Difluoromethyltriazolone compounds, use of the same and intermediates for the production thereof

Abstract

A triazolone compound of the formula [I]: wherein; R 1 represents optionally substituted phenyl or the like, T represents m-phenylene optionally substituted by methyl or the like; and a fungicidal composition containing it as an active ingredient.

1 . A triazolone compound of the formula [I]:  
       
         
           
           
               
               
           
         
       
       wherein, 
 R 1  represents A 1 -L 1 -, A 1 -ON═CA 2 -, A 1 -ON═C(Me)CH 2 ON═CA 2 -, A 1 -C(A 2 )=N—OCH 2 —, A 1 S—C (A 2 )=N—, A 1 -C(═S)NH—, A 1 S—C(═S)NH—, A 1 S—C(SA 2 )=N—, A 1 -ON═C(CN)—, A 1 -ON═C(Me)CH 2 ON═C(CN)—, A 1 -C(CN)═N—OCH 2 —, halogen atom, nitro or cyano; 
 wherein, L 1  represents single bond, oxygen atom, sulfur atom, carbonyl, —OCH 2 —, —SCH 2 —, —C(═O)O—, —OC(═O)—, —C(═O)OCH 2 —, —NH— or C 1 -C 6  alkylimino;  
 A 1  and A 2 , which are the same or different, represent hydrogen atom, C 1 -C 10 alkyl, C 2 -C 10 alkenyl, C 2 -C 10 alkynyl, C 3 -C 10  cycloalkyl, (C 3 -C 10  cycloalkyl) alkyl, C 5 -C 10  cycloalkenyl, (C 5 -C 10  cycloalkenyl) alkyl, phenyl, naphthyl, phenyl C 1 -C 10 alkyl, naphtyl C 1 -C 10 alkyl, 5- or 6-membered heterocyclic group optionally condensed with a benzene ring, or methyl substituted by a 5- or 6-membered heterocyclic group optionally condensed with a benzene ring;  
 the alkyl, the alkenyl, the alkynyl, the cycloalkyl, the cycloalkylalkyl, the cycloalkenyl and the cycloalkenylalkyl, represented by A 1  and A 2 , may optionally be each substituted by one or more substituents selected from the group consisting of halogen atom(s), cyano, nitro, C 1 -C 10  alkoxy, C 1 -C 10  haloalkoxy, C 1 -C 10  alkylthio, C 1 -C 10  haloalkylthio, (C 1 -C 9  alkyl) carbonyl, (C 1 -C 9  alkoxy) carbonyl, (C 1 -C 9  alkyl) carbonylamino, phenyl, phenoxy, benzyloxy and tri(C 1 -C 10  alkyl) silyl;  
 the phenyl, the naphthyl, the benzene ring in the phenylalkyl, the naphthalene ring in the phenylnaphthyl, the heterocyclic group, and the heterocyclic ring in the methyl substituted by a heterocylic group, represented by A 1  and A 2 , may optionally be each substituted by one or more substituents selected from the group consisting of halogen atom(s), cyano, nitro, C 1 -C 10  alkyl, C 1 -C 10  haloalkyl, C 3 -C 10  cycloalkyl, C 1 -C 10  alkoxy, C 1 -C 10  haloalkoxy, C 1 -C 10  alkylthio, C 1 -C 10  haloalkylthio, (C 1 -C 9  alkyl) carbonyl, (C 1 -C 9  alkoxy) carbonyl, (C 1 -C 9  alkyl) carbonylamino, phenyl, phenoxy, benzyloxy, tri(C 1 -C 10  alkyl) silyl, methylenedioxy and difluoromethylene dioxy;  
 with the proviso, when L 1  is single bond, A 1  is not a hydrogen atom;  
 
 T represents optionally substituted m-phenylene, optionally substituted m-azaphenylene or optionally substituted m-diazaphenylene bonded to R 1  and to CH 2  each via a carbon atom; 
 wherein the substituent(s) are one or more substituents selected from the group consisting of halogen atom(s), cyano, nitro, C 1 -C 6  alkyl, C 1 -C 6  haloalkyl, C 1 -C 6  alkoxy, C 1 -C 6 haloalkoxy, C 1 -C 6 alkylthio, C 1 -C 6 haloalkylthio and (C 1 -C 5  alkoxy) carbonyl.  
 
