5 2,5-dimethylpyrrolidinylQ5 2,5-dimethyl-3-pyrrolinylQ5 2,6-dimethylpiperidylQ6 pyrrolidinylQ6 piperidylQ6 morpholinylQ6 2,5-dimethylpyrrolidinylQ7 pyrrolidinylQ7 piperidylQ7 morpholinylQ8 pyrrolidinylQ8 piperidylQ8 morpholinylQ8 2-methylpiperidylQ8 2,5-dimethylpyrrolidinylQ8 2,5-dimethyl-3-pyrrolinylQ8 2,6-dimethylpiperidylQ9 pyrrolidinylQ9 piperidylQ9 morpholinylQ9 2,6-dimethylpiperidylQ10 pyrrolidinylQ10 piperidylQ10 morpholinylQ11 pyrrolidinylQ11 piperidylQ11 morpholinylQ12 pyrrolidinylQ12 piperidylQ12 morpholinylQ13 pyrrolidinylQ13 piperidylQ13 morpholinylQ14 pyrrolidinylQ14 piperidylQ14 morpholinylQ14 2-methylpiperidylQ14 2,5-dimethylpyrrolidinylQ14 2,5-dimethyl-3-pyrrolinylQ14 2,6-dimethylpiperidylQ15 pyrrolidinylQ15 piperidylQ15 morpholinylQ15 2,6-dimethylpiperidylQ16 pyrrolidinylQ16 piperidylQ16 morpholinylQ17 pyrrolidinylQ17 piperidylQ17 morpholinylQ18 pyrrolidinylQ18 piperidylQ18 morpholinylQ18 2,6-dimethylpiperidylQ19 pyrrolidinylQ19 piperidylQ19 morpholinylQ19 2,5-dimethylpyrrolidinylQ19 2,5-dimethyl-3-pyrrolinylQ19 2,6-dimethylpiperidylQ20 pyrrolidinylQ20 piperidylQ20 morpholinylQ20 2-methyl-1,2,3,4-tetrahydroquinolylQ21 pyrrolidinylQ21 piperidylQ21 morpholinylQ21 2-methylpiperidylQ22 pyrrolidinylQ22 piperidylQ23 pyrrolidinylQ23 piperidylQ23 morpholinylQ23 2,5-dimethylpyrrolidinylQ23 2,6-dimethylpiperidylQ24 pyrrolidinylQ24 piperidylQ24 morpholinylQ24 2-methylpiperidylQ24 2,5-dimethylpyrrolidinylQ24 2,5-dimethyl-3-pyrrolinylQ24 2,6-dimethylpiperidylQ25 pyrrolidinylQ25 piperidylQ25 morpholinylQ25 2,5-dimethylpyrrolidinylQ25 2,6-dimethylpiperidylQ26 pyrrolidinylQ26 piperidylQ26 morpholinylQ26 2,5-dimethylpyrrolidinylQ26 2,6-dimethylpiperidylQ26 2,5-dimethyl-3-pyrrolinylQ27 pyrrolidinylQ27 piperidylQ28 pyrrolidinylQ28 piperidylQ28 morpholinylQ28 2-methylpiperidylQ28 2,5-dimethylpyrrolidinylQ28 2,6-dimethylpiperidylQ28 2-methyl-1,2,3,4-tetrahydroquinolylQ28 2,5-dimethyl-3-pyrrolinylQ29 pyrrolidinylQ29 piperidylQ29 morpholinylQ29 2,5-dimethylpyrrolidinylQ29 2,5-dimethyl-3-pyrrolinylQ29 2,6-dimethylpiperidylQ30 pyrrolidinylQ30 piperidylQ30 morpholinylQ30 2-methylpiperidylQ30 2,5-dimethylpyrrolidinylQ30 2,5-dimethyl-3-pyrrolinylQ30 2,6-dimethylpiperidylQ30 2-methyl-1,2,3,4-tetrahydroquinolylQ31 pyrrolidinylQ31 piperidylQ31 morpholinylQ32 pyrrolidinylQ32 piperidylQ32 morpholinylQ32 2-methylpiperidylQ32 2,5-dimethylpyrrolidinylQ32 2,6-dimethylpiperidylQ32 2-methyl-1,2,3,4-tetrahydroquinolylQ33 pyrrolidinylQ33 piperidylQ33 2,6-dimethylpiperidylQ33 morpholinylQ33 2-methylpiperidylQ33 2,5-dimethylpyrrolidinylQ33 2,6-dimethylpiperidylQ33 2-methyl-1,2,3,4-tetrahydroquinolylQ34 pyrrolidinylQ34 piperidylQ34 morpholinylQ34 2,5-dimethylpyrrolidinylQ34 2,5-dimethyl-3-pyrrolinylQ34 2,6-dimethylpiperidylQ35 pyrrolidinylQ35 piperidylQ35 morpholinylQ35 2,5-dimethylpyrrolidinylQ35 2,5-dimethyl-3-pyrrolinylQ35 2,6-dimethylpiperidylQ36 pyrrolidinylQ36 piperidylQ36 morpholinylQ36 2-methylpiperidylQ36 2,5-dimethylpyrrolidinylQ36 2,5-dimethyl-3-pyrrolinylQ36 2,6-dimethylpiperidylQ36 2-methyl-1,2,3,4-tetrahydroquinolylQ37 pyrrolidinylQ37 piperidylQ37 morpholinylQ37 2-methylpiperidylQ37 2,5-dimethyl-3-pyrrolinylQ37 2,5-dimethylpyrrolidinylQ37 2,6-dimethylpiperidylQ37 2-methyl-1,2,3,4-tetrahydroquinolylQ38 pyrrolidinylQ38 piperidylQ38 morpholinylQ38 2,6-dimethylpiperidylQ38 2-methylpiperidylQ38 2,5-dimethylpyrrolidinylQ38 2,5-dimethyl-3-pyrrolinylQ38 2-methyl-1,2,3,4-tetrahydroquinolylQ39 pyrrolidinylQ39 piperidylQ39 morpholinylQ40 pyrrolidinylQ40 piperidylQ40 morpholinylQ40 2-methyl-1,2,3,4-tetrahydroquinolylQ41 pyrrolidinylQ41 piperidylQ41 morpholinylQ41 2,5-dimethylpyrrolidinyl______________________________________

When in the process (a), for example, 1-(2-chloro-3-pyridyl)-5(4H)-tetrazolinone and diethylcarbamoyl chloride are used as starting materials, the course of the reaction can be represented by the following equation: ##STR8##

In the process (a), the starting materials of the formula (II) mean those based on the above definition of R.sup.3 and n, and preferably those based on the above preferred definitions.

