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
AssigneeBayer Aktiengesellschaft
InventorKarl-Heinz Aleksander Ostoja Starzewski
Life of this patent
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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 R19 denotes hydrogen, C1-C4-alkyl, vinyl or chlorine and R38 denotes C1-C4-alkyl, C2-C4-alkenyl, C2-C7-acyl, flourine, chlorine or bromine and m assumes values of 4-104, with the exception of compounds wherein R19 denotes hydrogen and R38 denotes i-butyl or benzoyl, and m assumes the value 4, are new.
Claims14
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
- R19 denotes hydrogen, C1-C4-alkylvinyl or chlorine,
- R38 denotes C1-C4-alkyl, C2-C4-alkenyl, C2-C7-acyl, fluorine chlorine or bromine, and
- m has a value of 4 to 104,
- with the exception of compounds wherein R19 is hydrogen and R38 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
- R4, R5, R6, R7 and R8 independently of one another denote straight-chain or branched C1-C20-alkyl, C2-C20-alkenyl, C1-C20-alkoxy, C3-C8-cycloalkyl, C6-C12-aryl, C6-C12-aryloxy, C7-C15-aralkyl or C7-C15-aralkoxy, where
- R7 can additionally denote hydrogen and
- R8 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
- R4, R5 and R6 have the meaning mentioned.
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
- R11, R12 and R13 independently of one another denote C1-C8-alkyl, phenyl or benzyl,
- R14 represents hydrogen, C1-C8-alkyl or phenyl,
- R15, R16 and R17 independently of one another denote C1-C8-alkyl or phenyl, where R17 can additionally denote hydrogen or acyl, and
- R20 denotes phenyl or C1-C4-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
- R15 and R16 have the meaning mentioned,
- and a compound of the formula (IV).
The process of claim 5, wherein 0.1 to 10 mmol of nickel catalyst are employed per mol of styrene derivative.
The process of claim 6, wherein 0.2 to 5 mmol of nickel catalyst are employed per mol of styrene derivative.
The process of claim 8, wherein a styrene derivative of the formula
- is employed in which
- R28 is hydrogen, methyl, ethyl, i-butyl, C2-C7-acyl, vinyl or chlorine and
- R29 is hydrogen, vinyl, methyl or chlorine.
A styrene derivative extended with ethylene and having a double bond remaining in the extension formed, of the formula
- in which
- R48 is i-butyl or benzoyl, and
- m is an even number from 6 to 204.
A styrene derivative extended with ethylene and having a double bond remaining in the extension formed, of the formula
- in which
- R48 is vinyl, and
Dependencies are inferred from the claim text.