PLÍŠTIL, Lukáš, Tomáš ŠOLOMEK, Jakob WIRZ, Dominik HEGER a Petr KLÁN. Photochemistry of 2-Alkoxymethyl-5-methylphenacyl Chloride and Benzoate. Journal of Organic Chemistry. Columbus, OH, USA: the American Chemical Society, 2006, roč. 71, č. 21, s. 8050-8058. ISSN 0022-3263. |
Další formáty:
BibTeX
LaTeX
RIS
@article{698312, author = {Plíštil, Lukáš and Šolomek, Tomáš and Wirz, Jakob and Heger, Dominik and Klán, Petr}, article_location = {Columbus, OH, USA}, article_number = {21}, keywords = {Photochemistry; phenacyl group; photoenolization}, language = {eng}, issn = {0022-3263}, journal = {Journal of Organic Chemistry}, title = {Photochemistry of 2-Alkoxymethyl-5-methylphenacyl Chloride and Benzoate}, volume = {71}, year = {2006} }
TY - JOUR ID - 698312 AU - Plíštil, Lukáš - Šolomek, Tomáš - Wirz, Jakob - Heger, Dominik - Klán, Petr PY - 2006 TI - Photochemistry of 2-Alkoxymethyl-5-methylphenacyl Chloride and Benzoate JF - Journal of Organic Chemistry VL - 71 IS - 21 SP - 8050-8058 EP - 8050-8058 PB - the American Chemical Society SN - 00223263 KW - Photochemistry KW - phenacyl group KW - photoenolization N2 - 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. ER -
PLÍŠTIL, Lukáš, Tomáš ŠOLOMEK, Jakob WIRZ, Dominik HEGER a Petr KLÁN. Photochemistry of 2-Alkoxymethyl-5-methylphenacyl Chloride and Benzoate. \textit{Journal of Organic Chemistry}. Columbus, OH, USA: the American Chemical Society, 2006, roč.~71, č.~21, s.~8050-8058. ISSN~0022-3263.
|