Quantum-Chemical Study of Catalysis in the Reaction of N,O-Dimethyl Carbamate with Methylamine

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Abstract

Non-catalytic and sodium acetate and sodium methoxide catalyzed reactions of N,O-dimethyl carbamate with methylamine were studied using quantum-chemical hybrid density functional methods M06 and B3LYP. All interactions proceed through concerted cyclic transition states. Non-catalytic and sodium acetate-catalyzed reactions are characterized by a large activation free energy barrier. The transformation catalyzed by sodium methoxide is characterized by a negative enthalpy of activation and a low free energy of activation.

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About the authors

A. Y. Samuilov

Kazan National Research Technological University

Email: ysamuilov@yandex.ru
ORCID iD: 0000-0001-7763-8326
Russian Federation, Kazan, 420015

E. P. Kozhanova

Kazan National Research Technological University

Email: ysamuilov@yandex.ru
ORCID iD: 0009-0004-6676-9629
Russian Federation, Kazan, 420015

Y. D. Samuilov

Kazan National Research Technological University

Author for correspondence.
Email: ysamuilov@yandex.ru
ORCID iD: 0000-0002-5943-7448
Russian Federation, Kazan, 420015

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Supplementary files

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2. Fig. 1. Ball-rod models of intermediates IM1, IM2 and the TS1 transition state in the reaction of N,O-dimethyl carbamate with methylamine. Calculation data M06/6-311++G(df, p).

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3. Fig. 2. Ball-rod models of intermediates IM3, IM4, and the TS2 transition state in the zinc acetate-catalyzed reaction of N,O-dimethicarbamate with methylamine. Calculation data M06/6-311++G(df, p).

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4. 3. Ball-rod models of AM5, AM6 intermediates and S3 transition state in the sodium methylate-catalyzed reaction of N,O-dimethicarbamate with methylamine. Calculation data M06/6-311++G(df, p).

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5. Scheme 1.

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