The compounds of the formula (II) are novel, and can be obtained when (b) compounds of the formula (IV) ##STR9## wherein R.sup.3 and n have the same meanings as mentioned above, are reacted with trimethylsilylazide (at least 2 mols) and then with water or--preferably--with methanol, or (c) compounds of the formula (V) ##STR10## wherein R.sup.3 and n have the stone meanings as mentioned above, are reacted first with trimethylsilylazide and then with water or--preferably--with methanol, or (d) compounds of the formula (VI) ##STR11## wherein R.sup.3 and n have the stone meanings as mentioned above, are reacted with an inorganic base (optionally in aqueous solution), in the presence of inert solvents, and if appropriate, in the presence of acid binders, or (e) compounds of the formula (VII) ##STR12## wherein R.sup.3 and n have the same meanings as mentioned above, are reacted with sodium azide, in the presence of anhydrous aluminum chloride and in the presence of inert solvents.

The compounds of the formula (IV) are well known compounds in the field of organic chemistry (being sold generally as a reagent). The following compounds, are illustrative:

picolinic acid chloride, nicotinic acid chloride, isonicotinic acid chloride, 2-methylthio nicotinic acid chloride, and 2,6-dichloroisonicotinic acid chloride.

The compounds of the formula (IV) can easily be obtained by chlorinating, in a usual manner, the compounds represented by the formula (VIII) ##STR13## wherein R.sup.3 and n have the same meanings as mentioned above.

The preferred compounds of the formula (VIII) are those wherein R.sup.3 and n have the preferred definitions set forth hereinabove.

The compounds of the formula (VIII) are well known compounds in the field of organic chemistry. For example, said compounds may be synthesized by the processes described in WO 93/8005, French Patent Laid-Open 2686340, EP-A 166907, 181311, 55011, Japanese Patent Laid-Open Application Hei 3-81263, Journal of the Chemical Society of London, vol. 67, page 407, vol. 73, page 590, Journal of Organic Chemistry, vol. 19, page 1633, 1954, Tetrahedron, vol. 50(No. 4), pages 1129-1134, 1994, Bulletin de la Societe Chimiqque de France, (3-4, Pt.2), pages 530-532, 1976, Applied Radiation. Isotopes, vol. 42 (No. 3), pages 215-220, 1991, Chemisch Berichte, vol. 14, page 645, 1881, vol. 19, page 1305, 1886, vol. 35, page 1352, 1902, vol. 61, page 2202, 1928, Journal of Chemical Research, Synopsis, (1), pages 20-21, 1986, Journal of Pharmacie de Belgique, vol. 35(No. 2), pages 98-102, 1980, or by processes similar thereto, some sold as reagents. The following compounds, for example, are illustrative:

picolinic acid, nicotinic acid, isonicotinic acid, 2-chloronicotinic acid, 6-chloronicotinic acid, 2-methylnicotinic acid, 2-methoxynicotinic acid, 4-trifluoromethylnicotinic acid, 2,6-dichloronicotinic acid, 2-chloro-6-methylnicotinic acid, 4-fluoronicotinic acid, 4-chloronicotinic acid, 3-fluoroisonicotinic acid, 3-bromoisonicotinic acid, 2-chloroisonicotinic acid, 3-chloroisonicitinic acid, 4-methylnicotinic acid, 3-methylisonicotinic acid, 3-methylthioisonicotinic acid, 2-trifluoromethylnicotinic acid, 3,5-dichloroisonicotinic acid, 2-chloro-4-methylnicoticic acid, 2,6-dimethylnicoticinic acid, 2,4-dimethylnicotinic acid, 4-ethylnicotinic acid, 2-methylthionicotinic acid, 5-trifluoromethoxypicolicinc acid, 2-chloro-4,6-dimethylnicotinic acid, 6-chloro-2,4-dimethylnicotinic acid, 5-tricluoromethoxypicolinic acid, and 4,6-dimethoxy-2-trifluoromethylnicotinic acid.

The reaction of the above-mentioned process (b) can be carried out in a similar manner to the synthesis of tetrazolinones described in Journal of Chemical Society, Perkin Transaction 1, 1992, pages 1101-1104, or The Journal of American Chemical Society, Vol. 81, 1959, pages 3076-3079.

In the process (c) according to the invention, the preferred starting compounds of the formula (V) are those based on the above preferred definition of R.sup.1 and n.

The compounds of the formula (V) are well known compounds in the field of organic chemistry, for example, 2,6-dichloro-4-pyridyl isocyanate. Said compounds can also easily be obtained by Curtius rearrangement of the compounds of the above mentioned formula (IV) or by Schmidt rearrangement of compounds of the above-mentioned formula (VIII).

The reaction of the above-mentioned process (c) can be carried out in a similar manner to the synthesis of tetrazolinones described in The Journal of Organic Chemistry, Vol. 45, 1980, pages 5130 -5136 or The Journal of American Chemical Society, vol. 81, 1959, pages 3076-3079.

In the above-mentioned process (d), preferred starting compounds of the formula (VI) are those based on the above preferred definitions of R.sup.1 and n.

The compounds of the formula (VI) can easily be prepared by the following process (f): (f) compounds of the following formula(IX) ##STR14## wherein R.sup.3 and n have the same meanings as mentioned above are reacted with oxidizing agents, in the presence of inert solvents.

In the above-mentioned process (f), the preferred starting compounds of the formula (IX) are those based on the above preferred definitions of R.sup.1 and n.

In the above-mentioned process (f), the oxidizing agents preferably have a suitable oxidative effect such that one nitrogen atom of the pyridine ring is not oxidized. As examples of said oxidizing agent, there may be mentioned: OXONE.RTM. potassium permanganate, potassium hydrogen persulfate, ruthenium oxide, osmium oxide, sodium metapedodate, dinitrogen tetroxide, hydrogen peroxide, peracid, hydroperoxide and ozone. When hydrogen peroxide is used as oxidizing agent, it is advantageous to use a tungsten catalyst such as sodium tungstate.

The compounds of the formula (IX) can easily be prepared by the following process (g): (g) compounds of the following formula (X) ##STR15## wherein R.sup.3 and n have the same meanings mentioned above, are reacted with dimethyl sulfate and then, under acid conditions, the resulting products are reacted with sodium nitrite or potassium nitrite.

The reaction of the process (g) can be carried out in a manner similar to the synthesis of tetrazolinones described in Chemische Berichte vol. 34, page 3115, 1901.

In the above-mentioned process (g), the preferred starting compounds of the formula (X) are those based on the above preferred definitions of R.sup.1 and n.

The compounds of the formula (X) can be obtained by the following known process (h): (h) compounds of the following formula (XI) ##STR16## wherein R.sup.3 and n have the same meaning mentioned above, are reacted with hydrazine.

In the reaction of the process (h), the preferred starting compounds of the formula (XI) are those based on the above preferred definitions of R.sup.1 and n.

