Quantum-chemical investigation of isocyanate reactions with linear methanol associates: IV. Mechanism of autocatalytic reaction of methyl isocyanate with linear methanol associates |
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Authors: | A Ya Samuilov T A Kamalov F B Balabanova Ya D Samuilov A I Konovalov |
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Institution: | 1.Kazan State Technological University,Kazan,Russia;2.Arbuzov Institute of Organic and Physical Chemistry, Kazan Scientific Center,Russian Academy of Sciences,Kazan,Russia |
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Abstract: | It was shown by quantum-chemical method B3LYP/6-311++G(df,p) that in the autocatalytic reaction the molecules of methyl carbamate
formed prereaction complexes with the monomer and dimer of methanol. The complexes possess higher electron-donor properties
than free alcohol molecules thus increasing the activity of complexes in the reaction with isocyanates. The products of the
autocatalytic reaction are new molecules of carbamate and azomethinenol. The conversions occur through concerted asymmetric
late transition states. The isomerization of azomethinenols into carbamates is catalyzed by molecules of alcohols and their
associates. The autocatalytic reaction of isocyanates with alcohols becomes possible owing to the ability of alcohols to catalyze
the mentioned isomerization. |
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