Selective hydrogenation of 1,5-cyclooctadiene with PdCl/sub 2/(P(phi)/sub 3/)/sub 2/ and the formation of a. pi. -allylic reaction intermediate

Journal Article · Wed Nov 01 00:00:00 EST 1978 · J. Catal.; (United States)

OSTI ID:7147711

Fujii, Y; Bailar, J C

The selective hydrogenation of 1,5-cyclooctadiene to cyclooctene with dichloro-bis(triphenylphosphine)-palladium as catalyst at 90/sup 0/C and 51 atm hydrogen pressure in a variety of solvents was poisoned by tin chloride and promoted by dichloromethane, methanol, or acetic acid in the solvent. Hydrogen chloride also promoted the reaction, but no reaction occurred under a nitrogen atmosphere. Hydrogenation was faster than isomerization to 1,3-cyclooctadiene at room temperature but slower above 70/sup 0/C. A reaction intermediate was isolated and identified as PdCl(C/sub 8/H/sub 13/)(Po/sub 3/) in which the C/sub 8/H/sub 13/ group is the 2-cycloocten-1-yl anion of m-allyl structure. It decomposed in solution above 90/sup 0/C to give palladium black and was a more reactive catalyst than the initial PdCl/sub 2/(Pq/sub 3/) complex. A reaction mechanism was derived.

• Research Organization: Univ. of Illinois, Urbana
• OSTI ID: 7147711
• Journal Information: J. Catal.; (United States), Vol. 55:2
• Country of Publication: United States
• Language: English

Related Subjects

10 SYNTHETIC FUELS
DIENES
HYDROGENATION
OCTENES
SYNTHESIS
PALLADIUM
ACTIVATION ENERGY
REACTION INTERMEDIATES
REACTION KINETICS
TEMPERATURE EFFECTS
ALKENES
CHEMICAL REACTIONS
ELEMENTS
ENERGY
HYDROCARBONS
KINETICS
METALS
ORGANIC COMPOUNDS
PLATINUM METALS
POLYENES
TRANSITION ELEMENTS
090121* - Hydrocarbon Fuels- Chemical Synthesis- (1976-1989)