The compounds of the formula (XI) can be obtained by the following process (i): (i) compounds of the following formula (XII) ##STR17## wherein R.sup.3 and n have the same meanings mentioned above, are reacted with methyliodide.

In the reaction of the process (i), the starting compounds of the formula (XII) mean those based on the above definitions of R.sup.3 and n, and preferably based on the above preferred definitions.

The compounds of the formula (XII) can be obtained by the following process (j): (j) aminopyridines of the following formula (XlII) ##STR18## wherein R.sup.3 and n have the same meanings mentioned above, are reacted with carbon disulfide, in the presence of tertiary amines such as triethyl amine, and if appropriate in the presence of inert solvents.

In the reaction of the process (j), the starting compounds of the formula (XIII) mean those based on the above definitions of R.sup.3 and n, and preferably based on the above preferred definitions.

In the reactions of the processes (i) and (j) can be carried out in a similar manner to the method of preparing tetrazolinones described in Journal of the Chemical Society, pages 796-802, 1955 or pages 1644-1649, 1956 The compounds of the formula (XIII) are well known compounds in the field of organic chemistry. For example, said compounds may be synthesized by the processes described in Recueil des Travaux Chimiques des Pays. Bas, vol. 69, pages 673, 1950, The Journal of American Chemical Society, vol. 69, page 63, 1947, vol. 69, page 69, 1947, vol, 73 pages 5043-5046, 1951, The Journal of Organic Chemistry, vol. 19, page 1633, 1954 or by processes similar thereto, or are commercially available. As examples of said compounds, there may he mentioned:

2-aminopyridine, 3-aminopyridine, 4-aminopyridine, 2-amino-3-chloropyridine, 2-amino-3-methylpyridine, 3-amino-2-methylpyridine, 4-amino-3-methylpyridine, 2-amino-3-methoxypyridine, 2-amino-3,5-dichloropyridine, 4-amino-2,6-dichloropyridine, and 2-amino-3-chloro-5-trifluoromethylpyridine.

The compounds of the formula (XIII) can be obtained by the following known process (k): (k) chloropyridines of the formula (XIV) ##STR19## wherein R.sup.3 and n have the same meanings mentioned above, are aminated.

The above-mentioned process (k) can be carried out similarly to that described in, for example, Heterocycles vol. 26, pages 2065-2068, 1987, Vol. 22, pages 117-124, 1984, or Japanese Patent Laid-Open Application Sho 62-155260.

In the reaction of the process (k), the starting compounds of the formula (XIV) mean those based on the above definitions of R.sup.3 and n, and preferably based on the above preferred definitions.

Chloropyridines represented by the formula (XIV) are well known compounds in the field of organic chemistry, being sold as reagents, and for example there may be mentioned:

2-chloro-3-trifluoromethylpyridine, 2-chloro-5-trifluoromethylpyridine, and 2-chloro-3,5-ditrifluoromethylpyridine.

In the process (d), as examples of the inorganic bases, there may be mentioned:

sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, and potassium bicarbonate.

In the reaction of the process (e), the starting compounds of the formula (VII) mean those based on the above definitions of R.sup.3 and n, and preferably based on the above preferred definitions.

The compounds of the formula (VII) can easily be obtained by the following known process (I): (I) aminopyridines represented by the above-mentioned formula (XIII) are reacted with phenylchloroformate, if appropriate in the presence of inert solvents.

In carrying out the process (e) mentioned above, use may be made, as suitable diluent, of any inert solvent.

Examples of such diluents are aliphatic, cycloaliphatic and aromatic, optionally chlorinated, hydrocarbons such as toluene, xylene, chlorobenzene, dichlorobenzene, and the like; ethers such as ethyl ether, methyl ethyl ether, isopropyl ether, butyl ether, dioxane, dimethoxyethane (DME), tetrahydrofurane (THF), dimethylene glycol, dimethyl ether (DGM) and the like; acid amides such as dimethyl formamide (DMF), dimethyl acetamide (DMA), N-methylpyrrolidone, 1,3-dimethyl-2-imidazolidinone, hexamethylphosphoric triamide (HMPA), and the like; sulfones and sulfoxides such as dimethyl sulfoxide (DMSO), sulfolane and the like.

In the above mentioned process (e), the reaction temperature can be varied within a substantially wide range. In general, the reaction is carried out at a temperature of from about 0.degree. C. to about 200.degree. C., preferably from 20.degree. C. to about 150.degree. C.

Further, the reaction is carried out under normal pressure, although it is also possible to employ a higher or reduced pressure.

When the above mentioned process (e) according to the present invention is carried out, use is made, for example, of about 1 to 3 mols of sodium azide in a diluent such as dimethyl formamide per mol of the compounds represented by the general formula (VII) to obtain the desired compounds.

As specific examples of the formula (II), in the above-mentioned process (a), there may be mentioned:

1-(2-chloro-3-pyridyl)-5(4H)-tetrazolinone, 1-(2-chloro-4-pyridyl)-5(4H)-tetrazolinone, 1-(2-pyridyl)-5(4H)-tetrazolinone, 1-(3-pyridyl)-5(4H)-tetrazolinone, 1-(4-pyridyl)-5(4H)-tetrazolinone, 1-(3-chloro-2-pyridyl)-5(4H)-tetrazolinone, 1-(4-fluoro-3-pyridyl)-5 (4H)-tetrazolinone, 1-(3-chloro-4-pyridyl)-5(4H)-tetrazolinone, 1-(3-bromo-4-pyridyl)-5(4H)-tetrazolinone, 1-(6-chloro-3-pyridyl)-5(4H)-tetrazolinone, 1-(3-methyl-2-pyridyl)-5(4H)-tetrazolinone, 1-(3-fluoro-4-pyridyl)-5(4H)-tetrazolinone, 1-(2-methyl-3-pyridyl)-5(4H)-tetrazolinone, 1-(4-chloro-3-pyridyl)-5(4H)-tetrazolinone, 1-(3-methoxy-2-pyridyl)-5(4H)-tetrazolinone, 1-(4-methyl-3-pyridyl)-5(4H)-tetrazolinone, 1-(2-methylthio-3-pyridyl)-5(4H)-tetrazolinone, 1-(3-methyl-4-pyridyl)-5(4H)-tetrazolinone, 1-(2-trifluoromethyl-3-pyridyl)-5(4H)-tetrazolinone, 1-(2,6-dichloro-3-pyridyl)-5(4H)-tetrazolinone, 1-(3-trifluoromethyl-2-pyridyl)-5(4H)-tetrazolinone, 1-(2-chloro-6-methyl-3-pyridyl)-5(4H)-tetrazolinone, 1 -(2-methoxy-3-pyridyl)-5(4H)-tetrazolinone, 1 -(2,6-dichloro-4-pyridyl)-5(4H)-tetrazolinone, 1 -(4-trifluoromethyl-3-pyridyl)-5(4H)-tetrazolinone, 1 - (3,5-dichloro-2-pyridyl)-5(4H)-tetrazolinone, 1-(3-methylthio-4-pyridyl)-5(4H)-tetrazolinone, 1-(5-trifluoromethyl-2-pyridyl)-5(4H)-tetrazolinone, 1-(3,5-dichloro-4-pyridyl)-5(4H)-tetrazolinone, 1-(2-chloro-4-methyl-3-pyridyl)-5(4H)-tetrazolinone, 1-(3-chloro-5-trifluoromethyl-2-pyridyl)-5(4H)-tetrazolinone, 1 -(4,6-dimethoxy-2-trifluoromethyl-3-pyridyl)-5(4H)-tetrazolinone, 1-(2,6-dimethyl-3-pyridyl)-5(4H)-tetrazolinone, 1 -(6-chloro-2,4-dimethyl-3-pyridyl)-5(4H)-tetrazolinone, 1 -(3-ethyl-pyridyl)-5(4H)-tetrazolinone, 1-(2-chloro-4,6-dimethyl-3-pyridyl)-5(4H)-tetrazolinone, 1-(5-trifluoromethoxy-2-pyridyl)-5(4H)-tetrazolinone, 1-(2,4-dimethyl-3-pyridyl)-5(4H)-tetrazolinone, 1 -(3-nitro-2-pyridyl-pyridyl)-5(4H)-tetrazolinone, 1-(3,5-bis(trifluoromethyl)-2-pyridyl)-5(4H)-tetrazolinone, and 1-(2-phenoxy-3-pyridyl)-5(4H)-tetrazolinone.

