Sangam: A Confluence of Knowledge Streams

Studies of intramolecular S<sub>RN</sub>1 reactions of carbanions derived from 2-(o-halobenzyl)amides and 3-(o-halobenzyl)imides: application to the synthesis of succinimido[3,4-b]indane, a potential anticonvulsant

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dc.contributor Chemistry
dc.contributor Wolfe, James F.
dc.contributor Kingston, David G. I.
dc.contributor Mason, John G.
dc.contributor Tanko, James M.
dc.contributor Gibson, Harry W.
dc.creator Dandekar, Sushama A.
dc.date 2014-03-14T21:22:00Z
dc.date 2014-03-14T21:22:00Z
dc.date 1992-03-05
dc.date 2005-10-24
dc.date 2005-10-24
dc.date 2005-10-24
dc.date.accessioned 2023-02-28T16:59:04Z
dc.date.available 2023-02-28T16:59:04Z
dc.identifier etd-10242005-124048
dc.identifier http://hdl.handle.net/10919/40096
dc.identifier http://scholar.lib.vt.edu/theses/available/etd-10242005-124048/
dc.identifier.uri http://localhost:8080/xmlui/handle/CUHPOERS/264610
dc.description The possibility of inducing intramolecular SRN! reactions in two 2-(o-halobenzyl)- amides, 2-(o-iodobenzyl)-N,N,N’N’-tetramethylsuccinamide (77) and 2-(o-iodobenzyl)- N,N,N’N’-tetramethylglutaramide (80), and three 3-(o-halobenzyl)imides, 3-(oiodobenzyl)succinimide (99), 3-(α-cyano-o-bromobenzyl)succinimide (82) and 3-(oiodobenzyl)glutarimide (108), was investigated. All of these substrates were prepared during the course of the investigation. Treatment of 77 and 80 with excess potassium amide in liquid ammonia under photostimulated conditions afforded reasonably good yields of the expected cyclized products, 1,2-bis-(N,N-dimethylcarboxamido)indane (78) and 1,3-bis-(N,N-dimethylcarboxamido)-1,2,3,4-tetrahydronaphthalene (81), respectively. When imide 99 was subjected to similar conditions, it also underwent the expected cyclization, affording succinimido[3,4-b]indane (61) in acceptable yield. Mechanistic investigations revealed that all of the above reactions appear to occur via intramolecular S<sub>RN</sub>1 processes. Attempts to induce similar cyclization reactions with 3-(α-cyano-o-bromobenzyl)- succinimide (82) and 3-(o-iodobenzyl)glutarimide (108) proved unsatisfactory. Substrate 82 failed to undergo cyclization to give the desired succinimido[3,4-b]indane-8-carbonitrile (83). Instead, 3-(α-cyano-α-phenylmethyleno)succinimide (107) was formed as the sole isolable product, presumably via an intramolecular β-hydrogen atom abstraction process. 3-(o-Iodobenzyl)glutarimide (108) did not undergo the desired cyclization to give 1,2,3,4,5,6-hexahydro- 1,5-methano-3-benzazocine-2,4-dione (62) either, presumably because of steric hindrance. This study was undertaken with the objective of investigating the possibility of inducing intramolecular S<sub>RN</sub>1 reactions in appropriately substituted amide and imide derivatives. The specific substrates, 77, 80, 82, 99 and 108, were selected for the study because it appeared that intramolecular S<sub>RN</sub>1 reactions with these substrates would result in the formation of products that might be useful in the development of new anticonvulsant agents. In this context, the preparation of succinimido[3,4-b]indane (61), which seemed likely to possess antiepileptic properties, fulfilled our proposed objective of applying novel chemistry to the preparation of a new potential anticonvulsant agent. The successful cyclization of 77 and 80 into the expected products, 1,2-bis-(N,Ndimethylcarboxamido)indane (78) and 1,3-bis-(N,N-dimethylcarboxamido)-1,2,3,4- tetrahydronaphthalene (81), respectively, also represented the application of novel chemistry to the formation of two other benzo-fused systems. The synthetic and mechanistic investigations undertaken during this study are expected to extend the scope of the synthetic utility of intramolecular S<sub>RN</sub>1 chemistry.
dc.description Ph. D.
dc.format x, 230 leaves
dc.format BTD
dc.format application/pdf
dc.format application/pdf
dc.language en
dc.publisher Virginia Tech
dc.relation OCLC# 26166944
dc.relation LD5655.V856_1992.D362.pdf
dc.rights In Copyright
dc.rights http://rightsstatements.org/vocab/InC/1.0/
dc.subject LD5655.V856 1992.D362
dc.subject Anticonvulsants -- Synthesis
dc.subject Carbanions
dc.subject Nucleophilic reactions
dc.subject Substitution reactions
dc.title Studies of intramolecular S<sub>RN</sub>1 reactions of carbanions derived from 2-(o-halobenzyl)amides and 3-(o-halobenzyl)imides: application to the synthesis of succinimido[3,4-b]indane, a potential anticonvulsant
dc.type Dissertation
dc.type Text


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