2-Acetyl-1,3-indandione Derivatives, Amines, Diazonium Salts 2-Acetyl-1,3-indandione (1) undergoes the Mannich reaction with piperidine or diethyl-amine hydrochloride to give compounds 2 and 3, respectively. On treatment 1 with ethylenediamine hydrochloride and formaldehyde, 2,2′-[ethylene bis[imino(1-oxotri-methylene)]]di-1,3-indandione (4) was obtained.
With primary aromatic amines it yielded 2-[N-(substituted phenyl)acetimidoyl]-1,3-indandione (5a-i). The condensation of 1 with o-aminophenol yielded a mixture of 5c and the oxazepinone (6), while condensation with 2,3-diaminopyridine gave the diazepinone (7). Mannich reaction of 5a and g with piperidine hydrochloride and formaldehyde gave 8a, b. The coupling of 1 with diazonium salts was investigated.
A series of 2-cinnamoyl-1,3-indandiones (2a-e) were obtained by condensing 1 with aldehydes. Treatment of 2 a with hydrazine or hydroxylamine hydrochloride gave 2-(5-phenyl-2-pyrazolinyl or -isoxazolinyl)-1,3-indandione (3 and 5) respectively, and when treated with thiourea gave 2-(6-phenyl-2-thioxo-4-pyrimidinyl)-1,3-indandione (6).
The formation of 2-(β-piperidino-, -morpholino- and -arylmercaptohydrocinnamoyl)- 1,3-indandiones (7a-b and 8a-b) from 2 a was investigated. Compound 7b when treated with hydrazine gave 9. The 2-(α, β-dimorpholinohydrocinnamoyl) derivative (11) was obtained by the action of morpholine on the dibromo derivative (10). The Michael condensation of 2a with ethyl acetoacetate or acetyl acetone was investigated. Treatment of 1 with benzaldehyde in (3:1) molar ratio gave 14, which reacted with diethyl oxalate to give 15. Cyclization of 15 with polyphosphoric acid lead to the formation of 16.
Treatment of ethyl α-phenylthiocarbamylacetoacetate (1) with aromatic diazonium salts effects acetyl cleavage with the formation of ethyl α-phenylthiocarbamylglyoxalate arylhydrazones derivatives (2 a-e) which afford the anilinopyrazolones (5) and (7) on treatment with hydrazine or phenylhydrazine. The pyrazolones 5 a-e undergo aminoalkylation with formaldehyde and piperidine to give the N-Mannich bases 7 a-e, also obtained by treating the N-hydroxymethyl derivatives (9 a-e) with piperidine.
A new series of hexahydro-bis-benzodipyrazolones (2a-e) were obtained by the inter-action of 1 with hydrazines. These pyrazolones underwent coupling reaction with different diazonium salts to give 7a-g. Compound 1 when treated with acid hydrazides gave 3 a, b, and when subjected to Japp-Klingemann reaction in alkaline medium gave 6a-e. The hexahydro-bis-benzodiazepine (8), and dithiopyrimidoquinazolinetetrone (10) were obtained by the interaction of 1 with o-phenylenediamine and thiourea respectively.