Pyrazinylpyrazoles

Abstract

Pyrazin-2-ylpyrazoles are described, as is the use thereof as insecticides and/or parasiticides. Additionally described are processes for preparation thereof, and compositions which comprise such pyrazin-2-ylpyrazoles.

1 . Pyrazinylpyrazoles of the general formula (I) 
       
         
           
           
               
               
           
         
         in which 
         X is 
         phenyl, 2-pyridyl or 3-pyridyl, each of which is substituted by one or more substituents selected from the group consisting of halogen, alkyl, haloalkyl, alkoxy, alkoxyalkyl, alkoxyalkoxy, cycloalkyl, alkenyloxy, alkynyloxy, benzyloxy, cycloalkylalkoxy, haloalkoxy, haloalkoxyalkyl, alkylsulphanyl, haloalkylsulphanyl, alkylsulphinyl, haloalkylsulphinyl, alkylsulphonyl, haloalkylsulphonyl, cyano, nitro, alkylcarbonyl, alkoxycarbonyl, alkoxycarbonylalkyl, carboxyl, carboxamide, dialkylcarboxamide, trialkylsilyl, amino, alkylamino, dialkylamino, alkylsulphonylamino, dialkylsulphonylamino, formyl, —CH═NO—H, —CH═NO-alkyl, —CH═NO-halolkyl, —C(CH 3 )═NO—H, —C(CH 3 )═NO-alkyl, —C(CH 3 )═NO-haloalkyl; or phenyl, 2-pyridyl and 3-pyridyl optionally substituted by one or more halogen atoms, cyano, nitro, alkyl, alkoxy or haloalkyl, where vicinal alkyl, haloalkyl, alkoxy and/or haloalkoxy groups on the phenyl substituent, 2-pyridyl substituent or 3-pyridyl substituent, together with the carbon atoms to which they are bonded, may form a five- to seven-membered cyclic system which contains 0 to 2 oxygen or nitrogen atoms, where no two oxygen atoms are directly bonded to one another, and the alkyl moiety of which may optionally be substituted by one or more halogen atoms and/or further alkyl radicals; 
         R 1  is 
         hydrogen, 
         alkyl which is optionally mono- or independently polysubstituted by alkoxy, haloalkoxy, alkylsulphanyl, haloalkylsulphanyl, alkylsulphinyl, haloalkylsulphinyl, alkylsulphonyl, haloalkylsulphonyl, alkylcarbonyl, alkoxycarbonyl, hydroxyl and/or cycloalkyl; 
         alkenyl which is optionally mono- or independently polysubstituted by halogen, alkoxy, haloalkoxy, alkylsulphanyl, haloalkylsulphanyl, alkylsulphinyl, haloalkylsulphinyl, alkylsulphonyl, haloalkylsulphonyl, alkylcarbonyl, alkoxycarbonyl and/or cycloalkyl; 
         cycloalkyl which is optionally mono- or independently polysubstituted by alkyl, haloalkyl and/or halogen; 
         haloalkyl which is optionally mono- or independently polysubstituted by alkoxy, alkylsulphanyl, haloalkylsulphanyl, alkylsulphinyl, haloalkylsulphinyl, alkylsulphonyl, haloalkylsulphonyl and/or phenyl, optionally mono- or independently polysubstituted by halogen, alkyl, haloalkyl and/or alkoxy; 
         phenyl which is optionally mono- or independently polysubstituted by halogen, alkyl, haloalkyl and/or alkoxy; 
         benzyl which is optionally mono- or independently polysubstituted by halogen, alkyl, haloalkyl and/or alkoxy; 
         cyano, formyl, alkylcarbonyl, —CH═NO—H, —CH═NO-alkyl, —CH═NO-haloalkyl, —C(CH 3 )═NO—H, —C(CH 3 )═NO-alkyl or —C(CH 3 )═NO-haloalkyl; 
         R 2  is 
         optionally substituted amino, where amino may be mono- or independently disubstituted by alkyl, haloalkyl, alkoxyalkyl, alkylsulphanylalkyl, alkylsulphinylalkyl, alkylsulphonylalkyl, alkylcarbonyl, cycloalkyl, cycloalkylalkyl, alkenyl, where the above radicals are optionally substituted by halogen, cyano, alkoxy, alkoxycarbonyl or phenyl, where the phenyl ring is optionally mono- or polysubstituted by one or more substituents selected independently from halogen, alkyl, haloalkyl and alkoxy; alkynyl, alkoxycarbonyl, alkenyloxycarbonyl, alkynyloxycarbonyl, alkoxycarbonylalkyl, alkoxycarbonylcarbonyl, heterocyclyl, heteroaryl, heterocyclylalkyl or heteroarylalkyl, where the heterocyclic or heteroaromatic ring may optionally be mono- or polysubstituted by one or more substituents selected independently from halogen, alkyl, haloalkyl and alkoxy; benzyl or phenylcarbonyl, where the phenyl ring in the benzyl and phenylcarbonyl is optionally mono- or polysubstituted by one or more substituents selected independently from halogen, alkyl, haloalkyl and alkoxy; and 
         R 3 , R 4  are each independently 
         hydrogen, halogen, alkyl, cycloalkyl, haloalkyl, cyano, hydroxyl, formyl, alkylcarbonyl, —CH═NO—H, —CH═NO-alkyl, —CH═NO-haloalkyl, —C(CH 3 )═NO—H, —C(CH 3 )═NO-alkyl, —C(CH 3 )═NO-haloalkyl, nitro, hydroxyl, SH, alkoxy, alkylsulphanyl, haloalkylsulphanyl, alkylsulphinyl, haloalkylsulphinyl, alkylsulphonyl or haloalkylsulphonyl; 
         R 5  is 
         halogen, alkyl, haloalkyl, hydroxyl, alkoxy, alkoxyalkyl, alkoxyalkoxy, cycloalkyl, alkenyloxy, alkynyloxy, benzyloxy, cycloalkylalkoxy, haloalkoxy, haloalkoxyalkyl, —SH, alkylsulphanyl, haloalkylsulphanyl, alkylsulphinyl, haloalkylsulphinyl, alkylsulphonyl, haloalkylsulphonyl, cyano, nitro, alkylcarbonyl, alkoxycarbonyl, alkoxycarbonylalkyl, carboxyl, carboxamide, dialkylcarboxamide, trialkylsilyl, nitro, amino, alkylamino, dialkylamino, alkylsulphonylamino, dialkylsulphonylamino, formyl, —CH═NO—H, —CH═NO-alkyl, —CH═NO-haloalkyl, —C(CH 3 )═NO—H, —C(CH 3 )═NO-alkyl, —C(CH 3 )═NO-haloalkyl or heteroaryl, where the heteroaromatic ring may optionally be mono- or polysubstituted by one or more substituents selected independently from halogen, alkyl, haloalkyl and alkoxy; 
         and the N-oxides and salts of the compounds of the general formula (I). 
       
