Effects of Chemical Complexity on the Autoxidation Mechanisms of Endocyclic Alkene Ozonolysis Products: From Methylcyclohexenes toward Understanding α-Pinene

Formation of highly oxidized, multifunctional products in the ozonolysis of three endocyclic alkenes, 1-methylcyclohexene, 4-methylcyclohexene, and alpha-pinene, was investigated using a chemical ionization atmospheric pressure interface time-of-flight (CI-APi-TOF) mass spectrometer with a nitrate ion (NO3-) based ionization scheme. The experiments were performed in borosilicate glass flow tube reactors at room temperature (T = 293 +/- 3 K) and at ambient pressure. An ensemble of oxidized monomer and dimer products was detected, with elemental compositions obtained from the high-resolution mass spectra. The monomer product distributions have O/C ratios from 0.8 to 1.6 and can be explained with an autocatalytic oxidation mechanism (=autoxidation) where the oxygen-centered peroxy radical (RO2) intermediates internally rearrange by intramolecular hydrogen shift reactions, enabling more oxygen molecules to attach to the carbon backbone. Dimer distributions are proposed to form by homogeneous peroxy radical recombination and cross combination reactions. These conclusions were supported by experiments where H atoms were exchanged to D atoms by addition of D2O to the carrier gas flow. Methylcyclohexenes were observed to autoxidize in accordance with out previous work on cyclohexene, whereas if alpha-pinene ozonolysis different mechanistic steps are needed to explain the product observed.