Cited by 56Chemical Reaction MechanismsChemical Synthesis and ReactionsOxidative Organic Chemistry Reactions

Acid-Promoted Reactions of Ethyl Linoleate with Nitrite Ions: Formation and Structural Characterization of Isomeric Nitroalkene, Nitrohydroxy, and Novel 3-Nitro-1,5-hexadiene and 1,5-Dinitro-1,3-pentadiene Products

Napolitano, Alessandra, Camera, Emanuela, Picardo, Mauro, d'Ischia, Marco·2000·The Journal of Organic Chemistry

Abstract

The reaction of ethyl linoleate (1) with NO(2)(-) in different air-equilibrated acidic media resulted in the formation of complex patterns of products, some of which could be isolated by repeated TLC fractionation and were formulated as the nitroalkenes 2-5, the novel (1E, 5Z)-3-nitro-1,5-hexadienes 6/7, the novel (E,E)-1, 5-dinitro-1,3-pentadiene derivatives 8 and 9, and the nitro alcohols 10/11 and 12/13 by extensive GC-MS and 2D NMR analysis, as aided by 1D Hartmann-Hahn proton mapping experiments. Similar reaction of methyl oleate gave mainly nitroalkene (14/15) and allylic nitro derivatives (16/17). Formation of 2-13 may be envisaged in terms of HNO(2)-mediated nitration pathways in which regioisomeric beta-nitroalkyl radical intermediates derived from attack of NO(2) to the 1,4-pentadiene moiety of 1 evolve through competitive H-atom abstraction and free radical combination routes.

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Crossref · 10.1021/jo000090q

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  • Nitrito functional groups undergo rapid hydrolysis to yield the corresponding alcohol, with further elimination of water, resulting in a vinyl nitro product.

    “Nitrito functional groups would undergo rapid hydrolysis to yield the corresponding alcohol, with further elimination of water, resulting in a vinyl nitro product (43).”

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Authors
Napolitano, A., Camera, E., Picardo, M., & d'Ischia, M.
Affiliations
  • San Gallicano Hospital (IT)
  • Department of Organic and Biological Chemistry, University of Naples Federico II, Via Mezzocanone 16, I-80134 Naples, Italy, and Istituto Dermatologico S. Gallicano, Via S. Gallicano 25a, 00153 Rome, Italy
Venue
The Journal of Organic Chemistry
Published
2000-07-15
Volume
65
Issue
16
Pages
4853-4860
ISSN
  • 0022-3263 (ISSN-L)
  • 1520-6904
OpenAlex
W1985824649
Cited by
56
References
19
Citations by year
2024: 2 · 2021: 2 · 2019: 2 · 2018: 1 · 2017: 1 · 2016: 1 · 2015: 1 · 2013: 5 · 2012: 1
FWCI
2.32
Type
journal article
Language
en
Open access
closed
Locations
  • The Journal of Organic Chemistry (publishedVersion)
  • PubMed (publishedVersion)
  • Scuola Normale Superiore di Pisa (submittedVersion)
Topics
  • Physical Sciences › Chemistry › Organic Chemistry › Chemical Reaction Mechanisms
  • Physical Sciences › Chemistry › Organic Chemistry › Chemical Synthesis and Reactions
  • Physical Sciences › Chemistry › Organic Chemistry › Oxidative Organic Chemistry Reactions
Keywords
ethyl linoleate, nitrite, nitration, nitroalkenes, nitroalcohols, methyl oleate, radical intermediates, regioisomerism
MeSH terms
Acids, Cell Line, Humans, Hydrogen-Ion Concentration, Isomerism, Linoleic Acids, Gas Chromatography-Mass Spectrometry, Nitric Oxide, Nitrites, Magnetic Resonance Spectroscopy, Oxygen, Structure-Activity Relationship, Keratinocytes

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