     
     
         2 . Pyrazinylpyrazoles of the general formula (I) according to  claim 1 , characterized in that
 the X radical is phenyl, 2-pyridyl or 3-pyridyl, each of which is substituted by one or more substituents selected from the group consisting of halogen, alkyl, haloalkyl, alkoxy, haloalkoxy, alkylsulphanyl, haloalkylsulphanyl, alkylsulphinyl, haloalkylsulphinyl, alkylsulphonyl, haloalkylsulphonyl, cyano, nitro and dialkylamino; or phenyl, 2-pyridyl and 3-pyridyl optionally substituted by one or more halogen atoms, cyano, nitro, alkyl, alkoxy or haloalkyl, where vicinal alkyl, haloalkyl and/or alkoxy groups on the phenyl substituent, 2-pyridyl substituent or 3-pyridyl substituent, together with the carbon atoms to which they are bonded, may form a five- to seven-membered cyclic system which contains 0 to 2 oxygen or nitrogen atoms, where no two oxygen atoms are directly bonded to one another, and the alkyl moiety thereof may optionally be substituted by one or more halogen atoms and/or further alkyl radicals;   the R 1  radical is hydrogen, alkyl which is optionally mono- or independently polysubstituted by alkoxy, haloalkoxy, alkylsulphanyl, haloalkylsulphanyl, alkylsulphinyl, haloalkylsulphinyl, alkylsulphonyl, haloalkylsulphonyl, alkylcarbonyl, alkoxycarbonyl, hydroxyl and/or cycloalkyl;   alkenyl which is optionally mono- or independently polysubstituted by halogen, alkoxy, haloalkoxy, alkylsulphanyl, haloalkylsulphanyl, alkylsulphinyl, haloalkylsulphinyl, alkylsulphonyl, haloalkylsulphonyl, alkylcarbonyl, alkoxycarbonyl and/or cycloalkyl;   cycloalkyl which is optionally mono- or independently polysubstituted by alkyl, haloalkyl and/or halogen;   haloalkyl which is optionally mono- or independently polysubstituted by alkoxy, alkylsulphanyl, haloalkylsulphanyl, alkylsulphinyl, haloalkylsulphinyl, alkylsulphonyl, haloalkylsulphonyl and/or phenyl;   CH═NOH, CH═NOCH 3  or CN,   the R 2  radical is amino and substituted amino, where the substituted amino may be mono- or independently disubstituted by alkyl, haloalkyl, cycloalkylalkyl, optionally halogen- or phenyl-substituted alkenyl, alkynyl, heterocyclylalkyl and/or heteroarylalkyl, where the heteroaromatic ring may optionally be mono- or polysubstituted by one or more substituents selected independently from halogen, alkyl, haloalkyl and alkoxy; benzyl, where the phenyl ring in the benzyl may optionally be mono- or polysubstituted by one or more substituents selected independently from halogen, alkyl, haloalkyl and alkoxy,   the R 3  and R 4  radicals are each independently hydrogen, halogen, alkyl, cycloalkyl, haloalkyl, cyano and/or hydroxyl and   the R 5  radical is halogen, alkyl, haloalkyl, hydroxyl, alkoxy, haloalkoxy, alkylsulphanyl, haloalkylsulphanyl, alkylsulphinyl, haloalkylsulphinyl, alkylsulphonyl, haloalkylsulphonyl, cyano, amino, alkylamino, dialkylamino, alkylsulphonylamino, dialkylsulphonylamino or heteroaryl, where the heteroaromatic ring may optionally be mono- or polysubstituted by one or more substituents selected independently from halogen, alkyl, haloalkyl and alkoxy.   
     
