Reactions of Free Radicals with Aldehydes. II. The Reactions of Methyl Radicals with Propionaldehyde

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Abstract
The reaction of radicals derived from the thermal decomposition of di‐t‐butyl peroxide with propionaldehyde in the gas phase has been studied. The gaseous products were carbon monoxide, methane, ethane, propane, butane, and ethylene. A mechanism to account for the induced chain decomposition and product formation involving H atom abstraction by radicals and radical decomposition, combination and disproportionation is given. The energetics of H atom abstraction by methyl and ethyl were similar and lead to an activation energy of about 7.5 kcal/mole and a steric factor of about 10—3. These values are in good agreement with those found for H atom abstraction from acetaldehyde. Evidence is presented that H atom abstraction takes place with the carbonyl attached H for both acetaldehyde and propionaldehyde.

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