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DC Field | Value | Language |
---|---|---|
dc.contributor.author | Kumar, Dalip | - |
dc.date.accessioned | 2021-10-27T04:22:59Z | - |
dc.date.available | 2021-10-27T04:22:59Z | - |
dc.date.issued | 2003-02 | - |
dc.identifier.uri | https://pubs.acs.org/doi/10.1021/jo0267192 | - |
dc.identifier.uri | http://dspace.bits-pilani.ac.in:8080/xmlui/handle/123456789/3085 | - |
dc.description.abstract | The factors that affect the kinetics of the aza-Bergman cyclization of aza-enediynes (C,N-dialkynyl imines) have not previously been elucidated. Here we report our kinetic studies of the aza-Bergman reactions of a series of 6-triisopropylsilyl and 6-unsubstituted 1-phenyl-4-aryl-3-aza-3-ene-1,4-diynes in which the aryl group is phenyl, o-(methoxy)phenyl, or p-(methoxy)phenyl. These aza-enediynes are prepared as single isomers in modest yield from the corresponding 1-aryl-3-(triisopropylsilyl)propynone oximes. These aza-enediynes undergo aza-Bergman reaction followed by a rapid retro-aza-Bergman cyclization to afford β-alkynyl acrylonitrile products. In no case are products corresponding to trapping the intermediate 2,5-didehydropyridine diradical isolated. While the rate of aza-Bergman cyclization is not greatly affected by the nature of the 4-aryl substituent, the rate is very dependent on the nature of the 6-substituent. 1-Phenyl-4-aryl-3-aza-3-ene-1,5-diynes that lack a 6-substituent undergo aza-Bergman cyclization spontaneously at 20 °C with first-order half-lives of 36−78 min. The effect of solvent on the kinetics of aza-Bergman cyclization of 1,4-diphenyl-3-aza-3-ene-1,5-diyne was investigated. The rate of this cyclization is solvent dependent, proceeding more rapidly in less polar solvents. | en_US |
dc.language.iso | en | en_US |
dc.publisher | ACS | en_US |
dc.subject | Chemistry | en_US |
dc.subject | Hydrocarbons | en_US |
dc.subject | Nitrogen compounds | en_US |
dc.subject | Cyclization | en_US |
dc.title | An Extremely Facile Aza-Bergman Rearrangement of Sterically Unencumbered Acyclic 3-Aza-3-ene-1,5-diynes | en_US |
dc.type | Article | en_US |
Appears in Collections: | Department of Chemistry |
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