Theoretical Study by DFT Method of the Arbuzov Reaction Mechanism Between Ethyl Halogenides and Trimethoxyphosphine

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The mechanism of the reaction between ethyl chloride or ethyl bromide with trimethoxyphosphine in a non-polar (ε = 1) and polar medium (methanol, ε = 32.7) was studied within the density functional theory (DFT) using MOLPRO program. It was shown that the reaction occurs in 2 stages: first, a nucleophilic attack of the carbon atom by phosphorus occurs, followed by the interaction of methyl of one of the methoxy groups with the halide. The limiting stage in all cases is the second stage of the reaction, the barrier of which is approximately 1.5 times higher than the barrier of the first. The reaction barriers are lower for the reaction of ethyl bromide, while the stabilization energies of the intermediate complexes and products are almost the same for chloride and bromide. Temperature in general has little effect on the reaction profile, with the exception of entropic destabilization of the initial complex. At the same time, the usage of a polar solvent accelerates the reaction process, lowering the barriers and stabilizing the intermediates, and can be recommended for carrying out the reaction.

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A. Filippova

Lomonosov Moscow State University

Email: osyzgantseva@gmail.com
俄罗斯联邦, Moscow

M. Syzgantseva

Mendeleev University of Chemical Technology

Email: osyzgantseva@gmail.com
ORCID iD: 0000-0001-8070-104X
俄罗斯联邦, Moscow

A. Galitsin

Lomonosov Moscow State University

Email: osyzgantseva@gmail.com
俄罗斯联邦, Moscow

O. Syzgantseva

Lomonosov Moscow State University

编辑信件的主要联系方式.
Email: osyzgantseva@gmail.com
ORCID iD: 0000-0002-0270-4621
俄罗斯联邦, Moscow

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2. Fig. 1. Applications of C-P bonded compounds in applications in organic synthesis and catalysis, agrochemistry and household chemistry

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3. Scheme 1. Stages of the Arbuzov reaction of ethyl halides with trimethylphosphite

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4. Fig. 2. Structure of intermediates, transition states and reaction products of phosphonate and methyl halide formation by the Arbuzov reaction: S0 - isolated reagents, S1 - reagent complex, TS1 - first transition state, S2 - intermediate complex, TS2 - second transition state, S3 - reaction products

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5. Fig. 3. C-P and P-O bond lengths in key intermediates and reaction products in the gas phase and methanol

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6. Fig. 4. Transient states, magnitudes and directions of imaginary frequencies of oscillations corresponding to transient states

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7. Fig. 5. Energy profiles of the Arbuzov reaction carried out in the gas phase. Here and in Fig. 6 green colour indicates the reaction pathway for chloroethane, red - for bromoethane

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8. Fig. 6. Energy profiles of the Arbuzov reaction carried out in a polar medium - methanol

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