Process for the Asymmetric Epoxidation of Olefins

Abstract

The present invention relates to a catalyst based on ruthenium complexes and to a process for the asymmetric epoxidation of olefins using catalysts based on ruthenium complexes.

1 . Compounds according to formula (V) comprising: 
     
       
         
         
             
             
         
       
       wherein R 9  is hydrogen, halogen, hydroxy, alkoxy, hydroxycarbonyl, alkoxycarbonyl, alkyl, arylalkyl or aryl and 
       L 1  and L 2  are each, independently of one another, a radical of the formula (VI) 
     
     
       
         
         
             
             
         
       
       wherein “*1” is an asymmetric carbon atom in the (R) or (S) configuration and “*2” can likewise be such a carbon atom, the arrow points to the point of bonding to the central pyridine ring and each R 10  and R 11  are each, independently of one another, alkyl, alkoxyalkyl, trialkylsiloxyalkyl, alkoxycarbonyl, arylalkyl or aryl or one R 10  and R 11  are part of a cyclic radical having a total of from 5 to 16 carbon atoms and the other R 10  is hydrogen said compound not including those radicals where L 1  and L 2  are radicals where both R 10  are each hydrogen and R 11  is isopropyl or phenyl. 
     
   
   
       2 . Compounds according to  claim 1  consisting of those selected from 4-Chloro-2,6-bis[4′-(S)-phenyloxazolin-2′-yl]pyridine, 4-phenyl-2,6-bis[4′-(S)-phenyl-oxazolin-2′-yl]pyridine, 2,6-bis[(R)-4′-(1″-naphthyl)-5′,6′-dihydro-4′H-[1′,3′]oxazin-2′-yl]pyridine, and 2,6-bis[(R)-4′-(2″-naphthyl)-5′,6′-dihydro-4′H-[1′,3′]oxazin-2′-yl]-pyridine. 
   
   
       3 . Ruthenium complexes comprising compounds of the formula (V) according to  claim 1 . 
   
   
       4 . Ruthenium complexes according to  claim 3  consisting of those selected from 4-Chloro-2,6-bis[4′-(S)-phenyloxazolin-2′-yl]pyridine, 4-phenyl-2,6-bis[4′-(S)-phenyloxazolin-2′-yl]pyridine, 2,6-bis[(R)-4′-(1″-naphthyl)-5′,6′-dihydro-4′H-[1′,3′]oxazin-2′-yl]pyridine, and 2,6-bis[(R)-4′-(2″-naphthyl)-5′,6′-dihydro-4′H-[1′,3′]oxazin-2′-yl]pyridine. 
   
   
       5 . Method of for preparing pharmaceuticals, agrochemicals, polymers or intermediates comprising preparing said pharmaceuticals, agrochemicals, polymer or intermediates by using compounds of the formula (I) 
     
       
         
         
             
             
         
       
       wherein 
       “*” is a carbon atom having an (R) or (S) configuration and R 1 , R 2 , R 3  and R 4  are each, independently of one another, hydrogen, alkyl, aryl, arylalkyl, haloalkyl or a radical of one of formulae (IIa) to (IIf)
   A-B-D-E  (IIa) 
   A-E  (IIb) 
   A-SO 2 -E  (IIc) 
   A-B-SO 2 R 6   (IId) 
   A-SO 3 W  (IIe) 
   A-COW  (IIf) 
 
       wherein, in the formulae (IIa) to (IIf) 
       A is absent or is an alkylene or haloalkylene radical and 
       B is absent or is oxygen or NR 5 , where 
       R 5  is nitrogen, arylalkyl or aryl, and 
       D is a carbonyl group and 
       E is R 6 , OR 6 , NHR 7  or N(R 7 ) 2 , 
       wherein 
       R 6  is alkyl, arylalkyl or aryl and the radicals R 7  are each, independently of one another, alkyl, arylalkyl or aryl or the moiety N(R 7 ) 2  is a cyclic amino radical having from 4 to 12 carbon atoms and 
       W is OH, NH 2 , or OM,
 where M is an alkali metal ion, half an equivalent of an alkaline earth metal ion, an ammonium ion or an organic ammonium ion, or two of the radicals R 1 , R 2 , R 3  and R 4  are together part of a 3- to 7-membered ring having a total of from 3 to 16 carbon atoms, 
 
     
     wherein compounds of formula (I) are prepared by reacting compounds of the formula (III), 
     
       
         
         
             
             
         
       
       where R 1 , R 2 , R 3  and R 4  are each, independently of one another, as defined above, 
       with compounds of the formula (IV),
   R 8 —OOH  (IV) 
 
       wherein R 8  is hydrogen, alkyl or arylalkyl, 
       in the presence of a ruthenium complex which bears as ligands both compounds of the formula (V) 
     
     
       
         
         
             
             
