Atmospheric chemistry of isopropyl formate and tert-butyl formate

This work describes experiments to define the oxidation mechanisms of isopropyl formate, HC(O)OCH(CH₃)₂, and tert-butyl formate, HC(O)OC(CH₃)₃. Product distributions are reported from both Cl- and OH-initiated oxidation, and reaction mechanisms are proposed to account for the observed products.

The proposed mechanisms include examples of the α-ester rearrangement reaction, novel isomerization pathways, and chemically activated intermediates. The atmospheric oxidation of isopropyl formate by OH radicals gives the following products (molar yields): acetic formic anhydride (43%), acetone (43%), and HCOOH (15–20%). The OH radical initiated oxidation of tert-butyl formate gives acetone, formaldehyde, and CO₂ as major products.