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

被引：0
|
作者：
A. Ya. Samuilov
F. B. Balabanova
T. A. Kamalov
Ya. D. Samuilov
A. I. Konovalov
机构：
[1] Kazan State Technological University,Arbuzov Institute of Organic and Physical Chemistry, Kazan Research Center
[2] Russian Academy of Sciences,undefined
来源：
Russian Journal of Organic Chemistry | 2010年 / 46卷
关键词：
Isocyanate; Carbamate; Phenyl Isocyanate; Prereaction Complex; Methyl Methyl;
D O I：
暂无
中图分类号：
学科分类号：
摘要：
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.
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页码：1452 / 1460
页数：8
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