Optically active 2,5-bisaryl-delta¹ -pyrrolines and their use as pest control agents

Abstract

Novel optically active Δ 1 -pyrrolines of the formula (I) in which R 1 , R 2 , R 3 , R 4 , and m are each as defined in the description, a plurality of the processes for preparing these substances and their use for controlling pests.

1 . Optically active Δ 1 -pyrrolines of the formula (I) 
     
       
         
         
             
             
         
       
       in which 
       * represents a chiral carbon atom having the (R)-configuration, 
       m represents 0, 1, 2, 3 or 4, 
       R 1  represents halogen or methyl, 
       R 2  represents hydrogen or halogen, 
       R 3  represents hydrogen, halogen, hydroxyl, alkyl, alkenyl, alkinyl, halogenoalkyl, halogenoalkenyl, alkoxy, —S(O) o R 6 , —OSO 2 R 6 , bisalkoxyborane, —B(OH) 2  or represents phenyl which is optionally mono- or polysubstituted by radicals from the list W 1 , 
       R 4  represents halogen, alkyl, alkoxy, halogenoalkyl, halogenoalkoxy or S(O) o R 6 , 
       W 1  represents cyano, halogen, hydroxyl, alkyl, halogenoalkyl, alkenyl, halogenoalkenyl, alkoxy, halogenoalkoxy, alkenyloxy, halogenoalkenyloxy, alkoxycarbonyl, trialkylsilyl, trialkylsilyloxy, —CONH 2 , —NR 7 R 8 , —S(O) o R 6  or —SO 2 NR 7 R 8 , 
       o represents 0, 1 or 2, 
       R 6  represents hydrogen, alkyl or halogenoalkyl, 
       R 7  and R 8  independently of one another each represent hydrogen, alkyl, halogenoalkyl or together represent alkylene or alkoxyalkylene. 
     
   
   
       2 . Optically active Δ 1 -pyrrolines of the formula (I) according to  claim 1  in which
 m represents 0, 1, 2 or 3,   R 1  represents fluorine, chlorine, bromine or methyl,   R 2  represents hydrogen, fluorine, chlorine or bromine,   R 3  represents hydrogen, fluorine, chlorine, bromine, iodine, hydroxyl, C 1 -C 6 -alkyl, C 2 -C 6 -alkenyl, C 2 -C 6 -alkinyl, C 1 -C 6 -halogenoalkyl, C 2 -C 6 -halogenoalkenyl, C 1 -C 6 -alkoxy, —S(O) o R 6 , —OSO 2 R 6 , bis(C 4 -C 8 -alkoxy)borane, —B(OH) 2  or represents phenyl which is optionally mono- or polysubstituted by radicals from the list W 1 ,   R 4  represents halogen, C 1 -C 6 -alkyl, C 1 -C 6 -alkoxy, C 1 -C 6 -halogenoalkyl, C 1 -C 6 -halogenoalkoxy or —S(O) o R 6 ,   W 1  represents cyano, halogen, hydroxyl, C 1 -C 6 -alkyl, C 1 -C 6 -alkoxy, C 1 -C 6 -halogenoalkyl, C 1 -C 6 -halogenoalkoxy, C 2 -C 6 -halogenoalkenyloxy, C 1 -C 6 -alkoxycarbonyl, tri(C 1 -C 4 -alkyl)silyl, tri(C 1 -C 4 -alkyl)silyloxy, —S(O) o R 6  or —SO 2 NR 7 R 8 ,   o represents 0, 1 or 2,   R 6  represents hydrogen, C 1 -C 6 -alkyl or C 1 -C 6 -halogenoalkyl,   R 7  and R 8  independently of one another each represent hydrogen, C 1 -C 6 -alkyl, C 1 -C 6 -halogenoalkyl or together represent C 2 -C 6 -alkylene or C 1 -C 4 -alkoxy-C 1 -C 4 -alkylene (for example morpholine).   
   