In the process (a), the starling materials of the formula (III) means those based on the above mentioned definition of R.sup.1 and R.sup.2, and preferably compounds based on the above preferred definitions.

The compounds of the formula (III) are well known in the field of organic chemistry.

As examples of the compounds of the formula (III), the following compounds may be mentioned:

Diisopropylcarbamoyl chloride and bromide, Diethylcarbamoyl chloride and bromide, Dimethylcarbamoyl chloride and bromide, N-methyl-N-ethylcarbamoyl chloride and bromide, N-methyl-N-n-propylcarbamoyl chloride and bromide, N-methyl-N-isopropylcarbamoyl chloride and bromide, N-methyl-N-cyclopropylcarbamoyl chloride and bromide, N-methyl-N-s-butylcarbamoyl chloride and bromide. N-methyl-N-cyclopenthylcarbamoyl chloride and bromide, N-methyl-N-cyclohexylcarbamoyl chloride and bromide, N-methyl-N-phenylcarbamoyl chloride and bromide, N-methyl-N-1-methyl-2-propenylcarbamoyl chloride and bromide, N-ethyl-N-propylcarbamoyl chloride and bromide, N-ethyl-N-isopropylcarbamoyl chloride and bromide, N-ethyl-N-cyclopropylcarbamoyl chloride and bromide, N-ethyl-N-s-butylcarbamoyl chloride and bromide, N-ethyl-N-cyclopentylcarbamoyl chloride and bromide, N-ethyl-N-cyclohexylcarbamoyl chloride and bromide, N-ethyl-N-phenylcarbamoyl chloride and bromide, N-n-propyl-N-isopropylcarbamoyl chloride and bromide, N-n-propyl-N-cyclopropylcarbamoyl chloride and bromide, N-n-propyl-N-s-butylcarbamoyl chloride and bromide, N-n-propyl-N-cyclopentylcarbamoyl chloride and bromide, N-n-propyl-N-cyclohexylcarbamoyl chloride and bromide, N-isopropyl-N-cyclohexylcarbamoyl chloride and bromide, N-isopropyl-N-phenylcarbamoyl chloride and bromide, N-isopropyl-N-allylcarbamoyl chloride and bromide, 4-morpholinylcarbamoyl chloride add bromide, 1-(2-methylpiperidine)carbamoyl chloride and bromide, 1-(2,5-dimethylpyrrolidine)carbamoyl chloride and bromide, 1-(2,6-dimethylpiperidine)carbamoyl chloride and bromide, 1-(2-methyl-1,2,3,4-tetrahydroquinoline)carbamoyl chloride and bromide, 1-Pyrrolidinylcarbamoyl chloride and bromide, 1-Piperidylacrbamoyl chloeide and bromide, and 1-(2,5-dimethyl-3-pyrroline)carbamoyl and bromide.

In carrying out the process (a) mentioned above, use may be made, as suitable diluent, of any inert solvent.

Examples of such diluents are aliphatic, cycloaliphatic and aromatic, optionally chlorinated, hydrocarbons such as pentane, hexane, cyclohexane, petroleum ether, ligroin, benzene, toluene, xylene, dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, chlorobenzene, dichlorobenzene, and the like; ethers such as diethyl ether, methyl ethyl ether, diisopropyl ether, dibutyl ether, dioxane, dimethoxyethane(DME), tetrahydrofurane (THF) dimethylene glycol dimethyl ether and the like; nitriles such as acetonitrile, propionitrile, and the like; acid amides such as dimethyl formamide (DMF), dimethyl acetamide (DMA), N-methylpyrrolidone, 1,3-dimethyl-2-imidazolidinone, hexamethylphosphoric triamide (HMPA),and the like; sulfones and sulfoxides such as dimethyl sulfoxide (DMSO), sulfolane and the like; and bases such as pyridine.

The process (a) according to the invention is carried out preferably in the presence of acid or acid binder.

As examples of such acid binder there may be mentioned: inorganic bases including hydroxide, carbonate, bicarbonate and alcoholate of alkali metals such as, for example, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium carbonate, potassium carbonate, and the like, inorganic, alkal metal amide including lithium amide, sodium amide, potassium amide, and the like organic bases including tertiary amines, dialkylaminoanilines and pyridines such as, for example, triethylamine, tributylamine, 1,1,4,4-tetra-methylenediamine (TMEDA), N,N-dimethylaniline, N,N-diethylaniline, pyridine, 4-dimethylaminopyridine (DMAP), 1,4-diaza-bicyclo-[2,2,2]octane (DABCO), 1,8-diaza-bicyclo[5,4,0]-undec-7-ene (DBU) and the like, organic lithium compounds including methyllithium, n-butyllithium, sec-butyllithium, tert-butyllithium, phenyllithium, dimethyl copper lithium, lithiumdiisopropylamide, lithiumcyclohexylisopropylamide, lithiumdicyclohexylamide, n-butyllithium DABCO n-butyllithium TMEDA,

In the above mentioned process (a), the reaction temperature can be varied within a substantially wide range. In general, the reaction is carried out at a temperature of from about -30.degree. C. to about 200.degree. C., preferably from -200.degree. C. to about 130.degree. C.

