Detailed Information on Publication Record
2006
Photochemistry of 2-Alkoxymethyl-5-methylphenacyl Chloride and Benzoate
PLÍŠTIL, Lukáš, Tomáš ŠOLOMEK, Jakob WIRZ, Dominik HEGER, Petr KLÁN et. al.Basic information
Original name
Photochemistry of 2-Alkoxymethyl-5-methylphenacyl Chloride and Benzoate
Name in Czech
Fotochemie 2-alkoxynethyl-5-methylfenacyl chloridu a benzoatu
Authors
PLÍŠTIL, Lukáš (203 Czech Republic), Tomáš ŠOLOMEK (703 Slovakia), Jakob WIRZ (756 Switzerland), Dominik HEGER (203 Czech Republic) and Petr KLÁN (203 Czech Republic, guarantor)
Edition
Journal of Organic Chemistry, Columbus, OH, USA, the American Chemical Society, 2006, 0022-3263
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: 3.790
RIV identification code
RIV/00216224:14310/06:00020996
Organization unit
Faculty of Science
UT WoS
000241053000016
Keywords in English
Photochemistry; phenacyl group; photoenolization
Tags
International impact, Reviewed
Změněno: 23/6/2009 15:15, prof. RNDr. Petr Klán, Ph.D.
V originále
Irradiation of 2-(alkoxymethyl)-5-methyl--chloroacetophenones (1a-c) and 2-(methoxymethyl)-5-methylphenacyl benzoate (1d) in dry, nonnucleophilic solvents afforded 3-alkoxy-6-methylindan-1-ones (3a-c) in very high chemical yields. 3-Methylisobenzofuran-1(3H)-one (2) was, however, isolated as a major photoproduct in the presence of trace amounts of water. Quenching experiments and laser flash spectroscopy revealed that the indanone derivatives 3 are formed by 1,5-hydrogen migration from the lowest triplet excited state of the acetophenones 1 and cyclization of the resulting photoenols. In contrast, production of the lactone 2 in wet solvents was found to result from two consecutive photochemical transformations. The photoenols produced by photolysis of 1a-c add water as a nucleophile to form 2-acetyl-4-methylbenzaldehyde (4), which is further converted to 2 via a second, singlet state photoenolization process. Exhaustive photolysis of 1a in methanol produced the acetal 2-(dimethoxymethyl)-5-methylacetophenone (7a) as the exclusive product. The remarkable selectivity of these photoreactions may well be useful in synthetic organic chemistry.
In Czech
Irradiation of 2-(alkoxymethyl)-5-methyl--chloroacetophenones (1a-c) and 2-(methoxymethyl)-5-methylphenacyl benzoate (1d) in dry, nonnucleophilic solvents afforded 3-alkoxy-6-methylindan-1-ones (3a-c) in very high chemical yields. 3-Methylisobenzofuran-1(3H)-one (2) was, however, isolated as a major photoproduct in the presence of trace amounts of water. Quenching experiments and laser flash spectroscopy revealed that the indanone derivatives 3 are formed by 1,5-hydrogen migration from the lowest triplet excited state of the acetophenones 1 and cyclization of the resulting photoenols. In contrast, production of the lactone 2 in wet solvents was found to result from two consecutive photochemical transformations. The photoenols produced by photolysis of 1a-c add water as a nucleophile to form 2-acetyl-4-methylbenzaldehyde (4), which is further converted to 2 via a second, singlet state photoenolization process. Exhaustive photolysis of 1a in methanol produced the acetal 2-(dimethoxymethyl)-5-methylacetophenone (7a) as the exclusive product. The remarkable selectivity of these photoreactions may well be useful in synthetic organic chemistry.
Links
| GA203/05/0641, research and development project |
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| MSM0021622413, plan (intention) |
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