Investigations of the mechanistic details and potential synthetic applications of the di-[pi]-methane rearrangement /
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| Other Authors: | , , |
| Format: | Thesis Book |
| Language: | English |
| Published: |
1978.
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| Subjects: | |
| Online Access: | Link to ProQuest copy Link to OAKTrust copy |
| Abstract: | The di-π-methane rearrangement has been shown to be of very general scope. During the course of a study designed to broaden the scope of this rearrangement by including a nitrogen atom in the backbone of the di-π-methane chromophore a novel photocyclization reaction of potential mechanistic and synthetic significance was uncovered. Irradiation of a methanolic solution of a 2-aza-1,4-diene (2-aza-3,3- dimethyl-1-phenyl-1 ,4-hexadiene) perchlorate salt lead to the production of a pyrrolidine ether and enol ether derivative of the starting inline. The photocyclization reaction leading to the pyrrolidine ether can be nicely rationalized using mechanisms in which initial electron transfer from olefin to singlet excited iminium salt leads to the production of a radical-radical cation pair. Subsequent nucleophilic solvent attack and ring closure or disproportionation produce the observed pyrrolidine ether and enol ether products. The details of this study including synthesis of the N-allyliminium salts, elucidation of product structures and discussion of mechanisms are described. During the course of studies related to mechanisms for the di-π-methane rearrangement involving the intermediacy of cyclopropyldicarbinyl diradicals, we investigated the gas-phase photodecarbonylation reactions of 3,3-dimethylbicyclo[3.1.0]hexan-3-one.. |
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| Item Description: | "Major subject: Chemistry." Typescript (photocopy). Vita. |
| Physical Description: | xiv, 117 leaves : illustrations ; 28 cm |
| Bibliography: | Includes bibliographical references (leaves 112-116). |