Patent GB-917103-A (GB)
Title: Process for the dimerisation or trimerisation of 1,3-diolefines
IPC: B01J31/16
Filed: 1960-12-13
Abstract: A catalyst for the dimerization and trimerization of 1,3-diolefins is formed by mixing a compound of a Group VIII metal with a metal hydride or complex hydride or an organometallic compound and an electron donor or is a complex compound of a Group VIII metal formed from a compound of the metal and a Group I-III organometallic compound in the presence of an electron donor. Suitable Group VIII metal compounds are acetyl acetonates, acetoacetic ester enolates, alcoholates, salts of weak organic acids or dimethyl glyoxime compounds of iron, cobalt or nickel. The metal hydride or organometallic compound is preferably of a Group I-III metal, e.g. metal alkyls or aryls or Grignard compounds or metal hydrides or complex hydrides, but other compounds, may be used, e.g. lead or tin tetraalkyls or organo-chromium compounds.  Suitable electron donors are ethers and tertiary amines particularly cyclic ethers and cyclic tertiary amines, alkyl and aryl phosphines and phosphites, tri-alkyl and -aryl arsenic, antimony and bismuth compounds, and acetylenes, particularly diphenylacetylene.  Typical complexes of Group VIII metals which may be used are Ni(P(C6H5)3)4; ((C6H5)3P) 2NiC8H12(cyclo-octadiene); Ni(P(C6H5)3)2; and bis-cyclo-octadiene nickel-(O).  Specifications 848,951, 860,377, 867,016, German Specification 881,511, and U.S.A.  Specification 2,686,209 are referred to.ALSO:The dimerisation and trimerisation of 1,3-diolefins is effected in the presence of a catalyst which is formed by mixing a compound of a Group 8 metal with a metal hydride or complex hydride or an organometallic compound and an electron donor or which is a complex compound of a Group 8 metal formed from a compound of the metal and a Group 1-3 organometallic compound in the presence of an electron donor.  Butadiene yields, depending on the catalyst and conditions used, 4-vinylcyclohexene, cyclooctadiene - 1,5, trans, trans, trans and trans, trans, cis-cyclododecatriene-1,5,9, and the new compound 5-methylheptatriene-1,3,6; piperylene and isoprene yield principally dimethylcyclooctadienes.  The process may be effected in an inert solvent, e.g. an aliphatic, aromatic or halogenated hydrocarbon, at 1-20 atm. and 20-150 DEG C.  Suitable Group 8 metal compounds are acetyl acetonates, acetoacetic ester enolates, alcoholates, salts of weak organic acids or dimethyl glyoxime compounds of iron, cobalt or nickel.  The metal hydride or organometallic compound is preferably of a Group 1-3 metal, e.g. metal alkyls or aryls or Grignard compounds or metal hydrides or complex hydrides, but other compounds, may be used, e.g. lead or tin tetra-alkyls or organo-chromium compounds.  Suitable electron donors are ethers and tertiary amines particularly cyclic ethers and cyclic tertiary amines, alkyl and aryl phosphines and phosphites, tri-alkyl and -aryl arsenic, antimony and bismuth compounds, and acetylenes, particularly diphenylacetylene. Typical complexes of Group 8 metals which may be used are Ni(P(C6H5)3)4; ((C6H5)3P)2 NiC8H12(cyclo-octadiene); Ni(P(C6H5)3)2; and bis-cyclo-octadiene nickel-(O).  Specifications 848,951, 860,377, 867,016, German Specification 881,511 and U.S.A.  Specification 2,686,209 are referred to.