2-Pyridinylethylcarboxamide derivatives and their use as fungicides

Abstract

A compound of general formula (I) A process for preparing this compound. A fungicidal composition comprising a compound of general formula (I). A method for treating plants by applying a compound of general formula (I) or a composition comprising it.

1 . A compound of general formula (I)  
       
         
           
           
               
               
           
         
       
       in which: 
 n is 1, 2 or 3;  
 R a  is a C 1 -C 6 -halogenoalkyl having 1 to 5 halogen atoms;  
 each substituent X is chosen, independently of the others, as being a hydrogen atom, a halogen atom, a C 1 -C 6 -alkyl or a C 1 -C 6 -halogenoalkyl;  
 R 1 , R 2 , R 3  and R 4  are chosen, independently of the others as being a hydrogen atom, a halogen atom, a cyano group, a hydroxy group, an amino group, a sulfanyl group, a formyl group, a formyloxy group, a formylamino group, a carboxy group, a carbamoyl group, a N-hydroxycarbamoyl group, a carbamate group, a (hydroxyimino)-C 1 -C 6 -alkyl group, a C 1 -C 6 -alkyl, a C 2 -C 6 -alkenyl, a C 2 -C 6 -alkynyl, a C 1 -C 6 -alkylamino, a di-C 1 -C 6 -alkylamino, a C 1 -C 6 -alkoxy, a C 1 -C 6 -halogenoalkyl having 1 to 5 halogen atoms, a C 1 -C 6 -halogenoalkoxy having 1 to 5 halogen atoms, a C 1 -C 6 -alkylsulfanyl, a C 1 -C 6 -halogenoalkylsulfanyl having 1 to 5 halogen atoms, a C 2 -C 6 -alkenyloxy, a C 2 -C 6 -halogenoalkenyloxy having 1 to 5 halogen atoms, a C 3 -C 6 -alkynyloxy, a C 3 -C 6 -halogenoalkynyloxy having 1 to 5 halogen atoms, a C 3 -C 6 -cycloalkyl, a C 3 -C 6 -halogenocycloalkyl having 1 to 5 halogen atoms, a C 1 -C 6 -alkylcarbonyl, a C 1 -C 6 -halogenoalkylcarbonyl having 1 to 5 halogen atoms, a C 1 -C 6 -alkylcarbamoyl, a di-C 1 -C 6 -alkylcarbamoyl, a N—C 1 -C 6 -alkyloxycarbamoyl, a C 1 -C 6 -alkoxycarbamoyl, a N—C 1 -C 6 -alkyl-C 1 -C 6 -alkoxycarbamoyl, a C 1 -C 6 -alkoxycarbonyl, a C 1 -C 6 -halogenoalkoxycarbonyl having 1 to 5 halogen atoms, a C 1 -C 6 -alkylcarbonyloxy, a C 1 -C 6 -halogenoalkylcarbonyloxy having 1 to 5 halogen atoms, a C 1 -C 6 -alkylcarbonylaamino, a C 1 -C 6 -halogenoalkylcarbonylamino having 1 to 5 halogen atoms, a C 1 -C 6 -alkylaminocarbonyloxy, a di-C 1 -C 6 -alkylaminocarbonyloxy, a C 1 -C 6 -alkyloxycarbonyloxy, a C 1 -C 6 -alkylsulphenyl, a C 1 -C 6 -halogenoalkylsulphenyl having 1 to 5 halogen atoms, a C 1 -C 6 -alkylsulphinyl, a C 1 -C 6 -halogenoalkylsulphinyl having 1 to 5 halogen atoms, a C 1 -C 6 -alkylsulphonyl, a C 1 -C 6 -halogenoalkylsulphonyl having 1 to 5 halogen atoms, a benzyl, a benzyloxy, a benzylsulfanyl, a benzylsulfinyl, a benzylsulfonyl, a benzylamino, a phenoxy, a phenylsulfanyl, a phenylsulfinyl, a phenylsulfonyl, a phenylamino, a phenylcarbonylamino, a 2,6 dichlorophenyl-carbonylamino group or a phenyl group; or R 1  and R 2  may form together a cyclopropyl, a cylcobutyl, a cyclopentyl or a cyclohexyl;  
 with the proviso that when three of the four substituents R 1 , R 2 , R 3  and R 4  are a hydrogen atom, then the fourth substituent is not a hydrogen atom;  
 R 5  is chosen as being a hydrogen atom, a cyano group, a formyl group, a hydroxy group, a C 1 -C 6 -alkyl, a C 1 -C 6 -halogenoalkyl having 1 to 5 halogen atoms, a C 1 -C 6 -alkoxy, a C 1 -C 6 -halogenoalkoxy having 1 to 5 halogen atoms, a C 3 -C 6 -cycloalkyl, a C 3 -C 6 -halogenocycloalkyl having 1 to 5 halogen atoms, a C 2 -C 6 -alkenyl, a C 2 -C 6 -alkynyl, a C 1 -C 6 -alkoxy-C 1 -C 6 -alkyl, a C 1 -C 6 -cyanoalkyl, a C 1 -C 6 -aminoalkyl, a C 1 -C 6 -alkylamino-C 1 -C 6 -alkyl, a di-C 1 -C 6 -alkylamino-C 1 -C 6 -alkyl, a C 1 -C 6 -alkylcarbonyl, a C 1 -C 6 -halogenalkylcarbonyl having 1 to 5 halogen atoms, a C 1 -C 6 -alkyloxycarbonyl, a C 3 -C 7 -cycloalkyl, a C 3 -C 7 -halogenocycloalkyl having 1 to 5 halogen atoms, a C 3 -C 7  -cycloalkyl-C 1 -C 6 -alkyl, a C 1 -C 6 -benzyloxycarbonyl, a C 1 -C 6 -alkoxy-C 1 -C 6 -alkylcarbonyl, a C 1 -C 6 -alkylsulfonyl or a C 1 -C 6 -halogenoalkylsulfonyl having 1 to 5 halogen atoms; and  
 Het represents a 5-, 6- or 7-membered non-fused heterocycle with one, two or three heteroatoms which may be the same or different, Het being linked by a carbon atom and being at least substituted in ortho position;  
 as well as its salts, N-oxydes, metallic complexes, metalloidic complexes and optically active isomers.  
 
