Process for the preparation of pesticides

Abstract

The invention relates to a process for the preparation of compounds of the formula or, if appropriate, a tautomer thereof, in each case in the free form or in salt form, in which A, X, Y, Z, R 2 , R 3 , R 4 , R 5 , R 7 , R 9 and n are as defined in claim 1 and the C═N double bond marked with E has the E configuration, which comprises a1) reacting either a compound of the formula (II) mentioned above with a compound of the formula (III) mentioned above, in which X 1 is a leaving group, or a2) a compound of the formula (IV) mentioned above, if appropriate in the presence of a base, with a compound of the formula (V) mentioned above, or b1) reacting a compound of the formula (VI) mentioned above with a compound of the formula R 7 -A-X 2 (VII), in which X 2 is a leaving group, and either further reacting the compound thus obtainable, of the formula (IV), for example according to method a2), or b2) reacting it with hydroxylamine or a salt thereof, if appropriate in the presence of a basic or acid catalyst, and further reacting the compound thus obtainable, of the formula (II), for example according to method a1), or c) reacting a compound of the formula (VIII), mentioned above with a C 1 -C 6 alkyl nitrite and further reacting the compound thus obtainable, of the formula (VI), for example according to method b), the E isomers of the compounds of the formulae (II), (IV) and (VI), a process for their preparation and their use for the preparation of compounds of the formula (I).

What is claimed is:  
     
         1 . A process for the preparation of a compound of the formula  
       
         
           
           
               
               
           
         
       
       and, where appropriate, their tautomers, in each case in the free form or salt form, in which either 
 X is CH or N, Y is OR 1  and Z is O, or  
 X is N, Y is NHR 8  and Z is O, S or S(═O);  
 R 1  is C 1 -C 4 alkyl;  
 R 2  is H, C 1 -C 4 alkyl, halogeno-C 1 -C 4 alkyl, C 3 -C 6 cycloalkyl or C 1 -C 4 alkoxymethyl;  
 R 3  and R 4  independently of one another are H, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, OH, CN, NO 2 , a (C 1 -C 4 alkyl) 3 -Si group, where the alkyl groups can be identical or different, halogen, (C 1 -C 4 alkyl)S(═O) m , (halogeno-C 1 -C 4 alkyl)S(═O) m , halogeno-C 1 -C 4 alkyl or halogeno-C 1 -C 4 alkoxy;  
 R 5  is C 1 -C 6 alkyl, halogeno-C 1 -C 6 alkyl, C 1 -C 6 alkoxy, halogeno-C 1 -C 6 alkoxy, C 1 -C 6 -alkylthio, halogen-C 1 -C 6 alkylthio, C 1 -C 6 alkylsulfinyl, halogeno-C 1 -C 6 -alkylsulfinyl, C 1 -C 6 alkylsulfonyl, halogeno-C 1 -C 6 alkylsulfonyl, C 1 -C 6 alkoxy-C 1 -C 6 alkyl, halogeno-C 1 -C 6 alkoxy-C 1 -C 6 alkyl, C 1 -C 6 alkylthio-C 1 -C 6 alkyl, halogeno-C 1 -C 6 alkylthio-C 1 -C 6 alkyl, C 1 -C 6 alkylsulfinyl-C 1 -C 6 alkyl, halogeno-C 1 -C 6 -alkylsulfinyl-C 1 -C 6 alkyl, C 1 -C 6 -alkylsulfonyl-C 1 -C 6 alkyl, halogeno-C 1 -C 6 -alkylsulfonyl-C 1 -C 6 alkyl, C 1 -C 6 -alkylcarbonyl, halogeno-C 1 -C 6 -alkylcarbonyl, C 1 -C 6 -alkoxycarbonyl, halogeno-C 1 -C 6 -alkoxycarbonyl, C 1 -C 6 -alkylaminocarbonyl, C 1 -C 4 -alkoxyiminomethyl; di(C 1 -C 6 alkyl)-aminocarbonyl, where the alkyl groups can be identical or different; C 1 -C 6 -alkylaminothiocarbonyl; di(C 1 -C 6 alkyl)-aminothiocarbonyl, where the alkyl groups can be identical or different; C 1 -C 6 -alkylamino, di(C 1 -C 6 alkyl)-amino, where the alkyl groups can be identical or different; halogen, NO 2 , CN, SF 5 , thioamido, thiocyanatomethyl; an unsubstituted or mono- to tetrasubstituted C 1 -C 4 alkylenedioxy group, where the substituents are selected from the group consisting of C 1 -C 4 alkyl and halogen; or QR 6 , where, if n is greater than 1, the radicals R 5  can be identical or different;  
 R 6  is C 2 -C 6 alkenyl or C 2 -C 6  alkynyl, which are unsubstituted or substituted by 1 to 3 halogen atoms; (C 1 -C 4 alkyl) 3 Si, where the alkyl groups can be identical or different; CN; or an unsubstituted or mono- to pentasubstituted C 3 -C 6 cycloalkyl, aryl or heterocyclyl group, where the substituents are selected from the group consisting of halogen, C 1 -C 6 alkyl, halogeno-C 1 -C 6 alkyl, C 1 -C 6 alkoxy, halogeno-C 1 -C 6 alkoxy, phenoxy, naphthoxy and CN;  
 A either is a direct bond, C 1 -C 6 akylene, —C(═O)—, —C(═S)— or halogeno-C 1 -C 10 alkylene and R 7  is a radical R 10 , 
 or is C 1 -C 10 alkylene, —C(═O)—, —C(═S)— or halogeno-C 1 -C 10 alkylene and  
 R 7  is OR 10 , N(R 10 ) 2 , where the radicals R 10  can be identical or different, or —S(═O) q R 10 ;  
 
