Paul Bourdauducq

Palladium catalyzed telomerization of butadiene with water in a two phase system : drastic effect of the amine structure on the rate and selectivity

Abstract Telomerization of butadiene with water in the presence of carbon dioxide and a trialkylamine using a palladium-hydrosoluble phosphine system was investigated. 2,7-Octadien-1-ol was obtained as the main product, whilst 1,7-octadien-3-ol, octatrienes, 4-vinylcyclohexene and dioctadienyl ethers were formed as side products. The reaction was carried out exclusively in an aqueous-organic medium in the absence of solvent or co-solvent. The conversion and the selectivity are strongly dependent on the structure of trialkylamine. The role of the amine was discussed.

Highly efficient telomerization of butadiene into octadienol in a micellar system: a judicious choice of the phosphine/surfactant combination

Abstract Telomerization of butadiene into octadienols in a micellar system and in the presence of hydrophilic or hydrophobic phosphines derived from triphenylphosphine has been investigated. Activities and selectivities were strongly dependent on the steric properties of the phosphine and on the nature of the surfactant/phosphine couple. The best results have been obtained with the water-soluble phosphine/cationic surfactant combinations (octadienols selectivities > 70% and turnover frequencies up to 830 h −1 . The phosphine/anionic surfactant couples gave rise to octadienols in poor selectivities (40%) and activities (100 h −1 ). With the phosphine/neutral surfactant combinations, the results are strongly dependent on the nature of the phosphine. These results are interpreted from electrostatic interactions at the micelle-water interfaces.

Solvent free telomerization of butadiene with water into octadienols in the presence of nonionic surfactant : efficient micellar catalysis

Telomerization of butadiene with water into 2,7-octadien-1-ol using a palladiumhydrosoluble phosphine system was investigated. The reaction was carried out without solvent in the presence of carbon dioxide and a nonionic surfactant. Promoted effect of neutral surfactant appeared above the critical micelle concentration and the conversion and the selectivity depended on the structure of nonionic surfactant hydrophilic part. The role of the nonionic surfactant is discussed.