Sterické a elektronické substituční vlivy při hydrolýze a aminolýze 4-alkyl-4-methyl-2-aryl-4,5-dihydro-1,3-oxazol-5-onů

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F00216275%3A25310%2F05%3A00003027" target="_blank" >RIV/00216275:25310/05:00003027 - 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

Steric and electronic substituent effects in hydrolysis and aminolysis of 4-alkyl-4-methyl-2-aryl-4,5-dihydro-1,3-oxazol-5-ones

Popis výsledku v původním jazyce

The kinetics and mechanism of the acid-catalysed hydrolysis of substituted 4-alkyl-4-methyl-2-aryt-4,5-dihydro-1, 3-oxazol-5-ones to the corresponding 2-alkyl-2-benzoylaminopropanoic acids were studied. The Taft correlation of rate constants of the acid-catalysed hydrolysis with alkyl substitution at the 4-position of the 1,3-oxazol-5-one ring is non-linear. In the Hammett correlation, the value of rho to decreases with increasing steric demand of the alkyl substituent. With the 4-isopropyl and tert-butyl derivatives, rho = -0.63 and -0.32, respectively. The protonated 4-isopropyl and tert-butyl derivatives undergo nucleophilic attack by water at the carbonyl carbon atom at the 5-position of the 1,3-oxazol-5-one ring to the extents of ca 70% and 60%, respectively. Another reaction path consists in nucleophilic attack by water at the 2-position of the 1,3-oxazol-5-one ring. The reaction kinetics of aminolyses of substituted 4-isopropyl-4-methyl-2-phenyl-1,3-oxazol-5(4H)-ones (1a, 1b, 1f

Název v anglickém jazyce

Steric and electronic substituent effects in hydrolysis and aminolysis of 4-alkyl-4-methyl-2-aryl-4,5-dihydro-1,3-oxazol-5-ones

Popis výsledku anglicky

The kinetics and mechanism of the acid-catalysed hydrolysis of substituted 4-alkyl-4-methyl-2-aryt-4,5-dihydro-1, 3-oxazol-5-ones to the corresponding 2-alkyl-2-benzoylaminopropanoic acids were studied. The Taft correlation of rate constants of the acid-catalysed hydrolysis with alkyl substitution at the 4-position of the 1,3-oxazol-5-one ring is non-linear. In the Hammett correlation, the value of rho to decreases with increasing steric demand of the alkyl substituent. With the 4-isopropyl and tert-butyl derivatives, rho = -0.63 and -0.32, respectively. The protonated 4-isopropyl and tert-butyl derivatives undergo nucleophilic attack by water at the carbonyl carbon atom at the 5-position of the 1,3-oxazol-5-one ring to the extents of ca 70% and 60%, respectively. Another reaction path consists in nucleophilic attack by water at the 2-position of the 1,3-oxazol-5-one ring. The reaction kinetics of aminolyses of substituted 4-isopropyl-4-methyl-2-phenyl-1,3-oxazol-5(4H)-ones (1a, 1b, 1f

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

2005

Kód důvěrnosti údajů

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

Název periodika

Journal of Physical Organic Chemistry

ISSN

0894-3230

e-ISSN

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Svazek periodika

18

Číslo periodika v rámci svazku

8

Stát vydavatele periodika

GB - Spojené království Velké Británie a Severního Irska

Počet stran výsledku

8

Strana od-do

743-750

Kód UT WoS článku

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EID výsledku v databázi Scopus

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