Further, the reaction is carried out under normal pressure, although it is also possible to employ a higher or reduced pressure.

When the above mentioned process (a) according to the present invention is carried out, use is made, for example, of about 1.0 to 1.5 mols of the compound of the formula (III) in a diluent such as toluene per mol of the compounds represented by the general formula (II) in the presence of 1 to 1.5 mols of the acid binder to obtain the desired compounds.

The active compounds according to the invention can be used as defoliants, desiccants, agents for destroying broad-leaved plants and, especially, as weedkillers.

By weeds, in the broadest sense, there are to be understood all plants which grow in locations where they are undesired. Whether the substances according to the invention act as total or selective herbicides depends essentially on the amount used.

The active compounds according to the invention can be used, for example, in connection with the following plants:

Dicotyledon weeds of the genera: Sinapis, Lepidium, Galium, Stellaria, Matricada, Anthemis, Galinsoga, Chenopodium, Urtica, Senecio, Amaranthus, Portulaca, Xanthium, Convolvulus, Ipomoea, Polygonum, Sesbania, Ambrosia, Cirsium, Carduus, Sonchus, Solanum, Rorippa, Rotala, Lindernia, Lamium, Veronica, Abutilon, Emex, Datura, Viola, Galeopsis, Papaver and Centaurea.

Dicotyledon cultures of the genera: Gossypium, Glycine, Beta, Daucus, Phaseolus, Pisum, Solanum, Linum, Ipomoea, Vicia, Nicotiana, Lycopersicon, Arachis, Brassica, Lactuca, Cucumis and Cucurbita.

Monocotyledon weeds of the genera: Echinochloa, Setaria, Panicum, Digitaria, Phleum, Poa, Festuca, Eleusine, Brachiaria, Lolium, Bromus, Avena, Cyperus, Sorghum, Agropyron, Cynodon, Monochoria, Fimbristylis, Sagittaria, Eleocharis, Scirpus, Paspalum, Ischaemum, Sphenoclea, Dactyloctenium, Agrostis, Alopecurus and Apera.

Monocotyledon cultures of the genera: Oryza, Zea, Triticum, Hordeurn, Avena, Secale, Sorghum, Panicum, Saccharum, Ananas, Asparagus and Allium.

However, the use of the active compounds according to the invention is in no way restricted to these genera, but also extends in the same manner to other plants.

The compounds are suitable, depending on the concentration, for the total combating of weeds, for example on industrial terrain and rail tracks, and on paths and squares with or without tree plantings. Equally, the compounds can be employed for combating weeds in perennial cultures, for example afforestations, decorative tree plantings, orchards, vineyards, citrus groves, nut orchards, banana plantations, coffee plantations, tea plantations, rubber plantations, oil palm plantations, cocoa plantations, soft fruit plantings and hopfields, and for the selective combating of weeds in annual cultures.

The active compounds can be converted into the customary formulations, such as solutions, emulsions, wettable powders, suspensions, powders, foams, pastes, granules, tablets, aerosols, natural and synthetic materials impregnated with active compound, very fine capsules in polymeric substances, coating compositions for on seed, and formulations used with burning equipment, such as fumigating cartridges, fumigating cans and fumigating coils, as well as ULV cold mist and warm mist formulations.

These formulations may be produced in known manner, for example by mixing the active compounds with extenders, that is to say liquid or liquefied gaseous or solid diluents or carriers, optionally with the use of surface-active agents, that is to say emulsifying agents and/or dispersing agents and/or foam-forming agents. In the case of the use of water as an extender, organic solvents can, for example, also be used as auxiliary solvents.

As liquid solvents diluents or carriers, there are suitable in the main, aromatic hydrocarbons, such as xylene, toluene or alkyl napthalenes, chlorinated aromatic or chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, for example mineral oil fractions, alcohols, such as butanol or glycol as well as their ethers and esters, ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, or strongly polar solvents, such as dimethylformamide and dimethylsulphoxide, as well as water.

By liquefied gaseous diluents or carriers are meant liquids which would be gaseous at normal temperature and under normal pressure, for example aerosol propellants, such as halogenated hydrocarbons as well as butane, propane, nitrogen and carbon dioxide.

As solid carriers there may be used ground natural minerals, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and ground synthetic minerals, such as highly-dispersed silicic acid, alumina and silicates. As solid carriers for granules there may be used crushed and fractionated natural rocks such as calcite, marble, pumice, sepiolite and dolomite, as well as synthetic granules of inorganic and organic meals, and granules of organic material such as sawdust, coconut shells, corn cobs and tobacco stalks.

As emulsifying and/or foam-forming agents there may be used non-ionic and anionic emulsifiers, such as polyoxyethylene-acid esters, polyoxyethylene-alcohol ethers, for example alkylaryl polyglycol ethers, alkyl sulphonates, alkyl sulphates, aryl sulphonates as well as albumin hydrolysis products.

Dispersing agents include, for example, lignin sulphite waste liquors and methylcellulose.

Adhesives such as carboxymethylcellulose and natural and synthetic polymers in the form of powders, granules or latices, such as gum arabic, polyvinyl alcohol and polyvinyl acetate, can be used in the formulation.

It is possible to use colorants such as inorganic pigments, for example iron oxide, titanium oxide and Prussian Blue, and organic dyestuffs, such as align dyestuffs, azo dyestuffs or metal phthalocyanine dyestuffs, and trace nutrients, such as salts of iron, manganese boron, copper, cobalt, molybdenum and zinc.

The formulations in general contain from 0.1 to 95 per cent by weight of active compound, preferably from 0.5 to 90 per cent by weight.

The active compounds according to the invention, as such or in the form of their formulations, can also be used, for combating weeds, as mixtures with known herbicides, finished formulations or tank mixes being possible.

Mixtures with other known active compounds, such as herbicides, fungicides, insecticides, acadcides, nematicides, bird repellents, plant nutrients and agents which improve soil structure, are also possible.

The active compounds can be used as such, in the form of their formulations or in the use forms prepared therefrom by further dilution, such as ready-to-use solutions, suspensions, emulsions, powders, pastes and granules.

They are used in the customary manner, for example by watering, spraying, atomizing or scattering.

The active compounds according to the invention can be applied either before or after emergence of the plants. They can also be incorporated into the soil before sowing. They are used, in particular, after emergence of the plants.

The amount of active compound used can vary within a substantial range. It depends essentially on the nature of the desired effect. In general, the amounts used are between 0.001 and 10 kg of active compound per hectare of soil surface, preferably between 0.01 and 5 kg per ha.

The preparation and use of the active compounds according to the invention can be seen from the following examples.