   
       3 . Optically active Δ 1 -pyrrolines of the formula (I) according to  claim 1  in which
 m represents 0, 1, or 2,   R 1  represents fluorine, chlorine or methyl,   R 2  represents hydrogen, fluorine or chlorine,   R 3  represents hydrogen, fluorine, chlorine, bromine, hydroxyl, C 1 -C 6 -alkyl, C 2 -C 6 -alkenyl, C 2 -C 6 -alkinyl, C 1 -C 6 -alkoxy; represents in each case fluorine- or chlorine-substituted C 1 -C 6 -alkyl or C 2 -C 6 -alkenyl; represents —S(O) o R 6 , —OSO 2 R 6 , (5,5-dimethyl-1,3,2-dioxoborinan)-2-yl, (4,4,5,5-tetramethyl-1,3,2-dioxoborolan)-2-yl, (4,4,6-trimethyl-1,3,2-dioxoborinan)-2-yl, 1,3,2-benzodioxaborol-2-yl, —B(OH) 2  or represents phenyl which is optionally mono- to trisubstituted by radicals from the list W 1 .   R 4  represents fluorine, chlorine, bromine, C 1 -C 6 -alkyl, C 1 -C 6 -alkoxy, in each case fluorine- or chlorine-substituted C 1 -C 6 -alkyl or C 1 -C 6 -alkoxy or represents —S(O) o R 6      W 1  represents cyano, fluorine, chlorine, bromine, iodine, hydroxyl, C 1 -C 4 -alkyl, C 1 -C 4 -alkoxy, in each case fluorine- or chlorine-substituted C 1 -C 4 -alkyl, C 1 -C 4 -alkoxy, C 2 -C 6 -alkenyloxy, represents C 1 -C 4 -alkoxycarbonyl, —OSi(Me 2 ) t -Bu, —S(O) o R 6  or —SO 2 NR 7 R 8 ,   o represents 0, 1, or 2,   R 6  represents hydrogen, C 1 -C 6 -alkyl or represents fluorine- or chlorine-substituted C 1 -C 4 -alkyl,   R 7  and R 8  independently of one another each represent hydrogen, C 1 -C 6 -alkyl, fluorine- or chlorine-substituted C 1 -C 6 -alkyl, or together represent C 4 -C 5 -alkylene.   
   
   
       4 . Optically active Δ 1 -pyrrolines of the formula (I) according to  claim 1  in which
 m represents 0, 1 or 2,   R 1  represents fluorine, chlorine or methyl,   R 2  represents hydrogen, fluorine or chlorine,   R 3  represents hydrogen, chlorine, bromine, hydroxyl, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, 2-propenyl, butenyl, propargyl, butinyl, methoxy, ethoxy, n-propoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, —SO 2 CF 3 , —SO 2 (CF 2 ) 3 CF 3 , —OSO 2 CF 3 , —OSO 2 (CF 2 ) 3 CF 3 , (5,5-dimethyl-1,3,2-dioxoborinan)-2-yl, (4,4,5,5-tetramethyl-1,3,2-dioxoborolan)-2-yl, (4,4,6-trimethyl-1,3,2-dioxoborinan)-2-yl, 1,3,2-benzodioxaborol-2-yl, —B(OH) 2  or represents fluorine- or chlorine-substituted C 1 -C 4 -alkyl or represents phenyl which is optionally mono- to trisubstituted by radicals from the list W 1 ,   R 3  furthermore represents isopropoxy,   R 4  represents fluorine, chlorine, bromine, methyl, ethyl, methoxy, ethoxy, trifluoromethyl, difluoromethoxy, trifluoromethoxy or —SO 2 CF 3 ,   W 1  represents cyano, fluorine, chlorine, bromine, hydroxyl, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, methoxy, ethoxy, n-propoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, trifluoromethoxy, difluoromethoxy, —CF 3 , —CHF 2 , —CClF 2 , —CF 2 CHFCl, —CF 2 CH 2 F, —CF 2 CCl 3 , —CH 2 CF 3 , —CF 2 CHFCF 3 , —CH 2 CF 2 H, —CH 2 CF 2 CF 3 , —CF 2 CF 2 H, —CF 2 CHFCF 3 , —OCF 2 CF 2 H, —OCF═CF 2 , —SCF 3 , —SOCF 3 , —SO 2 CF 3 , —SCHF 2 , —SOCHF 2 , —SO 2 CHF 2 , —OSi(Me 2 ) t -Bu, —SO 2 NMe 2  or —CO 2 Et,   W 1  furthermore represents isopropoxy.   
   
