Quantum chemical modeling of superbase-catalyzed reactions of acetophenone and methyl mesityl ketone with acetylene
| العنوان: | Quantum chemical modeling of superbase-catalyzed reactions of acetophenone and methyl mesityl ketone with acetylene |
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| المؤلفون: | Vladimir B. Kobychev, Boris A. Trofimov, Vladimir B. Orel, Nadezhda M. Vitkovskaya, Dmitry V. Zankov |
| المصدر: | Russian Chemical Bulletin. 66:2227-2233 |
| بيانات النشر: | Springer Science and Business Media LLC, 2017. |
| سنة النشر: | 2017 |
| مصطلحات موضوعية: | chemistry.chemical_classification, Ketone, 010405 organic chemistry, Superbase, General Chemistry, Activation energy, 010402 general chemistry, 01 natural sciences, Medicinal chemistry, 0104 chemical sciences, Catalysis, chemistry.chemical_compound, Acetylene, chemistry, Intramolecular force, Carbanion, Acetophenone |
| الوصف: | The mechanisms of furan formation and the competitive reaction of 1,5-diketone formation from 1-mesitylbut-2-en-1-one (1a) and 1-phenylbut-2-en-1-one (1b) were studied using the B3LYP/6-311++G**//B3LYP/6-31+G* quantum chemical approach taking into account solvation effects in terms of the IEFPCM model. The addition to 1a of the ethynide ion to form β-acetylene enolate ion (2a) occurs with the activation energy ΔG≠ = 13.3 kcal mol–1, while the further intramolecular O-vinylation with the closure of 2a to the dihydrofuran cycle of the dihydrofuran carbanion is the rate-determining step in the reaction pathway of substituted furan formation needing the activation energy G≠ = 19.5 kcal mol–1. The alternative addition of the mesitylethenolate ion to 1a to form the 1,5-diketone carbanion is associated with a higher (by 3.4 kcal mol–1) free activation energy than that of ethynide ion addition. In contrast, in the case of 1b, the addition at the C=C bond of the phenylethenolate ion rather than of the ethynide ion to form the 1,5-diketone carbanion is more preferable, since its activation free energy is 1.5 kcal mol–1 lower. The quantum chemical calculation results are consistent with the experimental data. |
| تدمد: | 1573-9171 1066-5285 |
| URL الوصول: | https://explore.openaire.eu/search/publication?articleId=doi_________::c6d3312a767810af613fe860d89d74ad https://doi.org/10.1007/s11172-017-2006-2 |
| حقوق: | CLOSED |
| رقم الأكسشن: | edsair.doi...........c6d3312a767810af613fe860d89d74ad |
| قاعدة البيانات: | OpenAIRE |
Find this article in full text from Springer Verlag. | تدمد: | 15739171 10665285 |
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