EXAMPLE 1 ##STR20##

1-(2-chloro-3-pyridyl)-5(4H)-tetrazolinone (1.0 g), diethylcarbamoyl chloride (0.7 g) and 4-dimethylaminopyridne (0.7 g) were suspended in toluene (15 ml). The resulting suspension was heated under reflux for 6 hours. The salts were removed, by filtration, and the solvent was distilled off under reduced pressure. The resulting residue was subjected to a silica gel chromatography (chloroform) so that 1-(2-chloro-3-pyridyl )-4-(N,N-diethylcarbamoyl)-5(4H)-tetrazolinone(1.3 g) was obtained.

n.sub.D.sup.20 =1.5511

Further compounds obtainable by the above-mentioned reaction procedure are shown in Table 3-1.

TABLE 3-1______________________________________ ##STR21##CompoundNo. Q R.sup.1 R.sup.2 Physical Constant______________________________________2 Q2 ethyl ethyl n.sub.D.sup.20 = 1.54263 Q3 ethyl ethyl m.p. 72.5-75.degree. C.4 Q5 methyl isopropyl m.p. 99.5-101.degree. C.5 Q5 ethyl isopropyl m.p. 87.5-89.5.degree. C.6 Q5 ethyl cyclohexyl m.p. 56.5-60.degree. C.7 Q5 allyl allyl n.sub.D.sup.20 = 1.56168 Q5 propargyl propargyl m.p. 142-145.5.degree. C.9 Q7 ethyl ethyl m.p. 61-62.degree. C.10 Q11 methyl isopropyl n.sub.D.sup.20 = 1.556111 Q11 ethyl ethyl m.p. 70-71.5.degree. C.12 Q12 ethyl ethyl m.p. 63-67.degree. C.13 Q12 ethyl isopropyl n.sub.D.sup.20 = 1.557914 Q14 ethyl ethyl m.p. 51.5-53.5.degree. C.15 Q14 ethyl isopropyl n.sub.D.sup.20 = 1.5388______________________________________ TABLE 3-2______________________________________CompoundNo. Q R.sup.1 R.sup.2 Physical Constant______________________________________16 Q19 methyl isopropyl m.p. 115.5-118.5.degree. C.17 Q19 ethyl ethyl m.p. 68.5-72.5.degree. C.18 Q19 ethyl isopropyl n.sub.D.sup.20 = 1.568519 Q24 ethyl ethyl n.sub.D.sup.20 = 1.503220 Q26 methyl isopropyl m.p. 113.5-115.5.degree. C.21 Q26 ethyl ethyl m.p. 104-109.5.degree. C.22 Q26 ethyl isopropyl m.p. 105-109.degree. C.23 Q27 ethyl ethyl m.p. 119.5-120.5.degree. C.24 Q29 methyl isopropyl m.p. 112-115.degree. C.25 Q29 ethyl ethyl m.p. 105.5-107.5.degree. C.26 Q29 ethyl isopropyl m.p. 126-128.degree. C.27 Q30 methyl isopropyl m.p. 124.5-127.5.degree. C.28 Q30 ethyl ethyl n.sub.D.sup.20 = 1.544229 Q30 ethyl isopropyl n.sub.D.sup.20 = 1.539730 Q41 ethyl ethyl m.p. 87.5-90.5.degree. C.______________________________________

Synthesis of starting materials

EXAMPLE 2 ##STR22##

2-Chloroisonicotinic acid (4.7 g) and thionyl chloride (10.0 g) were mixed and the resulting mixture was heated under reflux for 2 hours. The excess thionyl chloride was distilled off under reduced pressure, and trimethylsilyl azide (10.0 g) was added to the residue thus obtained. The resulting mixture was heated under reflux for 24 hours, and the excess trimethylsilyl azide was distilled off under reduced pressure and then methanol was added to the residue thus obtained. Thereafter, the methanol was distilled off and the resultant residue was subjected to a silica gel chromatography, using chloroform:ethanol=15: 1, so that 1-(2-chloro-4-pyridyl)-5(4H)-tetrazolinone (4.6 g) was obtained.

m.p. 182.5.degree.-184.degree. C. (decomposition).

1-(3-Pyridyl)-5(4H)-tetrazolinone (1.0 g) was obtained by the same process as was used in the Example 2 with the exception that nicotinic acid (1.1 g) was used instead of 2-chloroisonicotinic acid.

m.p. 201.5.degree.-202.5.degree. C.

1-(4-Pyridyl)-5(4H)-tetrazolinone (3.3 g) was obtained by the same process as was used in the Example 2 with the exception that isonicotinic acid (3.5 g) was used instead of 2-chloroisonicotinic acid.

m.p. more than 300.degree. C.

1-(6-Chloro-3-pyridyl)-5(4H)-tetrazolinone (3.8 g) was obtained by the same process as was used in the Example 2 with the exception that 6-chloronicotinic acid (3.5 g) was used instead of 2-chloroisonicotinic acid.

m.p. 212.degree.-212.5.degree. C.

1-(3-Chloro-4-pyridyl)-5(4H)-tetrazolinone (1.8 g) was obtained by the same process as was used in the Example 2 with the exception that 3-chloroisonicotinic acid (4.7 g) was used instead of 2-chloroisonicotinic acid.

m.p. 176.degree.-178.5.degree. C. (decomposition).

1-(2-Methyl-3-pyridyl)-5(4H)-tetrazolinone (3.9 g) was obtained by the same process as was used in the Example 2 with the exception that, 2-methyl-nicotinic acid(4.1 g) was used instead of 2-chloroisonicotinic acid.

m.p. 174.5.degree.-176.degree. C. (decomposition).

1-(2-Methylthio-3-pyridyl)-5(4H)-tetrazolinone (4.5 g) was obtained by the same process as was used in the Example 2 with the exception that 2-methylthionicotinic acid (5.1 g) was used instead of 2-chlomisonicotinic acid.

m.p. 168.degree. C. (decomposition).

1-(2-Chloro-6-methyl-3-pyridyl)-5(4H)-tetrazolinone (4.3 g) was obtained by the same process as was used in the Example 2 with the exception that 2-chloro-6-methylnicotinic acid (4.9 g) was used instead of 2-chloroisonicotinic acid.

m.p. 196.degree.-197.5.degree. C.

1-(4-trifluoromethyl-3-pyridyl)-5(4H)-tetrazolinone (1.2 g) was obtained by the same process as was used in the Example 2 with the exception that 4-trifluoromethylnicoticic acid (5.0 g) was used instead of 2-chloroisonicotinic acid.

m.p. 129.5.degree.-132.5.degree. C.

1-(2,6-Dichloro-4-pyridyl)-5(4H)-tetrazolinone (3.5 g) was obtained by the same process as was used in the Example 2 with the exception that 2,6-dichloroisonicotinic acid (6.8 g) was used instead of 2-chloroisonicotinic acid.

m.p. 123.degree.-128.degree. C.

