Mechanism of Debromination of 1-Aryl-1,2-dibromo-2-nitropropanes Promoted by Secondary Amines in Acetonitrile

Bong-Rae Cho, Sup Joo Lee, Yong Kwan Kim

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Abstract

Debromination reactions of erythro-dl-l-aryl-l,2-dibromo-2-nitropropanes with secondary amines in MeCN have been investigated kinetically. Reactions of erythro-dl-l-aryl-l,2-dibromo-2-nitropropanes with secondary amines in MeCN are stereospecific, producing (E)-l-aryl-2-nirropropenes quantitatively. The rate equation for the reaction is KobS = K2[R2NH] + K3[R2NH]2, indicating that the reactions proceed by both uncatalyzed and base-catalyzed pathways. The Hammett Q, Bronsted β, ΔH*, and ΔS* values for the k2 and k3 processes are 1.22 ± 0.04 and 1.20 ± 0.02, 0.77 ± 0.05 and 1.05 ± 0.13, 5.6 ± 0.3 and 1.7 ± 0.1 kcal/mol, and —49.1 ± 4.5 and —60.7 ± 204 eu, respectively. For dehalogenation reactions from vicinal dibromo and bromochloro compounds, the element effect of the leaving group KBR/KCI = 7.8 and 25 have been determined for the k2 and K3 processes. From these results, the mechanism and the transition-state character of these reactions are assessed.

Original languageEnglish
Pages (from-to)2072-2076
Number of pages5
JournalJournal of Organic Chemistry
Volume60
Issue number7
DOIs
Publication statusPublished - 1995

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Amines
Dehalogenation
2-nitropropane
acetonitrile

ASJC Scopus subject areas

  • Organic Chemistry

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Mechanism of Debromination of 1-Aryl-1,2-dibromo-2-nitropropanes Promoted by Secondary Amines in Acetonitrile. / Cho, Bong-Rae; Lee, Sup Joo; Kim, Yong Kwan.

In: Journal of Organic Chemistry, Vol. 60, No. 7, 1995, p. 2072-2076.

Research output: Contribution to journalArticle

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abstract = "Debromination reactions of erythro-dl-l-aryl-l,2-dibromo-2-nitropropanes with secondary amines in MeCN have been investigated kinetically. Reactions of erythro-dl-l-aryl-l,2-dibromo-2-nitropropanes with secondary amines in MeCN are stereospecific, producing (E)-l-aryl-2-nirropropenes quantitatively. The rate equation for the reaction is KobS = K2[R2NH] + K3[R2NH]2, indicating that the reactions proceed by both uncatalyzed and base-catalyzed pathways. The Hammett Q, Bronsted β, ΔH*, and ΔS* values for the k2 and k3 processes are 1.22 ± 0.04 and 1.20 ± 0.02, 0.77 ± 0.05 and 1.05 ± 0.13, 5.6 ± 0.3 and 1.7 ± 0.1 kcal/mol, and —49.1 ± 4.5 and —60.7 ± 204 eu, respectively. For dehalogenation reactions from vicinal dibromo and bromochloro compounds, the element effect of the leaving group KBR/KCI = 7.8 and 25 have been determined for the k2 and K3 processes. From these results, the mechanism and the transition-state character of these reactions are assessed.",
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T1 - Mechanism of Debromination of 1-Aryl-1,2-dibromo-2-nitropropanes Promoted by Secondary Amines in Acetonitrile

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AB - Debromination reactions of erythro-dl-l-aryl-l,2-dibromo-2-nitropropanes with secondary amines in MeCN have been investigated kinetically. Reactions of erythro-dl-l-aryl-l,2-dibromo-2-nitropropanes with secondary amines in MeCN are stereospecific, producing (E)-l-aryl-2-nirropropenes quantitatively. The rate equation for the reaction is KobS = K2[R2NH] + K3[R2NH]2, indicating that the reactions proceed by both uncatalyzed and base-catalyzed pathways. The Hammett Q, Bronsted β, ΔH*, and ΔS* values for the k2 and k3 processes are 1.22 ± 0.04 and 1.20 ± 0.02, 0.77 ± 0.05 and 1.05 ± 0.13, 5.6 ± 0.3 and 1.7 ± 0.1 kcal/mol, and —49.1 ± 4.5 and —60.7 ± 204 eu, respectively. For dehalogenation reactions from vicinal dibromo and bromochloro compounds, the element effect of the leaving group KBR/KCI = 7.8 and 25 have been determined for the k2 and K3 processes. From these results, the mechanism and the transition-state character of these reactions are assessed.

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