 R 8  is H or C 1 -C 4 alkyl;  
 R 9  is methyl, fluoromethyl or difluoromethyl;  
 R 10  is H; an unsubstituted or substituted C 1 -C 6 alkyl, C 2 -C 6 alkenyl or C 2 -C 6 alkynyl group, where the substituents are selected from the group consisting of halogen; (C 1 -C 4 alkyl) 3 Si, where the alkyl groups can be identical or different; Cs-C 6 cyclo-alkyl, which is unsubstituted or substituted by halogen; C 1 -C 6 alkoxycarbonyl, which is unsubstituted or substituted by halogen; unsubstituted or substituted aryl, where the substituents are selected from the group consisting of halogen, halogeno-C 1 -C 4 alkyl and CN; a (C 1 -C 4 alkyl) 3 Si group, where the alkyl groups can be identical or different; C 3 -C 6 cycloalkyl, which is unsubstituted or substituted by halogen; C 1 -C 6 alkoxycarbonyl which is unsubstituted or substituted by halogen; or an unsubstituted or substituted aryl or heterocyclyl group, where the substituents are selected from the group consisting of halogen and halogeno-C 1 -C 4 alkyl;  
 Q is a direct bond, C 1 -C 8 alkylene, C 2 -C 6 alkenylene, C 2 -C 6 alkynylene, O, O(C 1 -C 6 alkylene), (C 1 -C 6 alkylene)O, S(═O) p , S(═O) p (C 1 -C 6 alkylene) or (C 1 -C 6 alkylene)S(═O) p ;  
 m is 0, 1 or 2;  
 n is 0, 1, 2, 3, 4 or 5;  
 p is 0, 1 or 2; and  
 q is 0, 1 or 2,  
 and the C═N double bond marked with E has the E configuration,  
 which comprises  
 a1) reacting either a compound of the formula  
                     
 in which A, R 2 , R 5 , R 7  and n are as defined for formula (I) and the C═N double bond marked with E has the E configuration, or a possible tautomer thereof, in each case in the free form or in salt form, with a compound of the formula  
                     
 in which X, Y, Z, R 3 , R 4  and R 9  are as defined for formula (I) and X 1  is a leaving group, or a tautomer thereof, in each case in the free from or in salt form, or  
 a2) reacting a compound of the formula  
                     
 in which A, R 2 , R 5 , R 7  and n are as defined for formula (I) and the C═N double bond marked with E has the E configuration, or a possible tautomer thereof, in each case in the free form or in the salt form with a compound of the formula  
                     
 in which X, Y, Z, R 3 , R 4  and R 9  are as defined for formula (I), or, if appropriate, a tautomer thereof, in each case in the free form or in salt form, or  
 b1) reacting a compound of the formula  
                     
