Alcoholysis of epoxidized polyisoprenes by direct opening of oxirane rings with alcohol derivatives 1. Modelization of the reaction

• Published in: European polymer journal Vol. 37; no. 7; pp. 1315 - 1326
• Main Authors: Derouet, Daniel, Brosse, Jean-Claude, Challioui, Allal
• Format: Journal Article
• Language: English
• Published: Oxford Elsevier Ltd 01.07.2001; Elsevier
• Subjects: Alcohols; Alcoholysis; Applied sciences; Cerium ammonium nitrate; Chemical modifications; Chemical reactions and properties; Epoxidized polyisoprene; Exact sciences and technology; Mechanism; Modelization; Organic polymers; Physicochemistry of polymers; Cerium ammonium nitrate; Alcoholysis; Modelization; Epoxidized polyisoprene; Mechanism; Alcohols; Solvent effect; Catalytic reaction; Molecular structure; Isoprene derivative polymer; Experimental study; Alcohol polymer; Ammonium Cerium Nitrates; Structure processing relationship; Chemical modification; Side reaction; Reaction mechanism; Model reaction
• ISSN: 0014-3057; 1873-1945
• DOI: 10.1016/S0014-3057(00)00266-4

Alcoholysis of 4,5-epoxy-4-methyloctane selected as a model molecule of epoxidized 1,4-polyisoprene was achieved with various alcohols using cerium ammonium nitrate as catalyst. Next to the expected alkoxy alcohol, side products resulting from oxirane rearrangement were identified: 5-methyloctan-4-one, 5-methyloct-5-en-4-ol and 2- n-propylhexen-3-ol. One of them, 5-methyloct-3-en-4-ol, was demonstrated to be able to react with alcohols so leading to the formation of allylic ethers. From the diastereoisomer distribution, as well as the effect of temperature and solvent on the reaction, a coordinative S N2 mechanism able to explain the formation of the various products identified, is suggested.