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Title: Chemistry of some β-ketoesters derived from 9,10-phenanthraquinone
Author: Mahesar, Mohammed Ali
ISNI:       0000 0001 3616 6377
Awarding Body: University of Surrey
Current Institution: University of Surrey
Date of Award: 1975
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Reaction of the beta-ketoesters namely methyl (and ethyl) 3,3a-dihydro-3a-hydroxy-2-oxo-2H-cyclopenta(l)phenantherene-1-carboxylate (primary-condensate), of methyl (and ethyl) 2,3-dihydro-1-hydroxy-2-oxo-1H-cyclopenta(l)phenanthrene-1-carboxylate (iso-compound), and of methyl (and ethyl) 2,3-dihydro-1-oxo-1H-cyclopenta(l)phenanthrene-1-carboxylate (hydriodic acid reduced product) with ammonia, hydrazine, acetylhydrazine, and ethyl carbazate are investigated and several novel compounds are described. Reactions of the iso-compound with hydrazine, acetylhydrazine, and ethyl carbazate give the expected hydrazones and a second molecular proportion of hydrazine also reacts to afford the hydrazide-hydrazone. Reaction with ammonia includes rearrangement and leads to 3,3a-dihydro-3-hydroxy-2-oxo-2H-cyclopenta-(1)phenanthrene-1-carboxamide. The hydriodic acid reduced product reacts analogously with acetylhydrazine, and ethyl carbazate (to give hydrazones) but with ammonia the pentacyclic ring is opened and the half ester-half amide (-half hydrazide in the case of hydrazine) corresponding to 9,10-phenanthrenediacetic acid is obtained. The primary-condensate forms hydrazones with acetylhydrazine, and ethyl carbazate in acidified methanol, but isomerisation of the olefinic bond occurs and a methoxy group is incorporated in the reaction products methyl 2-acetylhydrazono-2,3-dihydro-1-methoxy-2-oxo-1H-cyclopenta(1)phenanthrene-1-carboxylate and methyl 2-ethoxycarbonylhydrazono-2,3-dihydro-l-methoxy-1H-cyclopenta(I)phenanthrene-1-carboxylate, Hydrazine participates in a Michael type addition reaction and a heterocyclic product 1, 2, 3, 4, 4a, 12b-hexahydro-12b-acetic acid ethyl ester -4a-hydroxy-3-oxo-1,2-diazatriphenylene is formed. This diazatriphenylene gives the acetyl derivative and undergoes thermal elimination of ethyl acetate and water to form a dibenzocinnolone namely 2,3-dihydro-3-oxo-1,2-diazatriphenylene, A Michael type addition occurs between the primary-condensate and ammonia, leading to 9-amino-9-carbamoylmethyl-10(9H)phe-nanthryleneacetamide.
Supervisor: Not available Sponsor: Not available
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID:  DOI: Not available