 in which R 2 , R 5  and n are as defined for formula (I) and the C═N double bond marked with E has the E configuration, or a possible tautomer thereof, in each case in the free form or in salt form with a compound of the formula  
 R 7 -A-X 2   (VII),  
 in which A and R 7  are as defined for formula (I) and X 2  is a leaving group, and either further reacting the compound thus obtainable, of the formula (IV), for example according to method a2), or  
 b2) reacting it with hydroxylamine or a salt thereof and further reacting the compound thus obtainable, of the formula (II), for example according to method a1), or  
 c) reacting a compound of the formula  
                     
 in which R 2 , R 3  and n are as defined for formula (I),  
 or a possible tautomer thereof, in each case in the free form or in salt form with a C 1 -C 6 alkyl nitrite and further reacting the compound thus obtainable, of the formula (VI), for example according to method b).  
 
     
     
         2 . A process according to  claim 1  for the preparation of a compound of the formula (I), which comprises reacting a compound of the formula (II) with a compound of the formula (III).  
     
     
         3 . A process according to  claim 2 , wherein a compound of the formula (III) in which X 1  is halogen is used.  
     
     
         4 . A process according to  claim 2 , wherein a compound of the formula (III) in which X 1  is chlorine is used.  
     
     
         5 . A process according to  claim 2 , wherein the reaction is carried out in the presence of a base.  
     
     
         6 . A process according to  claim 5 , wherein the reaction is carried out in the presence of a base selected from the group consisting of alkali metal and alkaline earth metal hydroxides hydrides, amides, alkanolates, acetates, carbonates, dialkylamides and alkylsilylamides.  
     
     
         7 . A process according to  claim 6 , wherein the base is sodium hydride.  
     
     
         8 . A process according to  claim 2 , wherein the reaction is carried out in the presence of a solvent or diluent or of a mixture thereof.  
     
     
         9 . A process according to  claim 8 , wherein the solvent is selected from the group consisting of N,N-dimethylformamide, N,N-diethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone and hexamethylphosphoric acid triamide.  
     
     
         10 . A process according to  claim 9 , wherein the solvent is N,N-dimethylformamide.  
     
     
         11 . A process according to  claim 2 , wherein the reaction is carried out in a temperature range from about 10° to about 30°.  
     
     
         12 . A process according to  claim 2 , wherein the reaction time is between about 0.5 and about 2 hours.  
     
     
         13 . A process according to  claim 1  for the preparation of a compound of the formula (I), which comprises reacting the compound of the formula (IV), with a compound of the formula (V).  
     
     
         14 . A process according to  claim 13 , wherein the reaction is carried out in the presence of a base.  
     
     
         15 . A process according to  claim 14 , wherein the reaction is carried out in the presence of a base selected from the group consisting of alkali metal and alkaline earth metal hydroxides, hydrides, amides, alkanolates, acetates, carbonates, dialkylamides and alkylsilylamides.  
     
     
         16 . A process according to  claim 15 , wherein the base is sodium hydroxide.  
     
     
         17 . A process according to  claim 13 , wherein the reaction is carried out in the presence of a solvent or diluent or of a mixture thereof.  
     
     
         18 . A process according to  claim 17 , wherein the solvent is selected from the group consisting of methanol, ethanol, propanol, isopropanol, butanol, ethylene glycol and glycerol.  
     
     
         19 . A process according to  claim 18 , wherein the reaction is carried out in methanol.  
     
     
         20 . A process according to  claim 13 , wherein the reaction is carried out in a temperature range from about 10° to about 30°.  
     
     
         21 . A process according to  claim 13 , wherein the reaction time is between about 0.5 and about 2 hours.  
     
     
         22 . A process according to  claim 1  for the preparation of a compound of the formula (I), which comprises reacting the compound of the formula (VI), with a compound of the formula (VII), and either reacting the compound thus obtainable, of the formula (IV), according to the process according to  claim 13 , or reacting it with hydroxylamine or a salt thereof, if appropriate in the presence of a basic or acid catalyst, and further reacting the compound thus obtainable, of the formula (II), according to the process according to  claim 2 .  
     
     
         23 . A process according to  claim 22 , wherein a compound of the formula (VII) in which X 2  is halogen is used.  
     
