Verfahren zur Herstellung von Octadienylestern

摘要

1,274,072. Octadienyl esters. UNION CARBIDE CORP. 3 Sept., 1969 [4 Sept., 1968], No. 43609/69. Heading C2C. Octadienyl or substituted octadienyl esters are prepared by reacting a 1,3-conjugated acyclic diolefine with a carboxylic acid in the presence of a palladium or platinum catalyst and a tertiary amine with a basicity constant Kb greater than 10-7. Acids specified are aliphatic monocarboxylic, cycloalkane, aromatic, ethylenically unsaturated and the acid esters and acids of dicarboxylic acids, and the dienes include butadiene, isoprene, piperylene and 1,3-hexadiene. Tertiary amines suitable are trimethyl, triethyl, triisopropyl and tributylamines, N-methylmorpholine, 2-dimethylaminoethanol, 2-dimethylaminoethylacetate, 2 - diethylaminoethanol, methyldiethanolamine, triethanolamine, 3-dimethyl amino-1-propanol, N,N,N1,N1-tetramethyl-1,3-propandiamine, N,N,N1,N1-tetramethyl-1,3-butanediamine, N,N,N1,N1-tetramethylethylene diamine and triethylene diamine. The reaction may be in a homogeneous liquid phase and palladium and platinum compounds such as alkanoates, cycloalkanecarboxylates, aryl carboxylates, olefine complexes, alkyl and aryl nitrite complexes, salts and complex salts, complexes with trihydrocarbylphosphines and arsines, phosphates and phosphites and bidentate ligands are listed. Catalyst modifiers may also be present and include trihydrocarbylphosphines, -arsines, and -phosphites and mixtures thereof; compounds such as diethyloxyphenylphosphine, ethoxy diphenylphosphine; and bicyclic phosphites. The catalysts may be formed in situ. Examples describe butadieneacetic acid telomerizations to yield octatriene, 3-acetoxy-1,7-octadiene, and 1-acetoxy-2,7-octadiene using various catalysts with various tert. amines; butadiene with isobutyric and propionic acids, benzoic acid, acrylic acid, and phthalic acids. 1-Octa-2,7-dienyl acrylate and 3-octa-1,7- dienyl acrylate are novel compounds prepared by this process.