2,5-Dimethylphenacyl Esters: A Photoremovable Protecting Group for Carboxylic Acids

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F00216224%3A14310%2F01%3A00004579" target="_blank" >RIV/00216224:14310/01:00004579 - 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

2,5-Dimethylphenacyl Esters: A Photoremovable Protecting Group for Carboxylic Acids

Popis výsledku v původním jazyce

Irradiation of 2,5-dimethylphenacyl (DMP) esters (1a) in benzene or cyclohexane solutions produces the corresponding free carboxylic acids (2a) in high chemical yields, along with 6-methyl-1-indanone (3). In methanol, 2-(methoxymethyl)-5-methylacetophenone (4) is formed as a co-product. Quantum yields for the photorelease of the DMP group are higher in non-polar solvents, fi = 0.2, than in methanol, fi = 0.1. The photoreaction is initiated by efficient photoenolization, fi = 1. Three transient intermediates were identified by laser flash photolysis of 1a, the triplet state photoenol and the two ground state photoenols of Z and E configuration. Release of the acids 2a occurs predominantly from the E isomer, which has a lifetime of about 2 ms in methanoland 0.5 s in benzene solution. The present data are essential for potential applications of the DMP moiety as a photoremovable protecting group in organic synthesis or biochemistry ("caged compounds").

Název v anglickém jazyce

2,5-Dimethylphenacyl Esters: A Photoremovable Protecting Group for Carboxylic Acids

Popis výsledku anglicky

Irradiation of 2,5-dimethylphenacyl (DMP) esters (1a) in benzene or cyclohexane solutions produces the corresponding free carboxylic acids (2a) in high chemical yields, along with 6-methyl-1-indanone (3). In methanol, 2-(methoxymethyl)-5-methylacetophenone (4) is formed as a co-product. Quantum yields for the photorelease of the DMP group are higher in non-polar solvents, fi = 0.2, than in methanol, fi = 0.1. The photoreaction is initiated by efficient photoenolization, fi = 1. Three transient intermediates were identified by laser flash photolysis of 1a, the triplet state photoenol and the two ground state photoenols of Z and E configuration. Release of the acids 2a occurs predominantly from the E isomer, which has a lifetime of about 2 ms in methanoland 0.5 s in benzene solution. The present data are essential for potential applications of the DMP moiety as a photoremovable protecting group in organic synthesis or biochemistry ("caged compounds").

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

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Rok uplatnění

2001

Kód důvěrnosti údajů

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

Název periodika

Journal of Physical Chemistry A

ISSN

1089-5639

e-ISSN

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Svazek periodika

105

Číslo periodika v rámci svazku

45

Stát vydavatele periodika

US - Spojené státy americké

Počet stran výsledku

5

Strana od-do

10329

Kód UT WoS článku

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EID výsledku v databázi Scopus

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