     
         24 . A process according to  claim 22 , wherein a compound of the formula (VII) in which X 2  is chlorine is used.  
     
     
         25 . A process according to  claim 22 , wherein the reaction of the compound of the formula (VI) with the compound of the formula (VII) is carried out in the presence of a base.  
     
     
         26 . A process according to  claim 25 , wherein the reaction is carried out in the presence of a base selected from the group consisting of alkali metal and alkaline earth metal hydroxides, hydrides, amides, alkanolates, acetates, carbonates, dialkylamides and alkylsilylamides.  
     
     
         27 . A process according to  claim 26 , wherein the base is potassium carbonate.  
     
     
         28 . A process according to  claim 22 , wherein the reaction of the compound of the formula (VI) with the compound of the formula (VII) is carried out in the presence of a solvent or diluent or of a mixture thereof.  
     
     
         29 . A process according to  claim 28 , wherein the solvent is selected from the group consisting of acetonitrile and propionitrile.  
     
     
         30 . A process according to  claim 29 , wherein the reaction is carried out in acetonitrile.  
     
     
         31 . A process according to  claim 22 , wherein the reaction of the compound of the formula (VI) with the compound of the formula (VII) is carried out in a temperature range of about 10° to about 80°.  
     
     
         32 . A process according to  claim 22 , wherein the duration of the reaction of the compound of the formula (VI) with the compound of the formula (VII) is between about 0.5 and about 2 hours.  
     
     
         33 . A process according to  claim 1  for the preparation of a compound of the formula (I), which comprises reacting the compound of the formula (VIII), with a C 1 -C 6  alkyl nitrite and further reacting the compound thus obtainable, of the formula (VI), according to the process according to  claim 22 .  
     
     
         34 . A process according to  claim 33 , wherein the reaction is carried out in the presence of a base.  
     
     
         35 . A process according to  claim 34 , wherein the reaction is carried out in the presence of a base selected from the group consisting of alkali metal and alkaline earth metal hydroxides, hydrides, amides, alkanolates, acetates, carbonates, dialkylamides and alkylsilylamides.  
     
     
         36 . A process according to  claim 35 , wherein the base is sodium methanolate.  
     
     
         37 . A process according to  claim 33 , wherein the reaction is carried out in the presence of a solvent or diluent or of a mixture thereof.  
     
     
         38 . A process according to  claim 37 , wherein the solvent is selected from the group consisting of methanol, ethanol, propanol, isopropanol, butanol, ethylene glycol and glycerol.  
     
     
         39 . A process according to  claim 38 , wherein the reaction is carried out in methanol.  
     
     
         40 . A process according to  claim 33 , wherein the reaction is carried out in a temperature range from about 0° C. to about 60° C.  
     
     
         41 . A process according to  claim 33 , wherein the reaction time is between about 0.5 and about 3 hours.  
     
     
         42 . A process for the preparation of a compound of the formula  
       
         
           
           
               
               
           
         
       
       in which A, R 2 , R 5 , R 7  and n are as defined for formula (I) and the C═N double bond marked with E has the E configuration, which comprises reacting the compound of the formula  
       
         
           
           
               
               
           
         
       
       in which R 2 , R 5  and n are as defined for formula (I) and the C═N double bond marked with E has the E configuration, with a compound of the formula  
       R 7 -A-X 2   (VII),  
       in which A and R 7  are as defined for formula (I) and X 2  is a leaving group.  
     
     
         43 . A process according to  claim 42 , wherein a compound of the formula (VII) in which X 2  is halogen is used.  
     
     
         44 . A process according to  claim 43 , wherein a compound of the formula (VII) in which X 2  is chlorine is used.  
     
     
         45 . A process according to  claim 42 , wherein the reaction is carried out in the presence of a base.  
     
     
         46 . A process according to  claim 45 , wherein the reaction is carried out in the presence of a base selected from the group consisting of alkali metal and alkaline earth metal hydroxides, hydrides, amides, alkanolates, acetates, carbonates, dialkylamides and alkylsilylamides.  
     
     
         47 . A process according to  claim 46 , wherein the base is potassium carbonate.  
     