     
     
         2 . A compound according to  claim 1 , characterised in that n is 1 or 2.  
     
     
         3 . A compound according to  claim 1 , characterised in that X is a halogen atom.  
     
     
         4 . A compound according to  claim 3 , characterised in that X is chlorine.  
     
     
         5 . A compound according to  claim 1 , characterised in that R a  is —CF 3 .  
     
     
         6 . A compound according to  claim 1 , characterised in that the 2-pyridyl is substituted in 3- and/or in 5-position.  
     
     
         7 . A compound according to  claim 6 , characterised in that the 2-pyridyl is substituted in 3-position by X and in 5-position by R a .  
     
     
         8 . A compound according to  claim 1 , characterised in that the 2-pyridyl is substituted in 3-position by —Cl and in 5-position by —CF 3 .  
     
     
         9 . A compound according to  claim 1 , characterised in that R 1  and R 2  are chosen, independently of each other, as being a hydrogen atom, a halogen atom, a cyano group, a hydroxy group, a C 1 -C 6 -alkyl, a C 1 -C 6 -halogenoalkyl having 1 to 5 halogen atoms, a C 2 -C 6 -alkenyl, a C 1 -C 6 -alkoxy, a C 1 -C 6 -alkylsulfanyl, a C 1 -C 6 -alkylsulfenyl, a C 1 -C 6 -alkylsulfinyl, a C 1 -C 6 -alkoxycarbonyl, a C 1 -C 6 -alkylcarbonylamino, a C 1 -C 6 -alkoxycarbonyloxy, a C 1 -C 6 -alkoxycarbonylamino or a phenyl group.  
     
     
         10 . A compound according to  claim 9 , characterised in that R 1  and R 2  are chosen, independently of each other, as being a halogen atom, a C 1 -C 6 -alkyl, a C 1 -C 6 -halogenoalkyl having 1 to 5 halogen atoms or a C 1 -C 6 -alkylcarbonylamino.  
     
     
         11 . A compound according to  claim 1 , characterised in that R 3  and R 4  are chosen, independently of each other, as being a hydrogen atom, a halogen atom, a cyano group, a C 1 -C 6 -alkyl, a C 1 -C 6 -halogenoalkyl having 1 to 5 halogen atoms, a C 1 -C 6 -alkylcarbonylamino or a phenyl group.  
     
     
         12 . A compound according to  claim 11 , characterised in that R 3  and R 4  are chosen, independently of each other, as being a halogen atom, a C 1 -C 6 -alkyl, a C 1 -C 6 -halogenoalkyl having 1 to 5 halogen atoms or a phenyl group.  
     
     
         13 . A compound according to  claim 1 , characterised in that R 5  is a hydrogen atom or a C 3 -C 7 -cycloalkyl.  
     
     
         14 . A compound according to  claim 1 , characterised in that Het is a five membered ring heterocycle.  
     
     
         15 . A compound according to  claim 1 , characterised in that Het is a six membered ring heterocycle.  
     
     
         16 . A process for the preparation of a compound of general formula (I) as defined in  claim 1 , which comprises reacting a 2-pyridine derivative of general formula (II) or one of its salt:  
       
         
           
           
               
               
           
         
       
       with a carboxylic acid derivative of the general formula (III)  
       
         
           
           
               
               
           
         
       
       in which: 
 and  
 L 2  is a leaving group chosen as being a halogen atom, a hydroxyl group, —OR 6 , —OCOR 6 , R 6  being a C 1 -C 6  alkyl, a C 1 -C 6  haloalkyl, a benzyl, 4-methoxybenzyl, pentafluorophenyl or a group of formula  
                     
 in the presence of a catalyst and, if L 2  is a hydroxyl group, in the presence of a condensing agent.  
 
     
     
         17 . A process according to  claim 16 , characterised in that R 5  is a hydrogen atom and that the process is completed by a further step according to the following reaction scheme:  
       
         
           
           
               
               
           
         
       
       in which: 
 L 5  is a leaving group chosen as being a halogen atom, a 4-methyl phenylsulfonyloxy or a methylsulfonyloxy; comprising the reaction of a compound of general formula (Id) with a compound of general formula (XXII) to provide a compound of general formula (I).  
 
     
     
         18 . A fungicidal composition comprising an effective amount of a compound according to  claim 1  and an agriculturally acceptable support.  
     
     
         19 . A method for preventively or curatively combating the phytopathogenic fungi of crops, characterised in that an effective and non-phytotoxic amount of a composition according to  claim 18  is applied to the plant seeds or to the plant leaves and/or to the fruits of the plants or to the soil in which the plants are growing or in which it is desired to grow them.