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Title: Studies of the reactions of 3H-pyrrolizines with acetylenes
Author: Johnson, David
Awarding Body: Keele University
Current Institution: Keele University
Date of Award: 1972
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An attempt was made to synthesise azonia-azulenium salts by the 2+2 cycloaddition of acetylenes to 3H-pyrrolizine, and the subsequent ring expansion of the cyclobutene product. In Part I the attempted syntheses of some new 3Hpyrrolizines are described and a review is included on the syntheses of 3H-pyrrolizines already known. Part II describes the reactions of 3H-pyrrolizines with dimethyl acetylenedicarboxylate and includes a brief review on the reactions of dimethyl acetylenedicarboxylate with compounds closely related to 3H-pyrrolizine. The thermal reactions of 3H,1-methyl-3H and 1,2-dimethyl-3Hpyrrolizines, with dimethyl acetylenedicarboxylate, gave derivatives of 3-carbomethoxy (carbomethoxymethyl) methylene- 3H-pyrrolizine and cycl [4,2,2] azine. Attempts to prepare the cycl [4,2,2] azini um sys tem from a cycl [4,2,2] azine derivative are described, and a review is included on the synthesis and properties of known cyclazines. The photochemical reaction of dimethyl acetylenedicarboxylate with 3H-pyrrolizine gave a low yield of cyclobutene derivatives and a larger yield of the thermal products. The photochemical reaction with 3,3-dimethyl-3H-pyrrolizine, however, gave a moderate yield of the cyclobutene derivative. The cyclobutene ring of this photolysis product was successfully opened to give a pyrrolo [1,2-a] azepine.
Supervisor: Not available Sponsor: Not available
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID:  DOI: Not available
Keywords: QD Chemistry