Process for the production of cyclic olefines

摘要

Methyl hydrogen polysiloxane is reacted with AlCl3 in cyclohexane solvent under an argon atmosphere and the product further reacted with TiCl4. The final product is used as a dimerization catalyst (see Division C5).ALSO:4-Vinyl cyclohexene and derivatives thereof are prepared by contacting an acyclic conjugated diene of formula C4X6, where each X is hydrogen or alkyl and the X's may be the same or different, in an anhydrous non-aromatic solvent with a catalyst comprising the reaction product of (i) a compound of B, Al, Ga, In or Tl, (ii) a silicon compound containing an Si-H bond, and (iii) a compound of a metal of Group IVa, Va or VIa of the Mendelaeef Periodic Table. Catalyst component (i) is suitably a halide, an alkoxide, or a halogen alkoxide, AlCl3 being preferred; component (ii) is suitable a silane or siloxane, e.g. trimethyl silane, triethyl silane, dimethyl phenyl silane, methyl diphenyl silane, and a methyl hydrogen polysiloxane; and component (iii) is suitable a halide, oxyhalide, alcoholate or acetylacetonate, preferably TiCl4. All three catalyst components may be reacted together simultaneously, but preferably (i) and (ii) are first reacted together and the product reacted with (iii). The diene starting material may be butadiene, isoprene or piperylene, and suitable non-aromatic solvents are cycloalkanes, e.g. cyclohexane, and acyclic alkanes, e.g. a commercial mixture of C16- 18 alkanes. In the example, butadiene is converted to 4-vinyl cyclohexene.ALSO:Catalysts for cyclodimerisation of conjugated dienes (see Division C5) comprise the reaction product of (i) a compound of B, Al, Ga, In or Tl, e.g. a halide, alkoxide or halogen alkoxide (only AlCl3 specified), (ii) a silicon compound containing an Si-H bond, e.g. trimethyl silane, triethyl silane, dimethyl phenyl silane, methyl diphenyl silane, and a methyl hydrogen polysiloxane, and (iii) a compound of a metal of Group IVa, Va or VIa of the Mendeleef Periodic Table, e.g. a halide, oxyhalide, alcoholate or acetylacetone (only TiCl4 mentogether simultaneously but preferably (i) and tioned). All three components may be reacted (ii) are first reacted together and the product reacted with (iii). The reaction is carried out in an inert solvent under an inert gas atmosphere at 40-100 DEG C.