Products obtained from vapor-phase oxidation of 1 -hexene and n-hexane differ considerably. Hexane is attacked mainly at the second carbon in the chain and gives a mixture of cyclic ethers (largely 2,5-dimethyltetrahydrofuran and 2,4-epoxyhexane), carbonyls (acetaldehyde and formaldehyde), and olefins (C2-Ce). Hexene apparently is attacked all along the chain and gives 1,2-epoxyhexane, C1-C3 carbonyls including acrolein, and hexenals as major products. Minor products from hexene are 2,5-dimethyltetrahydrofuran, 2,4-, 1,3-, and 3,4-epoxyhexanes (all via the abstraction of a hydrogen atom by the intermediate free radical), 2-methyl-5-ethyl-tetrahydrofuran (via the addition of a methyl group to the intermediate free radical), and 2-oxabicyclo [2,2,1 ] heptane (resulting from attack on the terminal methyl group). Hexene, unlike C2-C4 olefins, does not give Ci and Cs aldehydes in equivalent amounts. This work was undertaken to determine exactly how 1hexene compares with lower molecular-weight (C2-C4) olefins and n-hexane on vapor-phase oxidation. All experiments were carried out in the presence of a "rain" of fine particulate inert solids to prevent inflammation and achieve temperature control. Earlier work in this laboratory (Jones et al., 1969a,b) demonstrated that: The major products from C2-C4 olefins consisted of the olefin oxides plus the carbonyl or carbonyls formed by cleavage of the double bond; the inert solids eitherTable I. Distillation of Hydrocarbon-Rich Layer Product from Oxidation of 1-Hexene" Charge: 9232 grams Fractions Column efficiency Fraction Bp range, Ref. index, collected theor. plates6 wt, g °C n™D range