     
         48 . A process according to  claim 47 , wherein the reaction is carried out in the presence of a solvent or diluent or of a mixture thereof.  
     
     
         49 . A process according to  claim 48 , wherein the solvent is selected from the group consisting of acetonitrile and propionitrile.  
     
     
         50 . A process according to  claim 49 , wherein the reaction is carried out in acetonitrile.  
     
     
         51 . A process according to  claim 42 , wherein the reaction is carried out in a temperature range from about 10° to about 80°.  
     
     
         52 . A process according to  claim 42 , wherein the reaction time is between about 0.5 and about 2 hours.  
     
     
         53 . A process for the preparation of a compound of the formula  
       
         
           
           
               
               
           
         
       
       in which A, R 2 , R 5 , R 7  and n are as defined for formula (I) and the C═N double bond marked with E has the E configuration, which comprises reacting the compound of the formula  
       
         
           
           
               
               
           
         
       
       in which A, R 2 , R 5 , R 7  and n are as defined for formula (I) and the C═N double bond marked with E has the E configuration, with hydroxylamine or a salt thereof.  
     
     
         54 . A process according to  claim 53 , wherein the reaction is carried out with hydroxylamine hydrochloride.  
     
     
         55 . A process according to  claim 53 , wherein the reaction is carried out in the presence of a solvent or diluent or of a mixture thereof.  
     
     
         56 . A process according to  claim 55 , wherein the solvent is selected from the group consisting of methanol, ethanol, propanol, isopropanol, butanol, ethylene glycol and glycerol.  
     
     
         57 . A process according to  claim 56 , wherein the reaction is carried out in ethanol.  
     
     
         58 . A process according to  claim 53 , wherein the reaction is carried out in a temperature range from about 20° to about 100°.  
     
     
         59 . A process according to  claim 53 , wherein the reaction time is between about 0.5 and about 2 hours.  
     
     
         60 . A process for the preparation of a compound of the formula  
       
         
           
           
               
               
           
         
       
       in which R 2 , R 5  and n are as defined for formula (I) and the C═N double bond marked with E has the E configuration, which comprises reacting the compound of the formula  
       
         
           
           
               
               
           
         
       
       in which R 2 , R 5  and n are as defined for formula (I), with a C 1 -C 6 alkylnitrite.  
     
     
         61 . A process according to  claim 60 , wherein the reaction is carried out in the presence of a base.  
     
     
         62 . A process according to  claim 61 , wherein the reaction is carried out in the presence of a base selected from the group consisting of alkali metal and alkaline earth metal hydroxides, hydrides, amides, alkanolates, acetates, carbonates, dialkylamide and alkylsilylamides.  
     
     
         63 . A process according to  claim 62 , wherein the base is sodium methanolate.  
     
     
         64 . A process according to  claim 60 , wherein the reaction is carried out in the presence of a solvent or diluent or of a mixture thereof.  
     
     
         65 . A process according to  claim 64 , wherein the solvent is selected from the group consisting of methanol, ethanol, propanol, isopropanol, butanol, ethylene glycol and glycerol.  
     
     
         66 . A process according to  claim 65 , wherein the reaction is carried out in methanol.  
     
     
         67 . A process according to  claim 60 , wherein the reaction is carried out in a temperature range from about 0° to about 40°.  
     
     
         68 . A process according to  claim 60 , wherein the reaction time is between about 0.5 and about 2 hours.  
     
     
         69 . A compound of the formula  
       
         
           
           
               
               
           
         
       
       in which A, R 2 , R 5 , R 7  and n are as defined in  claim 1  for formula (I) and the C═N double bond marked with E has the E configuration, or if appropriate a tautomer thereof, in each case in the free form or in salt form.  
     
     
         70 . A compound of the formula  
       
         
           
           
               
               
           
         
       
       in which A, R 2 , R 5 , R 7  and n are as defined in  claim 1 , for formula (I) and the C═N double bond marked with E has the E configuration, or if appropriate a tautomer thereof, in each case in the free form or in salt form.  
     
     
         71 . A compound of the formula  
       
         
           
           
               
               
           
         
       
       in which R 2 , R 5  and n are as defined for formula (I) and the C═N double bond marked with E has the E configuration, or if appropriate a tautomer thereof, in each case in the free form or in salt form.