ANALYSIS OF THE ORTHO EFFECT: BASICITY OF 2-SUBSTITUTED BENZONITRILES

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F60461373%3A22340%2F06%3A00016732" target="_blank" >RIV/60461373:22340/06:00016732 - isvavai.cz</a>

Nalezeny alternativní kódy

RIV/61388963:_____/06:00041080

Výsledek na webu

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DOI - Digital Object Identifier

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Jazyk výsledku

angličtina

Název v původním jazyce

ANALYSIS OF THE ORTHO EFFECT: BASICITY OF 2-SUBSTITUTED BENZONITRILES

Popis výsledku v původním jazyce

Energies of 18 ortho-substituted benzonitriles and their protonated forms were calculated within the framework of the density functional theory at the level B3LYP/6-311+G(d,p). The substituent effects were evaluated in terms of isodesmic reactions as theeffects on the basicity on the one hand and separately in the nitrile molecules and in the cations on the other. The ortho effect was defined as the difference when compared to the 4-substituted isomers. It is smaller than in the case of ortho-substituted benzoic acids but not negligible (up to 25 kJ mol-1). In unprotonated molecules it may be classified as purely steric effect, in spite of the small dimension of the CN group and estimates made with the calotte models. In the protonated forms, polar properties of the substituent are decisive. In addition, a new, quite important substituent effect was discovered with the substituents OH, SH, CHO and COOCH3, which is controlled by different conformation of protonated and unprotonated mol

Název v anglickém jazyce

ANALYSIS OF THE ORTHO EFFECT: BASICITY OF 2-SUBSTITUTED BENZONITRILES

Popis výsledku anglicky

Energies of 18 ortho-substituted benzonitriles and their protonated forms were calculated within the framework of the density functional theory at the level B3LYP/6-311+G(d,p). The substituent effects were evaluated in terms of isodesmic reactions as theeffects on the basicity on the one hand and separately in the nitrile molecules and in the cations on the other. The ortho effect was defined as the difference when compared to the 4-substituted isomers. It is smaller than in the case of ortho-substituted benzoic acids but not negligible (up to 25 kJ mol-1). In unprotonated molecules it may be classified as purely steric effect, in spite of the small dimension of the CN group and estimates made with the calotte models. In the protonated forms, polar properties of the substituent are decisive. In addition, a new, quite important substituent effect was discovered with the substituents OH, SH, CHO and COOCH3, which is controlled by different conformation of protonated and unprotonated mol

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

2006

Kód důvěrnosti údajů

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

Název periodika

Collection of Czechoslovak Chemical Communications

ISSN

0010-0765

e-ISSN

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Svazek periodika

71

Číslo periodika v rámci svazku

8

Stát vydavatele periodika

CZ - Česká republika

Počet stran výsledku

17

Strana od-do

1239-1255

Kód UT WoS článku

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EID výsledku v databázi Scopus

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