Ipso Nitration. Preparation of 4-Methyl-4-nitrocyclohexadienols and Detection of Intramolecular Hydrogen Migration (NIH Shift) upon Solvolytic Rearomatization

Ken S. Feldman, McDermott Ann, P. C. Myhre

Research output: Contribution to journalArticle

9 Citations (Scopus)

Abstract

4-Alkyl-4-nitrocyclohexadienols are formally the 1,4 adducts of nitric acid and the parent alkylbenzene. Evidence of formation of these ipso nitration products during nitration in aqueous systems is convincing, although none of these intermediates have been isolated from direct nitration. In contrast, the acetate derivatives of these nitrodienols have been repeatedly isolated from nitrations in acetic anhydride. We have found that several 4-methyl-4-nitrocyclohexadienols may be readily prepared by reduction of the corresponding 4-methyl-4-nitrocyclohexadienones, and we report here studies of the solvolytic behavior that illustrate some interesting differences in the reactivity of nitrodienols and their acetate derivatives.

Original languageEnglish (US)
Pages (from-to)505-506
Number of pages2
JournalJournal of the American Chemical Society
Volume101
Issue number2
DOIs
StatePublished - Feb 1 1979

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Nitration
Hydrogen
Acetates
Nitric Acid
Derivatives
Nitric acid
acetic anhydride

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this

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Ipso Nitration. Preparation of 4-Methyl-4-nitrocyclohexadienols and Detection of Intramolecular Hydrogen Migration (NIH Shift) upon Solvolytic Rearomatization. / Feldman, Ken S.; Ann, McDermott; Myhre, P. C.

In: Journal of the American Chemical Society, Vol. 101, No. 2, 01.02.1979, p. 505-506.

Research output: Contribution to journalArticle

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T1 - Ipso Nitration. Preparation of 4-Methyl-4-nitrocyclohexadienols and Detection of Intramolecular Hydrogen Migration (NIH Shift) upon Solvolytic Rearomatization

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AU - Ann, McDermott

AU - Myhre, P. C.

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AB - 4-Alkyl-4-nitrocyclohexadienols are formally the 1,4 adducts of nitric acid and the parent alkylbenzene. Evidence of formation of these ipso nitration products during nitration in aqueous systems is convincing, although none of these intermediates have been isolated from direct nitration. In contrast, the acetate derivatives of these nitrodienols have been repeatedly isolated from nitrations in acetic anhydride. We have found that several 4-methyl-4-nitrocyclohexadienols may be readily prepared by reduction of the corresponding 4-methyl-4-nitrocyclohexadienones, and we report here studies of the solvolytic behavior that illustrate some interesting differences in the reactivity of nitrodienols and their acetate derivatives.

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