The Reaction of Carboxylic Acids and Hydrocarbons in a Silent Electric Discharge. II. The Reactions of Ethylene with Methyl Acetate and with Acetic Anhydride

Abstract

Abstract The present study was undertaken in order to ascertain the difference, if any, in the chemical behavior of methyl acetate and acetic anhydride submitted to a silent discharge between that in the presence and that in the absence of ethylene. (1) In the reaction of methyl acetate without ethylene, the main products were methanol, diacetyl, liquid hydrocarbons, formaldehyde, methane, carbon dioxide, carbon monoxide, and hydrogen. Although the methanol yield was almost the same, regardless of the presence or absence of ethylene, the yields of the hydrocarbons, all the carbonyl compounds, and of n-butyl acetate increased in the presence of ethylene. The great quantity of methanol produced might indicate that C–OCH3-bond breaking in the methyl acetate occurs preferably upon the discharge. (2) With acetic anhydride, on the other hand, acetaldehyde, acetone, ethyl acetate, ethyl methyl ketone, diacetyl, hydrocarbons, carbon monoxide, carbon dioxide, and hydrogen were obtained as the main products. The yields of acetone and diacetyl decreased remarkably in the presence of ethylene, while the yields of hydrocarbons, ethyl methyl ketone, n-butyl methyl ketone, and of n-butyl acetate increased. The CH3COO· and CH3CO· radicals are thought to be the main intermediates in this reaction. The formation of n-butyl acetate and of n-butyl methyl ketone in the presence of ethylene can be explained on the basis of the telomerization of ethylene initiated by these radicals.