         
       
       wherein R 9  is hydrogen, halogen, hydroxy, alkoxy, hydroxycarbonyl, alkoxycarbonyl, alkyl, arylalkyl or aryl and 
       L 1  and L 2  are each, independently of one another, a radical of the formula (VI) 
     
     
       
         
         
             
             
         
       
       wherein “*1” is an asymmetric carbon atom in the (R) or (S) configuration and “*2” can likewise be such a carbon atom, the arrow points to the point of bonding to the central pyridine ring and R 10  and R 11  are each, independently of one another, alkyl, alkoxyalkyl, trialkylsiloxyalkyl, alkoxycarbonyl, arylalkyl or aryl or R 10  and R 11  are part of a cyclic radical having a total of from 5 to 16 carbon atoms and R 10  may also be hydrogen, 
       and compounds of the formula (VII) 
     
     
       
         
         
             
             
         
       
       wherein 
       X 1 , X 2  and X 3  are each, independently of one another, N, CH or CR 12  and 
       R 12  is hydrogen, halogen, hydroxy, hydroxycarbonyl, alkoxycarbonyl, alkoxy, alkoxyalkyl, arylalkyl or aryl and 
       n is 0, 1, 2 or 3, preferably 0 or 1 and particularly preferably 0. 
     
   
   
       6 . A pharmaceutical comprising a compound of the formula (I) prepared according to  claim 5 . 
   
   
       7 . An agrochemical comprising a compound of the formula (I) prepared according to  claim 5 . 
   
   
       8 . A polymer comprising a compound of the formula (I) prepared according to  claim 5 . 
   
   
       9 . An intermediate compound for a pharmaceutical, an agro chemical or a polymer comprising a compound of the formula (I) wherein the compound of formula (I) wherein compounds of formula (I): 
     
       
         
         
             
             
         
       
       wherein 
       “*” is a carbon atom having an (R) or (S) configuration and R 1 , R 2 , R 3  and R 4  are each, independently of one another, hydrogen, alkyl, aryl, arylalkyl, haloalkyl or a radical of one of formulae (IIa) to (IIf)
   A-B-D-E  (IIa) 
   A-E  (IIb) 
   A-SO 2 -E  (IIc) 
   A-B-SO 2 R 6   (IId) 
   A-SO 3 W  (IIe) 
   A-COW  (IIf) 
 
       wherein, in the formulae (IIa) to (IIf) 
       A is absent or is an alkylene or haloalkylene radical and 
       B is absent or is oxygen or NR 5 , where 
       R 5  is nitrogen, arylalkyl or aryl, and 
       D is a carbonyl group and 
       E is R 6 , OR 6 , NHR 7  or N(R 7 ) 2 , 
       wherein 
       R 6  is alkyl, arylalkyl or aryl and 
       the radicals R 7  are each, independently of one another, alkyl, arylalkyl or aryl or the moiety N(R 7 ) 2  is a cyclic amino radical having from 4 to 12 carbon atoms and 
       W is OH, NH 2 , or OM,
 where M is an alkali metal ion, half an equivalent of an alkaline earth metal ion, an ammonium ion or an organic ammonium ion, or two of the radicals R 1 , R 2 , R 3  and R 4  are together part of a 3- to 7-membered ring having a total of from 3 to 16 carbon atoms, 
 
     
     are prepared by reacting compounds of the formula (III), 
     
       
         
         
             
             
         
       
       where R 1 , R 2 , R 3  and R 4  are each, independently of one another, as defined above, 
       with compounds of the formula (IV),
   R 8 —OOH  (IV) 
 
       wherein R 8  is hydrogen, alkyl or arylalkyl, 
       in the presence of a ruthenium complex which bears as ligands both compounds of the formula (V) 
     
     
       
         
         
             
             
         
       
       wherein R 9  is hydrogen, halogen, hydroxy, alkoxy, hydroxycarbonyl, alkoxycarbonyl, alkyl, arylalkyl or aryl and 
       L 1  and L 2  are each, independently of one another, a radical of the formula (VI) 
     
     
       
         
         
             
             
         
       
       wherein “*1” is an asymmetric carbon atom in the (R) or (S) configuration and “*2” can likewise be such a carbon atom, the arrow points to the point of bonding to the central pyridine ring and R 10  and R 11  are each, independently of one another, alkyl, alkoxyalkyl, trialkylsiloxyalkyl, alkoxycarbonyl, arylalkyl or aryl or R 10  and R 11  are part of a cyclic radical having a total of from 5 to 16 carbon atoms and R 10  may also be hydrogen, 
       and compounds of the formula (VII) 
     
     
       
         
         
             
             
         
       
       wherein 
       X 1 , X 2  and X 3  are each, independently of one another, N, CH or CR 12  and 
       R 12  is hydrogen, halogen, hydroxy, hydroxycarbonyl, alkoxycarbonyl, alkoxy, alkoxyalkyl, arylalkyl or aryl and 
       n is 0, 1, 2 or 3, preferably 0 or 1 and particularly preferably 0.