Conformational behaviour of methyl 2-fluoroesters through theoretical calculations, NMR and IR spectroscopy

文献情報

出版日 2004-02-10

DOI 10.1039/B311570D

インパクトファクター 3.676

著者

Cláudio F. Tormena, Matheus P. Freitas, Roberto Rittner, Raymond J. Abraham

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要旨

The conformational equilibrium of methyl 2-fluoropropionate (1) was studied through a combination of NMR, theoretical calculations and solvation theory. IR spectroscopy was used as an auxiliary technique for this analysis. The 1JCF couplings were analysed using theoretical and solvation calculations to give conformer energies in the solvents studied, vapour phase energies, and also the coupling constants for the distinct rotamers. The trans rotamer is more stable than the cis rotamer in the vapour phase by 0.4 kcal mol−1 and the conformers are of equal energy in CCl4. The more polar cis form is the major rotamer in the remaining solvents studied. Theoretical evaluation at the B3LYP/6-311++g(d,p) level for the α-alkyl substituent effect was carried out using methyl 2-fluorobutyrate (2), methyl 2-fluoro-tert-butylacetate (3) and methyl 2-fluorophenylacetate (4) as models, and showed the great effect of these substituents on the conformational stabilities. The governing interactions of these systems were rationalised in terms of both classical and non-classical effects, such as steric, electrostatic, O⋯H–C hydrogen bonding, gauche effect and hyperconjugative interactions.

掲載誌

Physical Chemistry Chemical Physics

CiteScore: 5.5

自己引用率: 10.3%

年間論文数: 3036

Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.

Conformational behaviour of methyl 2-fluoroesters through theoretical calculations, NMR and IR spectroscopy

文献情報

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Physical Chemistry Chemical Physics

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