Russian Journal of Organic Chemistry

, Volume 46, Issue 10, pp 1452–1460 | Cite as

Quantum-Chemical Study on Reactions of Isocyanates with Linear Methanol Associates: III.* Reaction of Methyl Isocyanate with Linear Methanol Associates

  • A. Ya. Samuilov
  • F. B. Balabanova
  • T. A. Kamalov
  • Ya. D. Samuilov
  • A. I. Konovalov
Review

Abstract

Addition of linear methanol associates at the C=N and C=O bonds of methyl isocyanate was studied in terms of the B3LYP/6-311++G(df,p) hybrid quantum-chemical method. The addition at the C=N bond is more favorable than the reaction at the carbonyl group. All reactions involve late asymmetric cyclic transition states. The activity of the reacting system increases in parallel with the degree of methanol association. Isomerization of methyl hydrogen methylcarbonimidate into carbamate is catalyzed by methanol associates. Thermal decomposition of carbamates with formation of isocyanates can occur in autocatalytic mode.

Keywords

Isocyanate Carbamate Phenyl Isocyanate Prereaction Complex Methyl Methyl 

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Copyright information

© Pleiades Publishing, Ltd. 2010

Authors and Affiliations

  • A. Ya. Samuilov
    • 1
  • F. B. Balabanova
    • 1
  • T. A. Kamalov
    • 1
  • Ya. D. Samuilov
    • 1
  • A. I. Konovalov
    • 2
  1. 1.Kazan State Technological UniversityTatarstanRussia
  2. 2.Arbuzov Institute of Organic and Physical Chemistry, Kazan Research CenterRussian Academy of SciencesTatarstanRussia

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