2006
Photochemistry of 2-Alkoxymethyl-5-methylphenacyl Chloride and Benzoate
PLÍŠTIL, Lukáš, Tomáš ŠOLOMEK, Jakob WIRZ, Dominik HEGER, Petr KLÁN et. al.Základní údaje
Originální název
Photochemistry of 2-Alkoxymethyl-5-methylphenacyl Chloride and Benzoate
Název česky
Fotochemie 2-alkoxynethyl-5-methylfenacyl chloridu a benzoatu
Autoři
PLÍŠTIL, Lukáš (203 Česká republika), Tomáš ŠOLOMEK (703 Slovensko), Jakob WIRZ (756 Švýcarsko), Dominik HEGER (203 Česká republika) a Petr KLÁN (203 Česká republika, garant)
Vydání
Journal of Organic Chemistry, Columbus, OH, USA, the American Chemical Society, 2006, 0022-3263
Další údaje
Jazyk
angličtina
Typ výsledku
Článek v odborném periodiku
Obor
10401 Organic chemistry
Stát vydavatele
Spojené státy
Utajení
není předmětem státního či obchodního tajemství
Impakt faktor
Impact factor: 3.790
Kód RIV
RIV/00216224:14310/06:00020996
Organizační jednotka
Přírodovědecká fakulta
UT WoS
000241053000016
Klíčová slova anglicky
Photochemistry; phenacyl group; photoenolization
Štítky
Příznaky
Mezinárodní význam, Recenzováno
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.
Česky
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.
Návaznosti
| GA203/05/0641, projekt VaV |
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| MSM0021622413, záměr |
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