EXAMPLE 3 ##STR23##

2-Chloro-3-pyridyl isocyanate (3.1 g) was mixed with trimethylsilyl azide (3.5 g), and the resulting mixture was heated under reflux for 20 hours. The excess trimethylsilyl azide was distilled off under reduced pressure, and methanol was added to the residue thus obtained. Thereafter, the methanol was distilled off, and the resultant residue was subjected to a silica gel column chromatography, using chloroform; ethanol=15:1, so that 1-(2-chloro-3-pyridyl)-5(4H)-tetrazolinone (3.0 g) was obtained.

m.p. 177.5.degree.-178.5.degree. C.

1-(2,6-Dichloro-4-pyridyl)-5(4H)-tetrazolinone (3.7 g) was obtained by the same process as was used in the Example 3 with the exception that 2,6-dichloro-4-pyridyl isocyanate (3.2 g) was used instead of 2-chloro-3-pyridyl isocyanate.

m.p. 191.degree.-191.5.degree. C.

1-(2,6-Dichloro-3-pyridyl)-5(4H)-tetrazolinone (3.5 g) was obtained by the same process as was used in the Example 3 with the exception that 2,6-dichloro-3-pyridyl isocyanate (5.7 g) was used instead of 2-chloro-3-pyridyl isocyanate.

m.p. 176.degree.-177.degree. C.

1-(2-Chloro-4-methyl-3-pyridyl)-5(4H)-tetrazolinone (4.1 g) was obtained by the same process as was used in the Example 3 with the exception that 2-chloro-4-methyl-3-pyridyl isocyanate (3.4 g) was used instead of 2-chloro-3-pyridyl isocyanate.

m.p. 160.degree.-162.degree. C.

EXAMPLE 4 ##STR24##

1-(2-Pyridyl)-5-methanesulfonyl-tetrazole (0.90 g) and tetrahydrofurane (15 ml) were added to water (1 ml) containing dissolved sodium hydroxide (0.80 g) and the resulting mixture was heated under reflux for 3. hours. After solvent was distilled off under reduced pressure, the resultant residue was subjected to a silica gel column chromatography, using chloroform:ethanol=15: 1, so that 1-(2-pyridyl)-5(4H)-tetrazolinone (0.2 g) was obtained.

m.p. 147.degree.-147.5.degree. C. (decomposition)

EXAMPLE 5

Starting material of Example 4 ##STR25##

1-(2-Pyridyl)-5-methylthiotetrazole(1.5 g), OXONE.RTM. (9.6 g ), water (15 ml) and ethanol (45 ml) were mixed and the resulting mixture was stirred at room temperature for 24 hours. After solvent was distilled off under reduced pressure, the resultant residue was subjected to a silica gel column chromatography (chloroform) so that 1-(2-pyridyl)-5-methanesulfonyl-tetrazole (1.0 g) was obtained.

m.p. 110.5.degree.-112.degree. C.

EXAMPLE 6

Starting material of Example 5 ##STR26##

4-(2-Pyridyl)-3-thiosemicarbazide (12.2 g), suspended to water (30 ml),and dimethylsufate (9.15 g) was added to the suspension. The resulting suspension was stirred for 3 hours. To this solution concentrated hydrochloric acid (30 ml) was added and the solution was cooled to 0.degree. C. An aqueous solution (15 ml) of sodium nitrite (5.8 g) was added dropwise to the solution while maintaining the temperature and, after having stirred at 0.degree. C. for 2 hours, the solution was neutralized by potassium carbonate and then extracted with chloroform. After drying with anhydrous sodium sulfate, the residue was subjected to a silica gel column chromatography (chloroform) so that 1-(2-pyridyl)-5-methylthiotetrazole (2.0 g) was obtained.

m.p. 106.degree.-108.degree. C.

EXAMPLE 7

Starting material of Example 6 ##STR27##

Methyl N-(2-pyridyl)dithiocarbamate (22.6 g), hydrazine monohydrate (12.3 g) and ethanol (300 ml) were mixed and the resulting mixture was heated under reflux for 3 hours. After distilling off the solvent under reduced pressure, water was added to the residue thus obtained, and a deposited material was obtained by filtration and dried by air, so that 4-(2-pyridyl)-3-thiosemicarbazide (18.9 g) was obtained.

m.p. 192.5.degree.-193.degree. C.

EXAMPLE 8 ##STR28##

Anhydrous aluminum chloride (8.6 g) was added to dimethylformamide (50 ml) under ice-cooling and the resulting mixture was stirred for 15 minutes. Sodium azide (3.8 g) was further added to that mixture and the mixture obtained was stirred for 15 minutes. After said stirring, phenyl N-(2-pyridyl)carbamate (6.3 g) was added to the mixture, and the resulting mixture was stirred at 80.degree. C. for 10 hours. The reaction solution was added to the mixture of sodium nitrite (4 g), water (500 ml) and ice (250 g). After acidifying with 10% hydrochloric acid solution (until coloring the potassium iodide starch paper), the solution was extracted by ethyl acetate, and then the ethyl acetate phase obtained was dried with sodium sulfate. Thereafter solvent was distilled off under reduced pressure, the resultant residue was subjected to a silica gel column chromatography, so that 1-(2-pyridyl)-5(4H)-tetrazolinone was obtained (0.2 g).

m.p. 147.degree.-147.5.degree. C. (decomposition).

EXAMPLE 9

Starting material of the Example 8 ##STR29##

2-Aminopyridine (9.4 g) was dissolved in pyridine (150 ml) and phenylchloroformate (15.7 g) was added dropwise to the resulting solution under cooling at 0.degree. C. After stirring at 0.degree. C. for 2 hours, the solvent was distilled off under reduced pressure, and water was added to the residue thus obtained. Deposited crystals were separated by filtration and dried by air to obtain phenyl N-(2-pyridyl) carbamate (18.9 g).

m.p. 161.degree.-162.5.degree. C.

EXAMPLE 10 ##STR30##

3-Amino-2-chloro-4-methylpyridine (4.3 g) was added to a solution of trichloromethyl chloformate (6.0 g) in ethyl acetate (100 ml) at 0.degree. to 5.degree. C. with stirring and the mixture was refluxed under heating for 6 hours. After removal of the solvent under reduced pressure, 2-chloro-4-methyl-3-pyridylisocyanate (4.9 g) was obtained. A mixture of 2-chloro-4-methyl-3-pyridylisocyanate (4.9 g) and trimethylsilyl azide (11 g) was refluxed under heating for 30 hours. After removal of excess trimethylsilyl azide under reduced pressure, methanol was added to the resulting residue. Thereafter, the methanol was distilled off under reduced pressure. The resulting residue was purified by flash column chromatography (eluent chloroform:ethanol=15:1) to obtain the desired 1-(2-chloro-4-methyl-3-pyridyl)-5(4H)-tetrazolinone (3.0 g). n.p. 160.degree.-162.degree. C.

