Process for the preparation of styrene derivatives extended at the double bond by ethylene and having a double bond remaining in the extension chain formed and new styrene derivatives extended with ethylene

Abstract

The title compounds can be prepared by reaction of a styrene derivative with ethylene in the presence of a nickel catalyst which carries a phosphorus-oxygen chelate ligand, at a temperature of 20° to 160° C. and an ethylene pressure of 1 to 200 bar. Styrene derivatives extended with ethylene, of the formula in which R 19 denotes hydrogen, C 1 -C 4 -alkyl, vinyl or chlorine and R 38 denotes C 1 -C 4 -alkyl, C 2 -C 4 -alkenyl, C 2 -C 7 -acyl, flourine, chlorine or bromine and m assumes values of 4-104, with the exception of compounds wherein R 19 denotes hydrogen and R 38 denotes i-butyl or benzoyl, and m assumes the value 4, are new.

What is claimed is:  
     
       1. A process for the preparation of styrene derivatives extended at the double bond with ethylene and having a double bond remaining in the extension chain formed, according to the formula                    
       in which 
       R 19  denotes hydrogen, C 1 -C 4 -alkylvinyl or chlorine,  
       R 38  denotes C 1 -C 4 -alkyl, C 2 -C 4 -alkenyl, C 2 -C 7 -acyl, fluorine chlorine or bromine, and  
       m has a value of 4 to 104,  
       with the exception of compounds wherein R 19  is hydrogen and R 38  is isobutyl or benzyl and m has the value 4, wherein a styrene derivative is reacted with ethylene in the presence of a nickel catalyst which carries a phosphorus-oxygen chelate ligand, at a temperature of 20 to 160° C. and an ethylene pressure of 1 to 200 bar, wherein the nickel catalyst is obtained by reaction of a nickel (O) compound, or a compound which can be converted in situ to a nickel (O) compound, with a phosphorus compound of the formula                    
       in which 
       R 4 , R 5 , R 6 , R 7  and R 8  independently of one another denote straight-chain or branched C 1 -C 20 -alkyl, C 2 -C 20 -alkenyl, C 1 -C 20 -alkoxy, C 3 -C 8 -cycloalkyl, C 6 -C 12 -aryl, C 6 -C 12 -aryloxy, C 7 -C 15 -aralkyl or C 7 -C 15 -aralkoxy, where  
       R 7  can additionally denote hydrogen and  
       R 8  can additionally denote hydrogen, acyl or sulphonate,  
       or a nickel catalyst which can be prepared by reaction of a nickel (O) compound, or a compound which can be converted in situ to a nickel (O) compound, with an adduct of a quinoid compound or maleic anhydride and a phosphine of the formula                    
       in which 
       R 4 , R 5  and R 6  have the meaning mentioned.  
     
     
       2. The process of claim  1 , wherein for the preparation of the nickel catalyst from a nickel(O) compound or a compound which can be converted in situ into a nickel(O) compound, and from a compound of the formula (I) or from an adduct of a quinoid compound or maleic anhydride and a compound of the formula (II), a compound of the formula                    
       in additionally used as a starting material in which 
       R 1 , R 2  and R 3  independently of one another denote straight-chain or branched C 1 -C 20 -alkyl, C 1 -C 20 -alkoxy, C 3 -C 8 -cycloalkyl, C 2 -C 20 -alkenyl, di-(C 1 -C 4 -alkyl)amino, C 6 -C 12 -aryl, C 6 -C 12 -aryloxy, C 7 -C 15 -aralkyl or C 7 -C 15 -aralkoxy,  
       X denotes doubly bonded oxygen, the doubly bonded group NR 9  or the doubly bonded group                    
       R 9  and R 10  independently of one another denote hydrogen, silyl, acyl, chlorophenyl, nitrophenyl, C 1 -C 6 -alkylphenyl, cyano, phenyl-C 2 -C 6 -alkenyl or R 1 , and  
       n assumes the value zero or one.  
     
     
       3. The process of claim  3 , wherein the reaction is carried out in the presence of a nickel catalyst which is obtained by reaction of a nickel(O) compound, or a compound which can be converted into a nickel(O) compound in situ, with phosphorus compounds of the formulae                    
       in which 
       R 11 , R 12  and R 13  independently of one another denote C 1 -C 8 -alkyl, phenyl or benzyl,  
       R 14  represents hydrogen, C 1 -C 8 -alkyl or phenyl,  
       R 15 , R 16  and R 17  independently of one another denote C 1 -C 8 -alkyl or phenyl, where R 17  can additionally denote hydrogen or acyl, and  
       R 20  denotes phenyl or C 1 -C 4 -alkyl,  
       or a nickel catalyst which can be prepared by reaction of a nickel(O) compound, or a compound which can be converted in situ into a nickel(O) compound, with an adduct of benzoquinone or maleic anhydride and a phosphine of the formula                    
       in which 
       R 15  and R 16  have the meaning mentioned,  
       and a compound of the formula (IV).  
     
     
       4. The process of claim  1 , wherein 0.01 to 100 mmol of nickel catalyst are employed per mol of styrene derivative. 
     
     
       5. The process of claim  5 , wherein 0.1 to 10 mmol of nickel catalyst are employed per mol of styrene derivative. 
     
     
       6. The process of claim  6 , wherein 0.2 to 5 mmol of nickel catalyst are employed per mol of styrene derivative. 
     
     
       7. The process of claim  1 , wherein a styrene derivative of the formula                    
       is employed in which 
       R 18  is hydrogen, C 1 -C 4 -alkyl, C 2 -C 4 -alkenyl, C 2 -C 7 -acyl, fluorine, chlorine or bromine and  
       R 19  is hydrogen, C 1 -C 4 -alkyl, vinyl or chlorine.  
     
     
       8. The process of claim  8 , wherein a styrene derivative of the formula                    
       is employed in which 
       R 28  is hydrogen, methyl, ethyl, i-butyl, C 2 -C 7 -acyl, vinyl or chlorine and  
       R 29  is hydrogen, vinyl, methyl or chlorine.  
     
     
       9. The process of claim  1 , which is carried out at a temperature of 30° to 160° C. 
     
     
       10. The process of claim  9 , which is carried out at a temperature of 40° to 120° C. 
     
     
       11. The process of claim  10 , which is carried out at a temperature of 50° to 100° C. 
     
     
       12. A styrene derivative extended with ethylene and having a double bond remaining in the extension formed, of the formula                    
       
         in which  
       
         R   48    is i - butyl or benzoyl, and    
       
         m is an even number from  6  to  204 . 
       
     
     
       13. A styrene derivative extended with ethylene and having a double bond remaining in the extension formed, of the formula                    
       
         in which  
       
       
         R 
         48  
         is vinyl, and  
         
           
           
               
               
           
         
       
     
     
       14. A derivative according to claim  12 , wherein m is up to  64 .