Syntheses on the basis of diethyl (2-morpholinoethyl)malonate

Abstract

New functionally substituted butan-4-olides were synthesized by reactions of diethyl (2-morpholinoethyl)malonate with 2-(allyloxymethyl)oxirane, 4-(oxiran-2-ylmethyl)morpholine, N-ethyl-N-(oxiran-2-ylmethyl)aniline, and 1-chloro-2,3-epoxypropane. 5-[2-(Morpholino)ethyl]barbituric and -thiobarbituric acids were also synthesized. † Deceased.Organic oxides are universal starting compounds for the synthesis of butanolides. Some publications in this field are related to syntheses of biologically active natural compounds [1][2][3][4][5]. We have developed a procedure for the preparation of diethyl (2-morpholinoethyl)-malonate (I) from diethyl malonate sodium salt and 4-(2-chloroethyl)morpholine in ethanol. Diester I may be used as a basis for the synthesis of new morpholinecontaining lactones. It is known that molecules of many biologically active compounds, in particular tranquilizers, synthetic narcotic analgesics, anticonvulsants, and antituberculous agents, include a morpholine fragment [6].By condensation of diester I with 2-(allyloxymethyl)oxirane, 4-(oxiran-2-ylmethyl)morpholine, and N-ethyl-N-(oxiran-2-ylmethyl)aniline (reactant ratio 1 : 1) in anhydrous ethanol we obtained 5-substituted 3-(2-morpholinoethyl)tetrahydrofuran-2-ones VI-VIII (Scheme 1). The reaction begins with heterolytic cleavage of the epoxide C-O bond according to the

Ring Expansions of Oxiranes and Oxetanes

“…Ring Expansions of Oxiranes and OxetanesGalstyan and coworkers have reported the ring expansion of oxiranes using dialkyl malonate substituted with a morpholine tether (Scheme 18)[26]. Sodium alkoxide is used to facilitate ring opening resulting in an alkoxide, which then proceeds to form a lactone.…”