 
     
     
         2 . The triazolone compound according to  claim 1 , wherein T is optionally substituted m-phenylene; 
 wherein the substituent(s) are one or more substituents selected from the group of halogen atom(s), cyano, nitro, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 1 -C 6 alkoxy, C 1 -C 6 haloalkoxy, C 1 -C 6  alkylthio, C 1 -C 6  haloalkylthio and (C 1 -C 5  alkoxy)carbonyl.    
     
     
         3 . The triazolone compound according to  claim 1 , wherein T is optionally substituted m-azaphenylene or optionally substituted m-diazaphenylene bonded to R 1  and to CH 2  each via a carbon atom; 
 wherein the substituent(s) are one or more substituents selected from the group of halogen atom(s), cyano, nitro, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 1 -C 6 alkoxy, Cl-C 6 haloalkoxy, C 1 -C 6  alkylthio, C 1 -C 6  haloalkylthio and (C 1 -C 5  alkoxy) carbonyl.    
     
     
         4 . The triazolone compound according to  claim 1 , wherein T is optionally substituted m-phenylene; 
 wherein the substituent(s) are halogen atom(s) or methyl; R 1  is optionally substituted phenyl;    wherein the substituent(s) are one or more substituents selected from the group consisting of halogen atom(s), cyano, nitro, C 1 -C 10  alkyl, C 1 -C 10  haloalkyl, C 3 -C 10  cycloalkyl, C 1 -C 10  alkoxy, C 1 -C 10  haloalkoxy, C 1 -C 10  alkylthio, C 1 -C 10  haloalkylthio, (C 1 -C 9  alkyl) carbonyl, (C 1 -C 9  alkoxy) carbonyl, (C 1 -C 9  alkyl) carbonylamino, phenyl, phenoxy, benzyloxy, tri(C 1 -C 10  alkyl) silyl, methylenedioxy and difluoromethylenedioxy.    
     
     
         5 . The triazolone compound according to  claim 1 , which is represented by the formula [LX]:  
       
         
           
           
               
               
           
         
       
       wherein; 
 R 1  is optionally substituted phenyl; 
 wherein the substituent(s) are one or more substituents selected from the group consisting of halogen atom(s), cyano, nitro, C 1 -C 10  alkyl, C 1 -C 10  haloalkyl, C 3 -C 10  cycloalkyl, C 1 -C 10  alkoxy, C 1 -C 10  haloalkoxy, C 1 -C 10  alkylthio, C 1 -C 10  haloalkylthio, (C 1 -C 9  alkyl) carbonyl, (C 1 -C 9  alkoxy) carbonyl, (C 1 -C 9  alkyl) carbonylamino, phenyl, phenoxy, benzyloxy, tri(C 1 -C 10  alkyl) silyl, methylenedioxy and difluoromethylenedioxy.  
 
 
     
     
         6 . 5-Difluoromethyl-2-methyl-4-(2-methyl-5-phenylbenzyl)-2,4-dihydro-3H-1,2,4-triazol-3-one; which is the triazolone compound according to  claim 4 , wherein R 1  is phenyl.  
     
     
         7 . A fungicidal composition containing the triazolone compound according to  claim 1  as an active ingredient, and an inactive carrier.  
     
     
         8 . The fungicidal composition according to  claim 6 , which is containing 5-difluoromethyl-2-methyl-4-(2-methyl-5-phenylbenzyl)-2,4-dihydro-3H-1,2,4-triazol-3-one as an active ingredient, and an inactive carrier.  
     
