Conformational analysis of 2-acetylcyclopentanone by the density functional and MP2 methods

被引：1

作者：

Glazunov, V. P. ^{[1
]}

Berdyshev, D. V. ^{[1
]}

Novikov, V. L. ^{[1
]}

机构：

[1] Russian Acad Sci, GB Elyakov Pacific Inst Bioorgan Chem, Far Eastern Branch, Vladivostok 690022, Russia

来源：

RUSSIAN CHEMICAL BULLETIN | 2012年 / 61卷 / 12期

关键词：

asymmetric beta-diketones; 2-acetylcyclopentanone; keto-enol and enol-enol tautomerism; quantum chemical calculations; density functional theory; B3LYP functional; Moller-Plesset second-order perturbation theory (MP2); rotamerism; potential energy surface; conformational analysis; NUCLEAR-MAGNETIC-RESONANCE; ENOL-ENOL TAUTOMERISM; BETA-DIKETONES; RING SIZE; EQUILIBRIA; METAL; 2-ACETYLCYCLOALKANONES; ACETYLACETONE; SPECTRA; FORMS;

D O I：

10.1007/s11172-012-0312-2

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Two-dimensional potential energy surfaces for internal rotation of the acetyl substituent and inversion of the five-membered ring in the gas phase and in acetonitrile were constructed by the B3LYP/6-31G(d) method for the diketo form of the 2-acetylcyclopentanone (2-ACPN) molecule. The diketo form of 2-ACPN exists in the gas phase and in low-polarity cyclohexane as a mixture of four rotamers K1, K2, K3, and K4. The fifth isomeric form K3a exists in polar acetonitrile. The estimation of the tautomeric composition of 2-ACPN taking into account the influence of the cyclohexane medium in the framework of the polarizable continuum model (PCM) using the MP 2/cc-pVTZ method agrees better with experimental data than the estimate obtained by the B3LYP/cc-pVTZ method. The constants of the enol-enol and keto-enol tautomeric equilibria of the 2-ACPN tautomers in solutions of aprotic solvents were estimated.

引用

页码：2195 / 2203

页数：9

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