Substituent Effect in the ortho Position: Model Compounds with a Removed Reaction Centre

Result code in IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F60461373%3A22340%2F07%3A00019331" target="_blank" >RIV/60461373:22340/07:00019331 - isvavai.cz</a>

Result on the web

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DOI - Digital Object Identifier

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Result language

angličtina

Original language name

Substituent Effect in the ortho Position: Model Compounds with a Removed Reaction Centre

Original language description

2 -Substituted phenylpropynoic acids 1 and - in less details - 2 -substituted (E)-phenyliminoacetic acids 3 were investigated theoretically as model for theortho substitution, in which direct steric interaction is prevented by the extended side chain bearing the reaction centre. Energies of the acid molecules and of their deprotonated forms were calculated within the framework of the density functional theory at the level B3LYP/6- 311+G(d,p)//B3LYP/6-311+G(d,p). The substituent effects were evaluated interms of isodesmic reactions, on the one hand for the acidity, on the other separately for the acid molecules or for the anions. Contrary to the expectation, the steric interaction of the substituent with the side chain is rather strong. The substituenteffects represent a blend of polar and steric effects, and cannot serve for deriving any set of standard ortho substituent constants free of proximity effects as it was originally believed.

Czech name

Substituent Effect in the ortho Position: Model Compounds with a Removed Reaction Centre

Czech description

2 -Substituted phenylpropynoic acids 1 and - in less details - 2 -substituted (E)-phenyliminoacetic acids 3 were investigated theoretically as model for theortho substitution, in which direct steric interaction is prevented by the extended side chain bearing the reaction centre. Energies of the acid molecules and of their deprotonated forms were calculated within the framework of the density functional theory at the level B3LYP/6- 311+G(d,p)//B3LYP/6-311+G(d,p). The substituent effects were evaluated interms of isodesmic reactions, on the one hand for the acidity, on the other separately for the acid molecules or for the anions. Contrary to the expectation, the steric interaction of the substituent with the side chain is rather strong. The substituenteffects represent a blend of polar and steric effects, and cannot serve for deriving any set of standard ortho substituent constants free of proximity effects as it was originally believed.

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

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Continuities

Z - Vyzkumny zamer (s odkazem do CEZ)

Publication year

2007

Confidentiality

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

Name of the periodical

Polish Journal of Chemistry

ISSN

0137-5083

e-ISSN

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Volume of the periodical

81

Issue of the periodical within the volume

5-6

Country of publishing house

PL - POLAND

Number of pages

14

Pages from-to

993-1006

UT code for WoS article

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EID of the result in the Scopus database

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