     
         9 . 5-Difluoromethyl-2-methyl-2,4-dihydro-3H-1,2,4-triazol-3-one of the formula [L]:  
       
         
           
           
               
               
           
         
       
     
     
         10 . A difluoroacetyl semicarbazide compound of the formula [XXVI]:  
       
         
           
           
               
               
           
         
       
       wherein, 
 R 1  represents A 1 -L 1 -, A 1 -ON═CA 2 -, A 1 -ON═C(Me)CH 2 ON═CA 2 -, A 1 -C(A 2 )=N—OCH 2 —, A 1 S—C(A 2 )=N—, A 1 -C(═S)NH—, A 1 S—C(═S)NH—, A 1 S—C(SA 2 )=N—, A 1 -ON═C(CN)—, A 1 -ON═C(Me)CH 2 ON═C(CN)—, A 1 -C(CN)═N—OCH 2 —, halogen atom, nitro or cyano; 
 wherein L 1  represents single bond, oxygen atom, sulfur atom, carbonyl, —OCH 2 —, —SCH 2 —, —C(═O)O—, —OC(═O)—, —C(═O)OCH 2 —, —NH— or C 1 -C 6  alkylimino;  
 A 1  and A 2 , which are the same or different, represent hydrogen atom, C 1 -C 10 alkyl, C 2 -C 10 alkenyl, C 2 -C 10 alkynyl, C 3 -C 10  cycloalkyl, (C 3 -C 10  cycloalkyl) alkyl, C 5 -C 10  cycloalkenyl, (C 5 -C 10  cycloalkenyl) alkyl, phenyl, naphthyl, phenyl C 1 -C 10  alkyl, naphtyl C 1 -C 10  alkyl, 5- or 6-membered heterocyclic group optionally condensed with a benzene ring, or methyl substituted by a 5- or 6-membered heterocyclic group optionally condensed with a benzene ring;  
 the alkyl, the alkenyl, the alkynyl, the cycloalkyl, the cycloalkylalkyl, the cycloalkenyl and the cycloalkenyl alkyl represented by A 1  and A 2 , may optionally be each substituted by one or more substituents selected from the group consisting of halogen atom(s), cyano, nitro, C 1 -C 10  alkoxy, C 1 -C 10  haloalkoxy, C 1 -C 10  alkylthio, C 1 -C 10  haloalkylthio, (C 1 -C 9  alkyl) carbonyl, (C 1 -C 9  alkoxy) carbonyl, (C 1 -C 9  alkyl) carbonylamino, phenyl, phenoxy, benzyloxy and tri (C 1 -C 10  alkyl) silyl;  
 the phenyl, the naphthyl, the benzene ring in the phenylalkyl, the naphthalene ring in the phenylnaphthyl, the heterocyclic group, and the heterocyclic ring in the methyl substituted by a heterocylic group, represented by A 1  and A 2 , may optionally be each substituted by one or more substituents selected from the group consisting of halogen atoms, cyano, nitro, C 1 -C 10  alkyl, C 1 -C 10  haloalkyl, C 3 -C 10  cycloalkyl, C 1 -C 10  alkoxy, C 1 -C 10  haloalkoxy, C 1 -C 10  alkylthio, C 1 -C 10  haloalkylthio, (C 1 -C 9  alkyl) carbonyl, (C 1 -C 9  alkoxy) carbonyl, (C 1 -C 9  alkyl) carbonylamino, phenyl, phenoxy, benzyloxy, tri(C 1 -C 10  alkyl) silyl, methylenedioxy and difluoromethylenedioxy;  
 with the proviso, when L 1  is single bond, A 1  is not a hydrogen atom;  
 
 T represents optionally substituted m-phenylene, optionally substituted m-azaphenylene or optionally substituted m-diazaphenylene bonded to R 1  and to CH 2  each via a carbon atom; 
 wherein the substituent(s) are one or more substituents selected from the group consisting of halogen atom(s), cyano, nitro, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 1 -C 6 alkoxy, C 1 -C 6  haloalkoxy, C 1 -C 6  alkylthio, C 1 -C 6  haloalkylthio and (C 1 -C 5  alkoxy) carbonyl.  
 
