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Environmentally friendly microwave enhanced syntheses of important cyclic imides and their derivatives

Posted on:2008-07-28Degree:Ph.DType:Thesis
University:Morgan State UniversityCandidate:Benjamin, Ellis TFull Text:PDF
GTID:2441390005954024Subject:Chemistry
Abstract/Summary:
The development of efficient environmentally friendly techniques is a desired objective in organic chemistry. The application of microwaves in organic synthesis provides excellent benefits; while being green chemistry it is efficient and simple. The application of microwaves for the manufacture of important moieties such as cyclic imides, their derivatives, thalidomide and its analogues, and enaminones and its derivatives are the objectives of this study.;The synthesis of the cyclic imides starts with cyclic anhydrides, such as substituted succinic anhydride obtained via the solventless microwave-enhanced Diels-Alder reaction of maleic anhydride. The nitrogen source utilized ammonium salts such as ammonium chloride (NH4Cl), ammonium acetate (NH 4OAc), hydroxylamine hydrochloride (NH2OH/HCl) and N-methoxyamine hydrochloride (NH2OCH3/HCl).;The use of multimode microwave and the monomode microwave with controlled temperature, pressure, and microwave power provided a comparison between the two available types of microwave ovens. The strategy used NH4Cl in the presence of dimethylaminopyridine (DMAP) as a base, which seemed to be efficient in providing the unsubstituted cyclic imides within minutes. Another alternative is ammonium acetate, which reacted without the addition of the base and provided the cyclic imides in shorter time in comparable yields under the microwave conditions. While N-hydroxy imides were not obtained in good yields using DMAP, unsubstituted cyclic imides were achieved in good yield using this protocol. Analogously, N-methoxy cyclic imides were acquired from N-methoxyamine, hydrochloride/DMAP.;In application of this strategy to compounds of importance, the synthesis of thalidomide and its analogues was a focus of this study and were achieved in good yield using cyclic anhydride, glutamic acid, ammonium chloride, and DMAP in a one-pot reaction under the solventless conditions developed. Another application was the synthesis of enaminones and its derivatives from 1,3-cycloalkanediones and ammonium acetate in the soventless conditions which were obtained in excellent yields.;This study provided efficient, easy, eco-friendly synthetic methods to a variety of cyclic imides, N-methoxyimides, thalidomide and its analogues, enaminones and its derivatives that can be of value for the synthesis of natural products and pharmaceutical drugs.
Keywords/Search Tags:Cyclic imides, Microwave, Derivatives, Synthesis, Application, Efficient, Thalidomide and its analogues
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