ESR study of electron reactions with esters and triglycerides
Reactions which occurred after electron attachment at 77K to a number of small carboxylic acid esters and triglycerides in an aqueous glass are reported. Most ester anions are found to decay on warming to form alkyl radicals by ..beta.. scission: RC(O/sup -/)OR' ..-->.. RCO/sub 2//sup -/ + R'.. The alkyl radical (R'.) produced by annealing is found to abstract hydrogen from the parent ester at an ..cap alpha..-carbon site, R'.+ R''CH/sub 2/CO/sub 2/R' ..-->.. R''CHCO/sub 2/R', or in the case of ethyl formate from the formate hydrogen, CH/sub 3/CH/sub 2/.+ HCO/sub 2/C/sub 2/H/sub 5/ ..-->.. C/sub 2/H/sub 6/ +.CO/sub 2/C/sub 2/H/sub 5/. Results found for the methyl formate anion suggest hydrogen abstraction by the anion itself may compete with alkyl radical formation. The anion of the triglyceride triacetin is found to undergo an analogous mechanism to the ester anions producing the propane diol diester radical, .CH/sub 2/CH(Ac)CH/sub 2/(Ac), Ac = acetate. This species subsequently abstracts hydrogen from the parent compound to produce the ..cap alpha..-carbon radical, .CH/sub 2/CO/sub 2/R. Results found after annealing the tripropionin radical anion give evidence for abstraction from the ..cap alpha.. carbon in the propionate side groups producing CH/sub 3/CHCO/sub 2/R. Studies of a ..gamma..-irradiated ester (ethyl myristate) and two triglycerides (tripalmitin and tristearin) yield results which suggest that the mechanism of ester anion decay found in aqueous glasses applies to ..gamma..-irradiated neat long-chain esters and triglycerides. Results found in this work are compared to the results of product analysis.
- Research Organization:
- Oakland Univ., Rochester, MI
- OSTI ID:
- 6507628
- Journal Information:
- J. Phys. Chem.; (United States), Vol. 85:7
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY
CARBOXYLIC ACID ESTERS
PHOTOLYSIS
RADIOLYSIS
TRIGLYCERIDES
AQUEOUS SOLUTIONS
ELECTRON ATTACHMENT
ELECTRON SPIN RESONANCE
GAMMA RADIATION
GLASS
LOW TEMPERATURE
RADICALS
CHEMICAL RADIATION EFFECTS
CHEMICAL REACTIONS
CHEMISTRY
DECOMPOSITION
DISPERSIONS
ELECTROMAGNETIC RADIATION
ESTERS
IONIZING RADIATIONS
LIPIDS
MAGNETIC RESONANCE
MIXTURES
ORGANIC COMPOUNDS
PHOTOCHEMICAL REACTIONS
RADIATION CHEMISTRY
RADIATION EFFECTS
RADIATIONS
RESONANCE
SOLUTIONS
400500* - Photochemistry
400600 - Radiation Chemistry