An attempted synthesis of a cycloheximide analog exploratory work on the reaction of cobalt (III) acetate manganese (III) acetate, telluorium dioxide, cerium (IV) trifluoroacetate and potassium superoxide on ring-A aromatic steroids
Piatak, David M.
M.S. (Master of Science)
Department of Chemistry
Organonitrogen compounds; Aromatic compounds; Organometallic compounds; Steroids
The glutarimide antibiotics are a group of biologically important, naturally occurring substances. Cycloheximide possesses antitumour, antifungal and powerful fungicidal properties and, more recently, anticonvulsant action. A synthesis whereby 1-carboxycyclopropane-2,3,-(N-phenyl)-dicarboximide would be used as the imide moiety and, in subsequent steps, would be condensed with the cyclohexanone position of the molecule to give a new analog with improved anticonvulsant action was undertaken. l-carbethoxycyclopropane-2,3,-(N-phenyl)dicarboximide was prepared by reported procedures. The subsequent hydrolysis of the ester to the acid caused opening of the 5-membered ring which could not be closed nor prevented in any way. The project was abandoned after various other methods to effect conversion of the ester to acid failed. The oxidizing properties of Co(III)OAc, Mn(III)OAc, TeO₂, Ce(IV)TFA and KO₂on aromatic hydrocarbons have been studied. These compounds are known to functionalize aromatic compounds on the nucleus or on the side chain. Mn(III)OAc affects nuclear substitution or side chain oxidation either by electron transfer or free radical pathway. Co(111)OAc affects only side-chain oxidation by 1-electron transfer. Aromatics undergo acetoxymethylation in the presence of TeO₂/LiBr/HOAc. Ce(IV)TFA gives biaryls, diarylmethanes and trifluoroacetate esters. Reactions with these reagents and some ring A aromatic steroids were conducted. Co(III)OAc, Mn(III)OAc, TeO₂, Ce(IV)TFA were found to have no effect on the aromatic steroids when the substituent on the aromatic ring A was the acetoxy group. Methoxy substituted aromatic steroids underwent reaction. KO₂ gave two components: a neutral simple hydrolysis product of the aromatic acetoxy moiety and a very minor acidic component whose yield could not be improved.
Purkayastha, Subhasish, "An attempted synthesis of a cycloheximide analog exploratory work on the reaction of cobalt (III) acetate manganese (III) acetate, telluorium dioxide, cerium (IV) trifluoroacetate and potassium superoxide on ring-A aromatic steroids" (1984). Graduate Research Theses & Dissertations. 1195.
vii, 98 pages
Northern Illinois University
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