Kinetics and mechanism of phosgenation of aliphatic alcohols. V. Quantum-chemical investigation of the mechanism of the reaction of phosgene with methanol
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), Journal Name: J. Org. Chem. USSR (Engl. Transl.); (United States) Vol. 23:11; ISSN JOCYA
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
400201* -- Chemical & Physicochemical Properties
ACTIVATION ENERGY
ALCOHOLS
BINDING ENERGY
CARBONIC ACID DERIVATIVES
CHEMICAL REACTION KINETICS
DISTANCE
ELECTRIC CHARGES
ELECTRON DENSITY
ELECTROSTATICS
ENERGY
FREE ENERGY
HYDROXY COMPOUNDS
INTERATOMIC DISTANCES
KINETICS
MATHEMATICAL MODELS
MECHANICS
METHANOL
MOLECULAR MODELS
MOLECULAR STRUCTURE
ORGANIC CHLORINE COMPOUNDS
ORGANIC COMPOUNDS
ORGANIC HALOGEN COMPOUNDS
PHOSGENE
PHYSICAL PROPERTIES
POINT CHARGE
POTENTIAL ENERGY
POTENTIALS
QUANTUM MECHANICS
REACTION KINETICS
SOLVATION
SURFACE ENERGY
SURFACE PROPERTIES
THERMODYNAMIC PROPERTIES