     
         3 . Pyrazinylpyrazoles of the general formula (I) according to  claim 1  or  2 , characterized in that
 the X radical is phenyl, 2-pyridyl or 3-pyridyl, each of which is substituted by one or more substituents selected from the group consisting of fluorine, chlorine, bromine, iodine, CF 3 , methoxy, ethoxy, propanyloxy, trifluoroethoxy, methylsulphanyl, 2,2,2-trifluoroethylsulphanyl, methylsulphinyl, 2,2,2-trifluoroethylsulphinyl, methylsulphonyl, 2,2,2-trifluoroethylsulphonyl, cyano and dimethylamino; or phenyl optionally substituted by one or more halogen atoms, cyano, nitro, methyl, methoxy or CF 3 , where vicinal alkyl or alkoxy groups on the phenyl substituent, together with the carbon atom to which they are bonded, may form a five- to seven-membered cyclic system which contains 1 or 2 oxygen atoms, where no two oxygen atoms are directly bonded to one another, and the alkyl moiety thereof may be substituted by one or more alkyl radicals; 
 the R 1  radical is CH 3 , CH 2 CH 3 , CH(CH 3 ) 2 , CH 2 CH 3 CH 3 , C(CH 3 ) 3 , C(OCH 3 )HCH 2 CH 3 , CH(OCH 3 ) 2 , CH═CH 2 , prop-1-en-2-yl, cyclopropyl, CF 3 , CHFCH 3 , CHF 2 , CF 2 Cl, CF 2 Br, CF 2 CF 3 , CF 2 CH 3 , CF 2 CF 2 CF 3 , CF 2 CF 2 H, 2-fluoropropan-2-yl, 1,1,2,2-tetrafluoro-2-methoxyethyl, CH═NOH, CH═NOCH 3  or CN, 
 the R 2  radical is amino, methylamino, dimethylamino, benzylamino, dibenzylamino, (4-chlorobenzyl)amino, bis(4-chlorobenzyl)amino, (4-methoxybenzyl)amino, bis(4-methoxybenzyl)amino, (2-methylprop-2-en-1-yl)amino, prop-2-en-1-ylamino, diprop-2-en-1-ylamino, bis(2-methylprop-2-en-1-yl)amino, prop-2-yn-1-ylamino, bis(prop-2-yn-1-yl)amino, (pyrazin-2-ylmethyl)amino, (6-methylpyridin-2-ylmethyl)amino, bis(6-methyl-pyridin-2-ylmethyl)amino or (pyridin-2-ylmethyl)amino; 
 the R 3  and R 4  radicals are each independently hydrogen, chlorine and/or methyl and 
 the R 5  radical is chlorine, bromine, methyl, CF 3 , methoxy, ethoxy, propoxy, propan-2-yloxy, dimethylamino, cyano, methylsulphanyl, methylsulphinyl, methylsulphonyl, 1H-pyrazol-1-yl, 1H-imidazol-1-yl or 4-fluoro-1H-pyrazol-1-yl. 
 
