J 2001

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

ZABADAL, Miroslav, Anna P. PELLICCIOLI, Petr KLÁN and Jakob WIRZ

Basic information

Original name

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

Authors

ZABADAL, Miroslav (203 Czech Republic), Anna P. PELLICCIOLI, Petr KLÁN (203 Czech Republic, guarantor) and Jakob WIRZ

Edition

Journal of Physical Chemistry A, USA, The American Chemical Society, 2001, 1089-5639

Other information

Language

English

Type of outcome

Článek v odborném periodiku

Field of Study

10401 Organic chemistry

Country of publisher

United States of America

Confidentiality degree

není předmětem státního či obchodního tajemství

Impact factor

Impact factor: 2.630

RIV identification code

RIV/00216224:14310/01:00004579

Organization unit

Faculty of Science

UT WoS

000172206100020

Keywords (in Czech)

fotochemie

Keywords in English

photochemistry

Tags

Změněno: 18/6/2009 11:58, prof. RNDr. Petr Klán, Ph.D.

Abstract

V originále

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 methanol and 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").

Links

MSM 143100005, plan (intention)
Name: Strukturně-funkční vztahy biomolekul a jejich role v metabolismu
Investor: Ministry of Education, Youth and Sports of the CR, Biomolecular Structure-function Relationships and their role in the Metabolism