10-Diazoanthrone (1) has been prepared by base-catalyzed decomposition of 9,10-anthraquinone mono-p-tosylhydrazone (8), by oxidation of 9,10-anthraquinone monohydrazone (7), and by amination of 9,10-anthraquinone monoxime (9). Reactions of 1 with acrylonitrile, methyl vinyl ketone, methyl methacrylate, trans-1,2-dibenzoylethylene, and p-benzoquinone yield spiro [anthrone-10,1’-cyclopropanes] (12-15, 18); with p-benzoquinone, 4’,7’-dihydroxyspiro[anthrone-10,3’-indazole] (17) is also obtained. N-Phenyl-9,10-anthraquinone monoimine N-oxide (19) and N,N-dicarbethoxy-9,10-anthraquinone monohydrazone (20) are formed from reactions of 1 with nitrosobenzene and with diethyl azodicarboxylate. Additions of 1 to dimethyl acetylenedicarboxylate and to benzyne give 4’,5 ’-dicarbomethoxyspiro [anthrone-10,3’ (3’H)-pyrazole] (21) and spiro-[anthrone-10,3’-indazole] (23). Photolysis of 21 results in 1’,2’-dicarbomethoxyspiro[anthrone-10,3’-cyclopropene] (22). Thermolysis of 1 in 9,10-phenanthrenequinone yields spiro [anthrone-10,2’-(phenanthro[9.10]- 1’,3’-dioxole)] (24) and Δ10,10’-bianthrone (26). 3-Methylnaphthalene 1,4-diazooxide (2) adds to. trans-1,2-dibenzoylethylene and to benzyne to form imns-2,3-dibenzoyl-2’-methylspiro[cyclopropane-1,4’-(1’[l’H,4’H]-naphthalenone)] (27) and 2’-methylspiro[indazole-3,4’-(1’[1’H,4’H]-naphthalenone)](28). 3,5-Dimethyl-trans-7,8-dibenzoylspiro[2.5]octa-2,5-dien-4-one (29) is obtained from 3,5-dimethylbenzene 1,4-diazooxide (3) and iraros-1,2-dibenzoylethylene. Thermolysis of 1 in benzene catalyzed by copper affords 9,10-anthraquinone azine (30) and 26. Photolysis of 1 in benzene produces biphenyl (35), 10,10’-bianthrone (36), 30, and 10-phenylanthrone (37). Decomposition of 1 in mesitylene yields 36 and 10,10-bis(3,5-dimethylbenzyl)anthrone. Triphenylphosphine reacts with 1, yielding 9,10-anthraquinone monotriphenylphosphazine (39). Photolysis of 1 in the presence of triphenylphosphine leads to 10-triphenylphosphoranylanthrone (38); under similar conditions 2 and triphenylphosphine give 2-methyl-1,4-naphthoquinone 4-triphenylphosphazine (40). Displacement of 10-bromoanthrone by triphenylphosphine results predominantly in anthracene-9-oxytriphenylphosphonium bromide (42). Both m- and p-nitrobenzaldehyde react with 38 to give benzylideneanthrones (44a and 44b). © 1969, American Chemical Society. All rights reserved.
