| Abstract
| - Preparation and varied thermal and photolytic reactions of 2-diazo-5,6-(disubstituted)acenaphthenones (11a−d) and 2-diazo-3,8-dimethoxyacenaphthenone (12) are reported. Alcohols reactthermally and photolytically with 11a−c with losses of N2 to yield 2-alkoxynaphthenones (24a,band 47a,b) and acenaphthenones (25 and 48a,b). Aniline and diphenylamine are converted by11a−c at 180 °C to acenaph[1,2-b]indoles (29a,b and 53a,b). Thermolyses of 11a−c at ∼450 °C(0.15 mmHg) yield reduction products 25 and 48a,b, respectively. Wolff rearrangements to 1,8-naphthyleneketenes (15a−d) and/or their derivatives are not observed in the above experiments.Oxygen converts 11a−c thermally to acenaphthenequinones (19a−c) and/or 1,8-naphthalicanhydrides. Insertion, addition, substitution, and/or isomerization reactions occur upon irradiationof 2-diazoacenaphthenones in cyclohexane, benzene, and tetrahydrofuran. Photolysis of 11d inbenzene in the presence of O2 yields the insertion−oxidation product 2-hydroxy-5,6-dinitro-2-phenylacenaphthenone (60). Photolyses of 11a−c in nitriles result in N2 evolution and dipolarcycloaddition to give acenaph[1,2-d]oxazoles (41 and 61a,b). Acetylenes undergo thermal andphotolytic cycloaddition/1,5-sigmatropic rearrangement reactions with 11a−d with N2 retentionto give pyrazolo[5,1-a]quinolin-7-ones (69f−j). 2-Diazoacenaphthenones 1a and 11a react thermallyand photolytically with electronegatively-substituted olefins with N2 expulsion to yield (E)- and(Z)-2-oxospiro[acenaphthylene-1(2H),1‘cyclopropanes] 73a−c and 74a−c, respectively. The mechanisms of the reactions of 1a, 11a−d, and 12 reported are discussed.
|