 
     
     
         11 . The difluoroacetyl semicarbazide compound according to  claim 10 , wherein T is optionally substituted m-phenylene; 
 wherein the substituent(s) are one or more substituents selected from the group of halogen atoms, cyano, nitro, C 1 -C 6  alkyl, C 1 -C 6  haloalkyl, C 1 -C 6  alkoxy, C 1 -C 6  haloalkoxy, C 1 -C 6  alkylthio, C 1 -C 6  haloalkylthio and (C 1 -C 5  alkoxy)carbonyl.    
     
     
         12 . The difluoroacetyl semicarbazide compound according to  claim 10 , wherein T is optionally substituted m-azaphenylene or optionally substituted m-diazaphenylene bonded to R 1  and to CH 2  each via a carbon atom; 
 wherein the substituent(s) are one or more substituents selected from the group of halogen atom(s), cyano, nitro, C 1 -C 6  alkyl, C 1 -C 6  haloalkyl, C 1 -C 6  alkoxy, C 1 -C 6  haloalkoxy, C 1 -C 6  alkylthio, C 1 -C 6  haloalkylthio and (C 1 -C 5  alkoxy) carbonyl.    
     
     
         13 . The difluoroacetyl semicarbazide compound according to  claim 10 , wherein T is optionally substituted m-phenylene; 
 wherein the substituent(s) are halogen atom(s) or methyl.    
     
     
         14 . 1-Difluoroacetyl-2-methyl-4-(2-methyl-5-phenylbenzyl)semicarbazide; which is the difluoroacetyl semicarbazide compound according to  claim 10 .  
     
     
         15 . A semicarbazide compound of the formula [VII]:  
       
         
           
           
               
               
           
         
       
       wherein; 
 R 1  represents A 1 -L 1 -, A 1 -ON═CA 2 -, A 1 -ON═C(Me)CH 2 ON═CA 2 -, A 1 -C(A 2 )=N—OCH 2 —, A 1 S—C(A 2 )=N—, A 1 -C(═S)NH—, A 1 S—C(═S)NH—, A 1 S—C(SA 2 )=N—, A 1 -ON═C(CN)—, A 1 -ON═C(Me)CH 2 ON═C(CN)—, A 1 -C(CN)═N—OCH 2 —, halogen atom, nitro or cyano; 
 wherein, L 1  represents single bond, oxygen atom, sulfur atom, carbonyl, —OCH 2 —, —SCH 2 —, —C(═O)O—, —OC(═O)—, —C(═O)OCH 2 —, —NH— or C 1 -C 6  alkylimino;  
 A 1  and A 2 , which are the same or different, represent hydrogen atom, C 1 -C 10  alkyl, C 2 -C 10  alkenyl, C 2 -C 10  alkynyl, C 3 -C 10  cycloalkyl, (C 3 -C 10  cycloalkyl) alkyl, C 5 -C 10  cycloalkenyl, (C 5 -C 10  cycloalkenyl) alkyl, phenyl, naphthyl, phenyl C 1 -C 10  alkyl, naphtyl C 1 -C 10  alkyl, 5- or 6-membered heterocyclic group optionally condensed with a benzene ring, or methyl substituted by a 5- or 6-membered heterocyclic group optionally condensed with a benzene ring;  
 the alkyl, the alkenyl, the alkynyl, the cycloalkyl, the cycloalkylalkyl, the cycloalkenyl and the cycloalkenylalkyl, represented by A 1  and A 2 , may optionally be each substituted by one or more substituents selected from the group consisting of halogen atom(s), cyano, nitro, C 1 -C 10  alkoxy, C 1 -C 10  haloalkoxy, C 1 -C 10  alkylthio, C 1 -C 10  haloalkylthio, (C 1 -C 9  alkyl) carbonyl, (C 1 -C 9  alkoxy) carbonyl, (C 1 -C 9  alkyl) carbonylamino, phenyl, phenoxy, benzyloxy and tri(C 1 -C 10  alkyl) silyl;  
 the phenyl, the naphthyl, the benzene ring in the phenylalkyl, the naphthalene ring in the phenylnaphthyl, the heterocyclic group, and the heterocyclic ring in the methyl substituted by a heterocylic group, represented by A 1  and A 2 , may optionally be each substituted by one or more substituents selected from the group consisting of halogen atom(s), cyano, nitro, C 1 -C 10  alkyl, C 1 -C 10  haloalkyl C 3 -C 10  cycloalkyl, C 1 -C 10  alkoxy, C 1 -C 10  haloalkoxy, C 1 -C 10  alkylthio, C 1 -C 10  haloalkylthio, (C 1 -C 9  alkyl) carbonyl, (C 1 -C 9  alkoxy) carbonyl, (C 1 -C 9  alkyl) carbonylamino, phenyl, phenoxy, benzyloxy, tri(C 1 -C 10  alkyl) silyl, methylenedioxy and difluoromethylenedioxy;  
 with the proviso, when L 1  is single bond, A 1  is not a hydrogen atom;  
 