     
     
         4 . Process for preparing pyrazinylpyrazoles of the general formula (I) according to any of  claims 1  to  3 , characterized by the following process steps:
 (a) condensation of keto nitriles or of the tautomers or hydrates thereof, of the formulae (IIA), (IIB) and/or (IIC), with pyrazinylhydrazines of the general formula (III) according to the following reaction scheme: 
 
       
         
           
           
               
               
           
         
         where X, R, R 1 , R 4  and R 5  are each as defined according to one of  claims 1  to  3 ; 
         (b) reaction of 1H-aminopyrazoles of the general formula (V) with pyrazinyl halides and/or pyrazinyl alkyl sulphones of the general formula (VI) in the presence of a base in organic solvents according to the following reaction scheme: 
       
       
         
           
           
               
               
           
         
         where X, R 1 , R 3 , R 4  and R 5  are each as defined according to one of  claims 1  to  3  and LG is halogen or an alkylsulphonyl; 
         (c) reactions of keto nitriles or of the tautomers or hydrates thereof, of the general formulae (IIA), (IIB) or (IIC), with chlorinating agents, optionally diluted in an inert organic solvent or promoted by auxiliary bases such as nitrogen bases, to give chloroacrylonitriles (VII) 
       
       
         
           
           
               
               
           
         
         
           where X, R 1 , R 3 , R 4  and R 5  are each as defined according to one of  claims 1  to  3 ; 
         
         (d) reaction of compounds of the general formula (IA) according to the following reaction scheme with one or two alkylating agents or acylating agents R 6 -LG and/or R 7 -LG to obtain compounds of the general formula (IB) and (IC) in which at least one radical of R 6  and R 1  is not hydrogen: 
       
       
         
           
           
               
               
           
         
         where 
         X, R 1 , R 3 , R 4  and R 5  are each as defined according to one of  claims 1  to  3 ; 
         LG is halogen or alkylsulphonyl; and 
         R 6  and R 7  are each independently hydrogen, alkyl, haloalkyl, alkoxyalkyl, alkylsulphanylalkyl, alkylsulphinylalkyl, alkylsulphonylalkyl, alkylcarbonyl, cycloalkyl, cycloalkylalkyl, alkenyl, where the above radicals are optionally substituted by halogen, cyano, alkoxy, alkoxycarbonyl and phenyl, where the phenyl ring is optionally mono- or polysubstituted by one or more substituents selected independently from halogen, alkyl, haloalkyl and alkoxy; alkynyl, alkoxycarbonyl, alkenyloxycarbonyl, alkynyloxycarbonyl, alkoxycarbonylalkyl, alkoxycarbonylcarbonyl, heterocyclyl, heteroaryl, heterocyclylalkyl or heteroarylalkyl, where the heterocyclic or heteroaromatic ring may optionally be mono- or polysubstituted by one or more substituents selected independently from halogen, alkyl, haloalkyl and alkoxy; benzyl or phenylcarbonyl, where the phenyl ring in the benzyl and phenylcarbonyl is optionally mono- or polysubstituted by one or more substituents selected independently from halogen, alkyl, haloalkyl and alkoxy; and 
         with the proviso that at least one radical of R 6  and R 7  is not hydrogen; or 
         (e) reaction of bromides or iodides of the general formula (VII) with boronic acids or boronic esters of the formula (IX) in the presence of suitable palladium catalysts and bases within a temperature range from −20° C. to 120° C. according to the following reaction scheme: 
       
       
         
           
           
               
               
           
         
         where X, R 1 , R 3 , R 4  and R 5  are each as defined according to one of  claims 1  to  3  and W is a protecting group. 
       
     
     
         5 . Compositions comprising at least one compound of the formula (I) as claimed in one of  claims 1  to  3 . 
     
     
         6 . Use of compounds of the formula (I) according to any of  claims 1  to  3  or of the composition according to  claim 5  for controlling animal pests. 
     
     
         7 . Method for controlling animal pests, characterized in that compounds of the formula (I) according to any of  claims 1  to  3  or compositions according to  claim 5  are allowed to act on animal pests and/or the habitat and/or seed thereof. 
     
     
         8 . Process for producing compositions, characterized in that compounds of the formula (I) according to any of  claims 1  to  5  are mixed with extenders and/or surfactants.