Eliminations from (E)-2,4-Dinitrobenzaldehyde O-Aryloximes Promoted by R3N in MeCN. Effects of β-Aryl Group and Base-Solvent on the Nitrile-Forming Transition-State
Nitrile-forming eliminations from (E)-2,4-(NO2)2C6H2CH=NOC6H4-2-X-4-NO2 (1a-e) promoted by R3N in MeCN have been studied kinetically. The reactions are second-order and exhibit Brönsted β = 0.83-1.0 and |βlg| = 0.41-0.46. The results have been interpreted in terms of highly E1cb-like transition stat...
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Veröffentlicht in: | Bulletin of the Korean Chemical Society 2012, 33(9), , pp.2976-2980 |
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Sprache: | eng |
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Zusammenfassung: | Nitrile-forming eliminations from (E)-2,4-(NO2)2C6H2CH=NOC6H4-2-X-4-NO2 (1a-e) promoted by R3N in MeCN have been studied kinetically. The reactions are second-order and exhibit Brönsted β = 0.83-1.0 and |βlg| = 0.41-0.46. The results have been interpreted in terms of highly E1cb-like transition state with extensive Cβ- H bond cleavage and limited Nα-OAr bond cleavage. Comparison with existing data reveals that the structure of the transition state changes from E2-central to highly E1cb-like either by the change of the β-aryl group from Ph to 2,4-dinitrophenyl under the same condition or by the base-solvent system variation from EtO−-EtOH to Et3N-MeCN for a given substrate (1a-e). KCI Citation Count: 2 |
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ISSN: | 0253-2964 1229-5949 |
DOI: | 10.5012/bkcs.2012.33.9.2976 |