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Kinetics and mechanism of phosgenation of aliphatic alcohols. VI. The role of the association of the alcohol

Journal Article · · J. Org. Chem. USSR (Engl. Transl.); (United States)
OSTI ID:5887489

Investigation of the effect of the association of a series of alcohols on the phosgenation rate in heptane showed that the tetramer of the alcohol enters exclusively into reaction with phosgene. This is explained by the formation of a bicyclic transition state (or tetrahedral intermediate), which does not require previous desolvation or association of the alcohol and secures effective intramolecular assistance to the elimination of hydrogen chloride. The electronic structure was determined by CNDO/2 quantum-chemical calculations, which reproduces the three-dimensional structure and electron density distribution in the molecules fairly well. Methanol was chosen as model alcohol in order to simplify the calculations.

Research Organization:
D.I. Mendeleev Moscow Chemical Technology Institute (USSR)
OSTI ID:
5887489
Journal Information:
J. Org. Chem. USSR (Engl. Transl.); (United States), Journal Name: J. Org. Chem. USSR (Engl. Transl.); (United States) Vol. 24:2; ISSN JOCYA
Country of Publication:
United States
Language:
English