Kinetics and mechanism of phosgenation of aliphatic alcohols. V. Quantum-chemical investigation of the mechanism of the reaction of phosgene with methanol

Journal Article · Wed Apr 20 00:00:00 EDT 1988 · J. Org. Chem. USSR (Engl. Transl.); (United States)

OSTI ID:5887396

Orlov, S I; Varnek, A A; Chimishkyan, A L; Sel', O B

Analysis of maps of the molecular electrostatic potential of phosgene showed that attack by methanol as nucleophile at the phosgene carbon atom takes place preferentially not in the plane of the molecule (the S/sub N/2 mechanism) but in a direction perpendicular to the COCl/sub 2/ plane (an AE addition-elimination mechanism). A fragment of the potential energy surface for the reaction of phosgene with methanol was calculated by the MNDO method. The reaction takes place by an AE-like mechanism through a late transition state, which represents a four-membered ring. There is not local minimum at a point corresponding to a tetrahedral intermediate, and this is explained by the absence of factors which stabilize it.

• Research Organization: D.I. Mendeleev Moscow Chemical Technology Institute (USSR)
• OSTI ID: 5887396
• Journal Information: J. Org. Chem. USSR (Engl. Transl.); (United States), Vol. 23:11; Other Information: Translated from Zh. Org. Khim.; 23: No. 11, 2412-2418 (Nov 1987)
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
METHANOL
CHEMICAL REACTION KINETICS
MOLECULAR MODELS
QUANTUM MECHANICS
PHOSGENE
ACTIVATION ENERGY
BINDING ENERGY
ELECTRON DENSITY
ELECTROSTATICS
INTERATOMIC DISTANCES
MOLECULAR STRUCTURE
POINT CHARGE
POTENTIAL ENERGY
POTENTIALS
SOLVATION
SURFACE ENERGY
ALCOHOLS
CARBONIC ACID DERIVATIVES
DISTANCE
ELECTRIC CHARGES
ENERGY
FREE ENERGY
HYDROXY COMPOUNDS
KINETICS
MATHEMATICAL MODELS
MECHANICS
ORGANIC CHLORINE COMPOUNDS
ORGANIC COMPOUNDS
ORGANIC HALOGEN COMPOUNDS
PHYSICAL PROPERTIES
REACTION KINETICS
SURFACE PROPERTIES
THERMODYNAMIC PROPERTIES
400201* - Chemical & Physicochemical Properties