Eliminations from (E)-2,4-dinitrobenzaldehyde O-aryloximes promoted by R 3N in MeCN. Effects of β-aryl group and base-solvent on the nitrile-forming transition-state

Bong-Rae Cho, Eun Mi Ryu, Sang Yong Pyun

Research output: Contribution to journalArticle

2 Citations (Scopus)

Abstract

Nitrile-forming eliminations from (E)-2,4-(NO 2) 2C 6H 2CH=NOC 6H 4-2-X-4-NO 2 (1a-e) promoted by R 3N 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 Et 3N-MeCN for a given substrate (1a-e).

Original languageEnglish
Pages (from-to)2976-2980
Number of pages5
JournalBulletin of the Korean Chemical Society
Volume33
Issue number9
DOIs
Publication statusPublished - 2012 Sep 20

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Nitriles
Substrates
2,4-dinitrobenzaldehyde

Keywords

  • E2 and E1cb-like
  • Elimination

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

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title = "Eliminations from (E)-2,4-dinitrobenzaldehyde O-aryloximes promoted by R 3N in MeCN. Effects of β-aryl group and base-solvent on the nitrile-forming transition-state",
abstract = "Nitrile-forming eliminations from (E)-2,4-(NO 2) 2C 6H 2CH=NOC 6H 4-2-X-4-NO 2 (1a-e) promoted by R 3N in MeCN have been studied kinetically. The reactions are second-order and exhibit Br{\"o}nsted 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 Et 3N-MeCN for a given substrate (1a-e).",
keywords = "E2 and E1cb-like, Elimination",
author = "Bong-Rae Cho and Ryu, {Eun Mi} and Pyun, {Sang Yong}",
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journal = "Bulletin of the Korean Chemical Society",
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TY - JOUR

T1 - Eliminations from (E)-2,4-dinitrobenzaldehyde O-aryloximes promoted by R 3N in MeCN. Effects of β-aryl group and base-solvent on the nitrile-forming transition-state

AU - Cho, Bong-Rae

AU - Ryu, Eun Mi

AU - Pyun, Sang Yong

PY - 2012/9/20

Y1 - 2012/9/20

N2 - Nitrile-forming eliminations from (E)-2,4-(NO 2) 2C 6H 2CH=NOC 6H 4-2-X-4-NO 2 (1a-e) promoted by R 3N 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 Et 3N-MeCN for a given substrate (1a-e).

AB - Nitrile-forming eliminations from (E)-2,4-(NO 2) 2C 6H 2CH=NOC 6H 4-2-X-4-NO 2 (1a-e) promoted by R 3N 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 Et 3N-MeCN for a given substrate (1a-e).

KW - E2 and E1cb-like

KW - Elimination

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JO - Bulletin of the Korean Chemical Society

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