 T represents optionally substituted m-phenylene, optionally substituted m-azaphenylene or optionally substituted m-diazaphenylene bonded to R 1  and to CH 2  each via a carbon atom; 
 wherein the substituent(s) are one or more substituents selected from the group consisting of halogen atom(s), cyano, nitro, C 1 -C 6  alkyl, C 1 -C 6  haloalkyl, C 1 -C 6  alkoxy, C 1 -C 6  haloalkoxy, C 1 -C 6  alkylthio, C 1 -C 6  haloalkylthio and (C 1 -C 5  alkoxy) carbonyl.  
 
 
     
     
         16 . The semicarbazide compound according to  claim 15 , wherein T is optionally substituted m-phenylene; 
 wherein the substituent(s) are one or more substituents selected from the group of halogen atom(s), cyano, nitro, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 1 -C 6 alkoxy, C 1 -C 6 haloalkoxy, C 1 -C 6  alkylthio, C 1 -C 6  haloalkylthio and (C 1 -C 5  alkoxy)carbonyl.    
     
     
         17 . The semicarbazide compound according to  claim 15 , wherein T is optionally substituted m-azaphenylene or optionally substituted m-diazaphenylene bonded to R 1  and to CH 2  each via a carbon atom; 
 wherein the substituent(s) are one or more substituents selected from the group of halogen atom(s), cyano, nitro, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 1 -C 6 alkoxy, C 1 -C 6 haloalkoxy, C 1 -C 6  alkylthio, C 1 -C 6  haloalkylthio and (C 1 -C 5 -alkoxy)carbonyl.    
     
     
         18 . The semicarbazide compound according to  claim 15 , wherein T is optionally substituted m-phenylene; 
 wherein the substituent(s) are halogen atom(s) or methyl.    
     
     
         19 . 2-Methyl-4-(2-methyl-5-phenylbenzyl)semicarbazide; which is the semicarbazide compound according to  claim 15 .  
     
     
         20 . 2-Methyl-5-phenylbenzylamine of the formula [XVI-1]:  
       
         
           
           
               
               
           
         
       
       its inorganic acid salt or its sulfonic acid salt.  
     
     
         21 . 2-Methyl-5-phenylbenzyl chloride of the formula [XIII-1]:  
       
         
           
           
               
               
           
         
       
     
     
         22 . A sulfonate ester compound of the formula [XIII-2]:  
       
         
           
           
               
               
           
         
       
       wherein R 9  represents methyl or p-tolyl.  
     
     
         23 . N,N-Dimethyl-(2-methyl-5-phenylbenzyl)amine of the formula [LI]:  
       
         
           
           
               
               
           
         
       
       its inorganic acid salt or its sulfonic acid salt.