双(2-氯丙-2-烯基)硫化物在水合肼/碱体系中的反应性:量子化学研究

IF 1.9 4区 化学 Q2 CHEMISTRY, ORGANIC
Nikita V. Teplyashin, Alexander S. Bobkov, Nikolai A. Korchevin, Igor B. Rozentsveig, Nadezhda M. Vitkovskaya
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引用次数: 0

摘要

用量子化学方法研究了双(2-氯丙-2-烯基)硫化物在水合肼/碱体系中的反应性。与高精度CBS//Q-B3方法相比,B2PLYP-D2//B3LYP方法在激活势垒的相对值之间有很好的一致性。计算了从气相到二元溶剂水合肼过渡过程中熵变的修正。对水合肼溶剂的IEF PCM模型进行了参数化。研究的反应途径包括(i) C=C键的迁移和二氯丙烯基硫化物的脱氢氯化之间的竞争;(ii)脱氢氯化引起的双烯基硫化物的1,3-亲原性重排;(iii)硫和氯原子可能被联氨取代。还对上述过程中可能形成的硫鎓和硫鎓阳离子的形成进行了评价。
本文章由计算机程序翻译,如有差异,请以英文原文为准。

Reactivity of bis(2-chloroprop-2-enyl)sulfide in the system hydrazine hydrate/alkali: A quantum chemical insight

Reactivity of bis(2-chloroprop-2-enyl)sulfide in the system hydrazine hydrate/alkali: A quantum chemical insight

The reactivity of bis(2-chloroprop-2-enyl)sulfide in the system hydrazine hydrate/alkali has been studied using quantum-chemical methods. The B2PLYP-D2//B3LYP approach shows a good agreement between the relative values of activation barriers compared to high-precision CBS//Q-B3. The correction for the entropy change during the transition from the gas phase to the binary solvent hydrazine hydrate is calculated. The IEF PCM model was parameterized for hydrazine hydrate solvent. The studied reaction routes includes (i) a competition between migration of the C=C bond and dehydrochlorination of bis(2-chloroprop-2-enyl)sulfide; (ii) 1,3-prototropic rearrangements of bis (allenyl)sulfide resulting from a dehydrochlorination; (iii) the possible substitution of sulfur and chlorine atoms with hydrazine. The probable formation of the thiiranium and thiirenium cations formation in the above has also been evaluated.

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来源期刊
CiteScore
3.60
自引率
11.10%
发文量
161
审稿时长
2.3 months
期刊介绍: The Journal of Physical Organic Chemistry is the foremost international journal devoted to the relationship between molecular structure and chemical reactivity in organic systems. It publishes Research Articles, Reviews and Mini Reviews based on research striving to understand the principles governing chemical structures in relation to activity and transformation with physical and mathematical rigor, using results derived from experimental and computational methods. Physical Organic Chemistry is a central and fundamental field with multiple applications in fields such as molecular recognition, supramolecular chemistry, catalysis, photochemistry, biological and material sciences, nanotechnology and surface science.
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