| Summary: | β-hydroxynitrates (HN) are a major class of products formed during OH and NO<sub>3</sub> initiated oxidation of terpenes. Their production contributes significantly to secondary organic aerosol (SOA) formation and NO<sub>x</sub> sequestration. However, studying the condensed phase reactions of this important class of molecules has been hindered by the lack of commercially available authentic standards. The goal of this work was to examine the influence of water concentration and solvent identity on product yields of a tertiary HN derived from 3-carene prepared in house. To assess the role of water on conversion chemistry, bulk-phase reactions were conducted in DMSO-<i>d</i><sub>6</sub>, a non-nucleophilic solvent, with a gradient of water concentrations, and analyzed with <sup>1</sup>H NMR. Product identifications were made by comparison with authentic standards prepared in house. Four major products were identified, including an unexpected diol produced from carbocation rearrangement, diol diastereomers, and <i>trans</i>-3-carene oxide, with varying yields as a function of water concentration. Product yields were also measured in two protic, nucleophilic solvents, MeOD-<i>d</i><sub>4</sub> and EtOD-<i>d</i><sub>6</sub>. Finally, reactions with added chloride formed alkyl chloride products in yields approaching 30%. These results are among the first to highlight the complexities of nucleophilic reactions of hydroxynitrates in bulk, mixed aqueous/organic media and to identify new, unexpected products.
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