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The reaction of low levels of nitrogen dioxide with methyl linoleate in the presence and absence of oxygen

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Lipids

Abstract

The reaction of methyl linoleate with low levels of nitrogen dioxide in a carrier gas, such as helium or air, at nitrogen dioxide concentrations ranging from 2 to 228 ppm was studied and the products formed were monitored. In both aerobic and anaerobic conditions, low concentrations of nitrogen dioxide reacted with methyl linoleate predominately to form allylic products. When a 1∶1 mixture of methyl palmitate/methyl linoleate was layered over an aqueous buffer and a nitrogen dioxide stream was passed from underneath, so that the stream passed through the aqueous layer before contacting the organic layer, allylic products again predominated. In the absence of air, the allylic products consisted of allylic nitro and nitrite derivatives of linoleate, whereas in the presence of air, allylic hydroperoxides were the principal products. The findings suggest that fatty acids with doubly allylic hydrogen atoms react preferentially by a hydrogen atom abstraction reaction rather than by the addition of nitrogen dioxide to a double bond.

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Abbreviations

AN:

allylic nitro or nitrite compounds

c :

cis double bond

DTPA:

diethylenetriaminepentaacetic acid

GC:

gas chromatography

GC/MS:

gas chromatography/mass spectrometry

HPLC:

high-performance liquid chromatography

IR:

infrared

NCI:

negative chemical ionization

NMR:

nuclear magnetic resonance

t :

trans double bond

UV:

ultraviolet

vinyl nitro:

mixture of methyl 9-nitro-9,12-octadecadienoate and methyl 13-nitro-9,12-octadecadienoate

vinyl nitrate:

mixture of methyl 9-nitrato-9,12-octadecadienoate, methyl 10-nitrato-9,12-octadecadienoate, methyl 12-nitrato-9,12-octadecadienoate, and methyl 13-nitrato-9,12-octadecadienoate

c,t-18∶2:

mixture of methylcis-9,trans 12-octadecadienoate and methyltrans-9,cis-12-octadecadienoate

9c, 11t-13AN:

mixture of methyl 13-nitrito-cis-9,trans-11-octadecadienoate and methyl 13-nitro-cis-9,trans-11-octadecadienoate

9c, 11t-13HP:

methyl 13-hydroperoxy-cis-9,trans-11-octadecadienoate

9c, 11t-13AN:

mixture of methyl 13-nitrito-trans-9,trans-11-octadecadienoate and methyl 13-nitro-trans-9,trans-11-octadecadienoate

9t,11t-13HP:

methyl 13-hydroperoxy-trans-9,trans-11-octadecadienoate

10t, 12c-9AN:

mixture of methyl 9-nitrito-trans-10,cis-12-octadecadienoate and methyl 9-nitro-trans-10,cis-12-octadecadienoate

10t, 12c-9HP:

methyl 9-hydroperoxy-trans-10,cis-12-octadecadienoate

10t, 12t-9AN:

mixture of methyl 9-nitrito-trans-10,trans-12-octadecadienoate and methyl 9-nitro-trans-10,trans-12-octadecadienoate

10t, 12t-9HP:

methyl-9-hydroperoxy-trans-10,trans-12-octadecadienoate

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Authors and Affiliations

  1. Chemistry Department, Louisiana State University, 70803, Baton Rouge, Louisiana

    Aris A. Gallon & William A. Pryor

  2. Biodynamics Institute, Louisiana State University, 711 Choppin Hall, 70803-1804, Baton Rouge, LA

    Aris A. Gallon & William A. Pryor

Authors
  1. Aris A. Gallon
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  2. William A. Pryor
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Gallon, A.A., Pryor, W.A. The reaction of low levels of nitrogen dioxide with methyl linoleate in the presence and absence of oxygen. Lipids 29, 171–176 (1994). https://doi.org/10.1007/BF02536725

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  • DOI: https://doi.org/10.1007/BF02536725

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