| 摘要 |
A process for the preparation of cyclo-olefins having at least 8 carbon atoms and at least two unsaturated carbon to carbon linkages in the ring comprises subjecting an open chain conjugated diene to elevated temperature in the presence of a catalyst prepared by reacting nickel carbonyl and a hydride, organohydride, organohalide or organo compound of boron or a non-transition metal of the sub-groups IA, IIA, IIB, IIIA or IVA of the Periodic Tabl and having an atomic weight of less than 208, the molar ratio of nickel carbonyl to other compound being 1 : 10 to 10 : 1. Specified diolefins are butadiene, chloroprene, isoprene, piperylene, phenyl diolefins, 2,3-dimethyl butadiene and 2,4-hexadiene. The reaction may be effected in the presence of inert solvents, e.g. liquid saturated open chain and cyclic hydrocarbons in which the catalyst has been prepared and from which it has not been isolated. Many suitable hydrides and organo compounds are listed and Example 5 describes the cyclooligomerization of butadiene in the presence of catalysts formed by reacting nickel tetracarbonyl with (1) triethyl aluminium in cyclohexane; (2) triethyl aluminium, ethyl lithium, allyl sodium and a mixture of allyl sodium, sodium isopropoxide and sodium chloride in a mixture of hexane, heptane and octane; and (3 and 4) triisobutyl aluminium in benzene; to give products comprising vinylcyclohexene, 1,5-cyclooctadiene and 1,5,9-cyclododecatriene.ALSO:Catalysts for the oligomerization of open chain conjugated diolefins to cycloolefins having at least 8 carbon atoms in the ring are prepared by reacting nickel carbonyl with a hydride, organohydride, organohalide, or organo compound of boron or a non-transition metal of the subgroups IA, IIA, IIB, IIIA or IVA of the Periodic Table and having an atomic weight below 208, the molar ratio of nickel carbonyl to other compounds being 1 : 1 to 10 : 1. The reaction may be effected in the presence of an inert solvent, e.g. liquid saturated open chain and cyclic hydrocarbons, and the catalyst is preferably aged before use until a colour develops therein. Many suitable hydrides and organo compounds are listed including organo compounds of aluminium, lithium, sodium, potassium, calcium, zinc, and lead; hydrides and mixed hydrides of lithium, sodium, potassium, rubidium, caesium, beryllium, magnesium, calcium, strontium, barium, zinc, cadmium, mercury, aluminium, gallium, indium, thallium, germanium, tin and lead; and organohalides of beryllium, magnesium, aluminium, and lead. Examples describe the preparation of catalysts by reacting nickel tetracarbonyl with (1) triethyl aluminium in cyclohexane, (2) triethyl aluminium, ethyl lithium, allyl sodium, and alfin (allyl sodium, sodium isopropoxide, and sodium chloride) in a mixture of hexane, heptane and octane; and (3 and 4) triisobutyl aluminium in benzene. The catalysts may be used for the cyclooligomerization of butadiene, chloroprene, isoprene, piperylene, phenyl diolefins, 2,3-dimethyl butadiene and 2,4-hexadiene. |
