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

Kód výsledku v 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>

Výsledek na webu

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DOI - Digital Object Identifier

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Jazyk výsledku

angličtina

Název v původním jazyce

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

Popis výsledku v původním jazyce

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.

Název v anglickém jazyce

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

Popis výsledku anglicky

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.

Druh

J_x - Nezařazeno - Článek v odborném periodiku (Jimp, Jsc a Jost)

CEP obor

CC - Organická chemie

OECD FORD obor

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Projekt

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Návaznosti

Z - Vyzkumny zamer (s odkazem do CEZ)

Rok uplatnění

2007

Kód důvěrnosti údajů

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

Název periodika

Polish Journal of Chemistry

ISSN

0137-5083

e-ISSN

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Svazek periodika

81

Číslo periodika v rámci svazku

5-6

Stát vydavatele periodika

PL - Polská republika

Počet stran výsledku

14

Strana od-do

993-1006

Kód UT WoS článku

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EID výsledku v databázi Scopus

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