   
       5 . Process for preparing compounds of the formula (I) according to  claim 1 , characterized in that
 A) racemic compounds of the formula (I-rac)   
     
       
         
         
             
             
         
       
       
         in which 
         R 1 , R 2 , R 3 , R 4  and m are each as defined in  claim 1 , 
         are chromatographed on a stationary chiral silica gel phase in the presence of an eluent or an eluent mixture as liquid phase, 
       
       or 
       B) (i) compounds of the formula (I-a) 
     
     
       
         
         
             
             
         
       
       
         in which 
         R 1 , R 2 , R 4  and m are each as defined in  claim 1  and 
         X 1  represents Cl, Br, I, —OSO 2 CF 3 , —OSO 2 (CF 2 ) 3 CF 3 , 
         are reacted with organometallic compounds of the formula (II)
   A-M  (II) 
 
         in which 
         A represents phenyl which is optionally mono- or polysubstituted by radicals from the list Wt, 
         where W 1  is as defined in  claim 1 , 
         M represents —B(OH) 2 , Sn( n Bu) 3  or ZnCl, 
         M furthermore represents MgCl, 
         in the presence of a catalyst, if appropriate in the presence of an acid binder and if appropriate in the presence of a diluent, 
       
       or 
       (ii) compounds of the formula (I-b) 
     
     
       
         
         
             
             
         
       
       
         in which 
         R 1 , R 2 , R 4  and m are each as defined in  claim 1 , 
         X 2  represents —B(OH) 2 , (4,4,5,5-tetramethyl-1,3,2-dioxoborolan)-2-yl, (5,5-dimethyl-1,3,2-dioxoborinan)-2-yl, (4,4,6-trimethyl-1,3,2-dioxoborinan)-2-yl, 1,3,2-benzodioxaborol-2-yl, Sn( n Bu) 3  or ZnCl, 
         are reacted with aromatic compounds of the formula (III)
   T-A  (III) 
 
         in which 
         A represents phenyl which is optionally mono- or polysubstituted by radicals from the list W 1 , 
         where W 1  is as defined in  claim 1 , 
         T represents Cl, Br, I, —OSO 2 CF 3 , —OSO 2 (CF 2 ) 3 CF 3 , 
         in the presence of a catalyst, if appropriate in the presence of an acid binder and if appropriate in the presence of a diluent, 
       
       or 
       (iii) compounds of the formula (I-a) 
     
     
       
         
         
             
             
         
       
       
         in which 
         R 1 , R 2 , R 4  and m are each as defined in  claim 1  and 
         X 1  is as defined above, 
         are reacted in a tandem reaction with aromatic compounds of the formula (III)
   T-A  (III) 
 
         in which 
         A and T are each as defined above, 
         in the presence of a catalyst, in the presence of 4,4,4′,4′,5,5,5′,5′-octamethyl-2,2′-bis-1,3,2-dioxaborolane or of 5,5,5′,5′-tetramethyl-2,2′-bis-1,3,2-dioxaborinane or of 4,4,4′,4′,6,6′-hexamethyl-2,2′-bis-1,3,2-dioxaborinane or of 2,2′-bis-1,3,2-benzodioxaborole and, if appropriate, in the presence of an acid binder and, if appropriate, in the presence of a diluent, 
       
       or 
       C) optically active Boc-protected aminoketones of the formula (IV) 
     
     
       
         
         
             
             
         
       
       
         in which 
         R 1 , R 2 , R 3 , R 4  and m are each as defined in  claim 1 , 
         are deprotected by treatment with a Lewis acid or protic acid and the amine that is formed in situ is cyclized in the presence of an acid. 
       
