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 ##STR1## in which R 19 denotes hydrogen, C 1 -C 4 -alkyl, vinyl or chlorine and R 38 denotes C 1 -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 ##STR20## 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 phosphorous-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 ##STR21## 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 ##STR22## 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 ##STR23## is 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 ##STR24## 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.]. .Iadd.2.Iaddend., 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 ##STR25## 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 ##STR26## 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.]. .Iadd.4 .Iaddend., wherein 0.1 to 10 mmol of nickel catalyst are employed per mol of styrene derivative. 
     
     
       6. The process of claim .[.6.]. .Iadd.5 .Iaddend., 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 ##STR27## 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.]. .Iadd.7 .Iaddend., wherein a styrene derivative of the formula ##STR28## is employed in which R 28  is hydrogen, methyl, ethyl, i-butyl, C 1  -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.