100621-65-6Relevant articles and documents
Photolytic, thermal, addition, and cycloaddition reactions of 2-diazo-5,6- and -3,8-disubstituted acenaphthenones
Blair, Patricia A.,Chang, Sou-Jen,Shechter, Harold
, p. 7123 - 7133 (2007/10/03)
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 react thermally and photolytically with 11a-c with losses of N2 to yield 2-alkoxynaphthenones (24a,b and 47a,b) and acenaphthenones (25 and 48a,b). Aniline and diphenylamine are converted by 11a-c at 180°C to acenaph[1,2-6]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-naphthalic anhydrides. Insertion, addition, substitution, and/or isomerization reactions occur upon irradiation of 2-diazoacenaphthenones in cyclohexane, benzene, and tetrahydrofuran. Photolysis of 11d in benzene 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 dipolar cycloaddition to give acenaph[1,2-d]oxazoles (41 and 61a,b). Acetylenes undergo thermal and photolytic cycloaddition/1,5-sigmatropic rearrangement reactions with 11a-d with N2 retention to give pyrazolo[5,1-a]quinolin-7-ones (69f-j). 2-Diazoacenaphthenones 1a and 11a react thermally and 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 la, 11a-d, and 12 reported are discussed.