     
   
   
       6 . Optically active Δ 1 -pyrrolines according to any of  claims 1  to  4 , characterized by the formulae (I-c), (I-d), (I-e), (I-f) and (I-g) 
     
       
         
         
             
             
         
       
       in which in each case 
       R 3  is as defined in any of  claims 1  to  4  and 
       R 4-1  represents hydrogen, methoxy or ethoxy. 
     
   
   
       7 . Optically active Δ 1 -pyrrolines according to any of  claims 1  to  4 , characterized by the formulae (I-h), (I-i), (I-j), (I-k) and (I-l) 
     
       
         
         
             
             
         
       
       in which in each case 
       W 1  is as defined in any of  claims 1  to  3 . 
     
   
   
       8 . Optically active Δ 1 -pyrrolines according to  claim 7 , characterized by the formulae (I-h), (I-i), (I-j), (I-k) and (I-l) 
     
       
         
         
             
             
         
       
       in which in each case 
       W 1  represents cyano, fluorine, chlorine, bromine, hydroxyl, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, trifluoromethoxy, difluoromethoxy, —CF 3 , —CHF 2 , —CClF 2 , —CF 2 CHFCl, —CF 2 CH 2 F, —CF 2 CCl 3 , —CH 2 CF 3 , —CF 2 CHFCF 3 , —CH 2 CF 2 H, —CH 2 CF 2 CF 3 , —CF 2 CF 2 H, —CF 2 CHFCF 3 , —OCF 2 CF 2 H, —OCF═CF 2 , —SCF 3 , —SOCF 3 , —SO 2 CF 3 , —SCHF 2 , —SOCHF 2 , —SO 2 CHF 2 , —OSi(Me 2 ) t -Bu, —SO 2 NMe 2  or —CO 2 Et. 
     
   
   
       9 . Optically active AI-pyrroline according to  claim 1 , characterized by the formula below 
     
       
         
         
             
             
         
       
     
   
   
       10 . Optically active Δ 1 -pyrroline according to  claim 1 , characterized by the formula below 
     
       
         
         
             
             
         
       
     
   
   
       11 . Optically active Δ 1 -pyrroline according to  claim 1 , characterized by the formula below 
     
       
         
         
             
             
         
       
     
   
   
       12 . Optically active aminoketones of the formula (IV) 
     
       
         
         
             
             
         
       
       in which 
       R 1 , R 2 , R 3 , R 4  and m are each as defined in  claim 1 . 
     
   
   
       13 . Optically active N-Boc-lactams of the formula (V) 
     
       
         
         
             
             
         
       
       in which 
       R 3 , R 4  and m are each as defined in  claim 1 . 
     
   
   
       14 . Optically active lactams of the formula (VII) 
     
       
         
         
             
             
         
       
       in which 
       R 3 , R 4  and m are each as defined in  claim 1 . 
     
   
   
       15 . Optically active lactam according to  claim 14 , characterized by the formula below 
     
       
         
         
             
             
         
       
     
   
   
       16 . Optically active lactam according to  claim 14 , characterized by the formula below 
     
       
         
         
             
             
         
       
     
   
   
       17 . Pesticides, characterized in that they comprise at least one compound of the formula (I) according to  claim 1 , in addition to extenders and/or surfactants. 
   
   
       18 . Use of compounds of the formula (I) according to  claim 1  for controlling pests. 
   
   
       19 . Method for controlling pests, characterized in that compounds of the formula (I) according to  claim 1  are allowed to act on pests and/or their habitats. 
   
   
       20 . Process for preparing pesticides, characterized in that compounds of the formula (I) according to  claim 1  are mixed with extenders and/or surfactants. 
   
   
       21 . Use of compounds of the formula (I) according to  claim 1  for preparing pesticides.