PROCESS FOR PREPARING 1,2-CIS-DIVINYLCYCLOBUTANE OR SUBSTITUTED 1,2-CIS-DIVINYLCYCLOBUTANE BY MEANS OF CATALYTIC DIMERIZATION OF 1,3-DIOLEFINES

摘要

1,214,513. Dimerizing dienes; cyclobulane derivatives. STUDIENGESELLSCHAFT KOHLE m.b.H. 27 March, 1968 [8 April, 1967], No. 14628/68. Heading C5E. 1,3 - Dienes are cylodimerized by contact with a catalyst prepared by either (1) mixing a reducible nickel compound with an electron donor and a metal, metal hydride or halogenfree organometallic compound, having in each case a reducing action on the nickel compound, or (2) mixing a nickel complex compound containing zero-valent nickel with an electron donor. The cyclodimerization is conducted under conditions resulting in incomplete conversion of the diene. Suitable catalysts are formed from these components: nickel acetylacetonate / diethyl aluminium ethoxyl / tri- (o - phenyl - phenyl) phosphite (i.e. type 1), and bis (cyclooctadienyl) nickel / tri - (o - phenylphenyl) phosphite (i.e. type 2). In examples: (1-5, 8, 11 - 12) butadiene yields mainly cis-divinylcyclobutane and cyclooctadiene; (6 and 7) butadiene yields the same plus 4-vinylcyclohexene; (9) piperylene yields mainly dimethylcyclooctadiene and a mixture of the novel compounds 1,2 - cis - divinyl - 3,4 - dimethylcyclobutane and 1 - propenyl - 2 - vinyl- 3 - methyl - cyclobutane; and (10) a butadiene/ 2-butyne mixture yields mainly cis-divinylcyclobutane, cyclooctadiene, and dimethylcyclodecatriene.