Quantum chemical study of the reaction of N,O-dimethylcarbamate with methylamine monomer and dimer

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Abstract

Reactions of N,O-dimethylcarbamate with methylamine monomer and dimer as a model for the polyurea preparation are studied by B3LYP and M06 quantum-chemical methods. Both a one-step interaction mechanism and a two-step route with an intermediate formed containing a tetracoordinated carbon atom are considered. The latter route is unlikely since the formation of the intermediate is characterized by small values of the equilibrium constants. Reactions involving the methylamine dimer are more favorable kinetically and thermodynamically. Kinetic preference of reactions with methylamine dimer participation is due to its increased donor and acid-base properties as compared to its monomer. The thermodynamic preference of interaction with methylamine dimer is due to a higher entropy of transformation as compared to the reaction with its monomer.

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About the authors

A. Y. Samuilov

Kazan National Research Technological University

Email: ysamuilov@yandex.ru
Russian Federation, Kazan

E. P. Kozhanova

Kazan National Research Technological University

Email: ysamuilov@yandex.ru
Russian Federation, Kazan

Ya. D. Samuilov

Kazan National Research Technological University

Author for correspondence.
Email: ysamuilov@yandex.ru
Russian Federation, Kazan

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7. Fig. 1. Dependences of the equilibrium constants (Kp) of the transformations of N,O-dimethylcarbamate with the monomer (1) and dimer (2) of methylamine in the gas phase on the temperature (T). The results of calculations by the B3LYP method were used.

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12. Fig. 2. Ball-and-stick models of transition states of reactions of N,O-dimethylcarbamate with a-monomer (PS1) and b-dimer (PS2) of methylamine, proceeding along a single-stage pathway. Bond lengths in Ӑ are indicated. Calculation data by the M06/6-311++G(df, p) method.

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14. Fig. 3. Ball-and-stick models of transition states of reactions of N,O-dimethylcarbamate with a-monomer (PS3) and b-dimer (PS4) of methylamine, leading to the formation of tetracoordinated intermediate (V). Bond lengths in Ӑ are indicated. Calculation data by the M06/6–311++G(df, p) method.

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17. Fig. 4. Ball-and-stick models of transition states of a – monomolecular (PS5) and b – methylamine monomer-catalyzed (PS6) transition of intermediate (V) to N,N1-dimethylurea. Bond lengths in Ӑ are indicated. Calculation data by the M06/6–311++G(df, p) method.

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