Basicity of carboxylic acids: resonance in the cation and substituent effects

Result code in IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F60461373%3A22310%2F05%3A00013515" target="_blank" >RIV/60461373:22310/05:00013515 - isvavai.cz</a>

Alternative codes found

RIV/61388963:_____/05:00021120

Result on the web

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DOI - Digital Object Identifier

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Result language

angličtina

Original language name

Basicity of carboxylic acids: resonance in the cation and substituent effects

Original language description

Basic properties of acetic, formic and substituted benzoic acids were investigated by the density functional theory at the levels B3LYP/6-311+G(d,p) and/or B3LYP/6-311++G(2d,2p). The protonated form prefers unsymmetrical conformation E,Z on the two partially double C#O bonds; only in the case of formic acid the E,E form is still observable. Lower basicity of carboxylic acids as compared to ketones is due to the higher energy of the cation while the effect in the uncharged acid molecule is negligible. Contribution of resonance and of the inductive effect was approximately estimated by means of relatively sophisticated model compounds. The inductive effect of the hydroxy group in the cation is the deciding factor for the lowered basicity. Resonance in the cation is strong, stronger than in the acid molecule or in the carboxylate anion, but cannot overcome the inductive effect. Relative basicities of meta- and para-substituted benzoic acids are controlled by the Hammett equation with mark

Czech name

Basicity of carboxylic acids: resonance in the cation and substituent effects

Czech description

x

Type

J_x - Unclassified - Peer-reviewed scientific article (Jimp, Jsc and Jost)

CEP classification

CC - Organic chemistry

OECD FORD branch

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Project

<a href="/en/project/LN00A032" target="_blank" >LN00A032: Structure and dynamics of complex molecular systems and biomolecules</a><br>

Continuities

Z - Vyzkumny zamer (s odkazem do CEZ)

Publication year

2005

Confidentiality

S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů

Name of the periodical

New Journal of Chemistry

ISSN

1144-0546

e-ISSN

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Volume of the periodical

29

Issue of the periodical within the volume

2

Country of publishing house

GB - UNITED KINGDOM

Number of pages

7

Pages from-to

336-342

UT code for WoS article

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EID of the result in the Scopus database

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