Biological tests

EXAMPLE 11

(Pre-emergence soil treatment test on upland weeds)

Formulation of Active Compounds

Carrier: 5 parts by weight of acetone Emulsifier: 1 part by weight of benzyloxy polyglycol ether

To prepare suitable formulations, 1 part by weight of each of the active compounds was mixed with the above-stated amounts of the carrier and the emulsifier, and the resulting emulsifiable concentrate was then diluted with water to the desired concentrations.

Test Procedure

In a greenhouse, a number of test pots each having an area of 120 cm.sup.2 were charged with soil taken from a cultivated field. Seeds of barnyard-grass and wild amaranth (Amaranthus blitum) were sown onto the soil surfaces in the respective test pots and each of the thus sown soil surfaces was covered with a soil layer.

Predetermined dosages of the active compounds of formulations prepared as mentioned above were uniformly sprayed onto the soil surface in the respective test pots.

Four weeks after the spraying of the active compound formulations, the herbicidal effects on the weeds were determined. The herbicidal effects were rated according to the following assessment:

Completely killed 100% Condition equivalent to non-treated pots 0%

In the above-mentioned test, for example, compound Nos. 1, 3, 4, 5, 11, 12, 13, 15, 17, 18, 21, 22, 25 and 26 according to the present invention showed 100% herbicidal effect against barnyard-grass and wild amaranth at a dosage of 1.0 kg/ha.

EXAMPLE 12

(Post-emergence foliage treatment on upland weeds)

Test Procedure

In a greenhouse, a number of test pots each having an area of 120 cm.sup.2 were charged with soil taken from a cultivated field. Seeds of barnyard-grass and wild amaranth (Amaranthus blitum) were sown onto the soil surfaces in the respective test pots and each of the thus sown soil surfaces was covered with a soil layer.

Ten days after sowing (average 2 leaf stage of weeds), predetermined dosages of active compounds of formulations prepared as in Example 10 were uniformly sprayed onto the foliage portions of the test plants in the respective test pots.

Three weeks after the spraying of the active compound formulations, the herbicidal effects on the weeds were determined.

In the above-mentioned test, for example, the compounds Nos. 1, 4, 13, 15 and 22 according to the present invention showed 100% herbicidal effect against barnyard-grass and wild amaranth at a dosage of 1.0 kg/ha.

It will be appreciated that the instant specification and the claims are set forth by way of illustration and not limitation, and that various modification and changes my be made without departing from the spirit and scope of the present invention.

Claims

1. A pyridyltetrazolinone of the formula ##STR31## in which R.sup.1 is C.sub.1-6 alkyl, C.sub.1-6 haloalkyl, C.sub.3-8 cycloalkyl, C.sub.2-6 alkenyl, C.sub.2-6 haloalkenyl, C.sub.3-6 alkynyl or phenyl, and

R.sup.2 is C.sub.1-6 alkyl, C.sub.1-6 haloalkyl, C.sub.3-8 cycloalkyl, C.sub.2-6 alkenyl, C.sub.2-6 haloalkenyl, C.sub.3-6 alkynyl or phenyl, or

R.sup.1 and R.sup.2 together with the nitrogen atom to which they are bonded are pyrrolidinyl, 2,5-dimethylpyrrolidinyl, pyrrolinyl, 2,5-dimethyl-3-pyrrolinyl, piperidyl, 2-methylpiperidyl, 2,6-dimethylpiperidyl, piperazinyl, morpholinyl, 1,2,3,4-tetrahydroquinolyl or 2-methyl-1,2,3,4-tetrahydroquinolyl,

n is 0, 1, 2, or 3, and

R.sup.3 is nitro, fluoro, chloro, bromo, C.sub.1-4 haloalkyl, C.sub.1-4 alkoxy, C.sub.1-4 haloalkoxy, C.sub.1-4 alkylthio or phenoxy.

2. A compound according to claim 1, in which

R.sup.1 is C.sub.1-4 alkyl, C.sub.1-4 haloalkyl, cyclopropyl, cyclopentyl, cyclohexyl, C.sub.2-4 alkenyl, C.sub.2-4 haloalkenyl, C.sub.3-4 alkynyl phenyl, and

R.sup.2 is C.sub.1-4 alkyl, C.sub.1-4 haloalkyl, cyclopropyl, cyclopentyl, cyclohexyl, C.sub.2-4 alkenyl, C.sub.2-4 haloalkenyl, C.sub.3-4 alkynyl or phenyl,

n is 0, 1 or 2, and

R.sup.3 each independently is nitro, fluoro, chloro, bromo, 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 or phenoxy.

3. A compound according to claim 1, wherein such compound is 1-(2-chloro-3-pyridyl)-4-(N,N-diethylcarbamoyl)-5(4H)-tetrazolinone of the formula ##STR32##

4. A compound according to claim 1, wherein such compound is 1-(2-chloro-3-pyridyl)-4-(N-methyl-N-isopropyl)-5(4H)-tetrazolinone of the formula ##STR33##

5. A compound according to claim 1, wherein such compound is 1-(3-chloro-4-pyridyl)-4(N-ethyl-N-isopropyl-carbamoyl)-5(4H)-tetrazolinone of the formula ##STR34##

6. A compound according to claim 1, wherein such compound is 1-(2-methyl-3-pyridyl)-4-(N-ethyl-N-isopropyl)-5(4H)-tetrazolinone of the formula ##STR35##

7. A compound according to claim 1, wherein such compound is 1-(2,6-dichloro-3-pyridyl)-4-(N-ethyl-N-isopropyl)-5(4H)-tetrazolinone of the formula ##STR36##

8. A herbicidal composition comprising a herbicidally effective amount of a compound according to claim 1 and a diluent.

9. A method of combating unwanted vegetation which comprises applying to such vegetation or to a locus from which it is desired to exclude such vegetation a herbicidally effective amount of a compound according to claim 1 and a diluent.

10. The method according to claim 10, wherein such compound is

1-(2-chloro-3-pyridyl)-4-(N,N-diethylcarbamoyl)-5(4H)-tetrazolinone,

1-(2-chloro-3-pyridyl)-4-(N-methyl-N-isopropyl)-5(4H)-tetrazolinone,

1-(3-chloro-4-pyridyl)-4-(N-ethyl-N-isopropyl-carbamoyl)-5-(4H)-tetrazolinone,

1-(2-methyl-3-pyridyl)-4-(N-methyl-N-isopropyl)-5(4H)-tetrazolinone, or

1-(2,6-dichloro-3-pyridyl)-4-(N-methyl-N-isopropyl)-5(4H)-tetrazolinone.