| 摘要 |
1,128,983. Hexadienes. TOYO RAYON K.K. 24 May, 1966 [25 May, 1965; 2 Aug., 1965; 20 Sept., 1965; 21 Sept., 1965; 4 Oct., 1965], No. 23089/66. Heading C5E. Hexadienes are prepared by co-dimerizing an alpha-olefin and a conjugated diene in the presence of a catalyst composition comprising the following three components:- (I) a cobalt compound consisting of either (a) an inorganic cobalt salt, (b) a cobalt carboxylate, or (c) a complex of cobalt with a beta-ketone or a beta-keto carboxylic acid ester; (II) a phosphorus compound having one of the formulµ: (a) PR m X 3-m ,(b) P(OR) n X 3-n , and (c) P(Z)X<SP>2</SP> 3 , where R is alkyl, aryl or substituted aryl, X is H, halogen, alkyl or aryl, X<SP>2</SP> is halogen or halogen-substituted alkoxy, Z is sulphur or oxygen, m is 0, 1, 2 or 3, and n is 1, 2 or 3; and (III) an organoaluminium compound having one of the formulµ: (a) R<SP>2</SP> p A1X<SP>3</SP> 3-p , and (b) R<SP>2</SP> 4 Al 2 SO 4 , where R<SP>2</SP> is a monovalent hydrocarbon group, X<SP>3</SP> is hydrogen or halogen, and p is 1, 1À5, 2 or 3. In certain cases the products may isomerize. The following specific reactions are exemplified, the main products being indicated: (1) Ethylene + butadiene # hexadiene-1,4, hexadiene-2,4, or hexadiene-1,3 depending on the catalyst and whether isomerization occurs. (3) Ethylene + isoprene # a mixture of 4- and 5-methyl hexadiene-1,4. (3) Ethylene + hexadiene-1,4 -> a mixture of 3-ethyl-hexadiene. 1,4 and 3-methyl-heptadiene-1,4. (4) Ethylene + pentadiene-1,3 # 3-methylhexadiene-1,4. |
