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l-Acetyl-l-methylcyclohexane: bp 68-70°(7 mm) [lit.26 bp 80-8.5°(16 mm)]; 13.8 g (66% based upon 150 mmol of olefin) isolated; ir 1700 cm-1; nmr r 8.0 and 9.0 [sharp s, H3CCOCCH8]; vpc (130°a nd 150°) 18 showed a single compound. The 2,4-DNP had a melting point of 131-132°( lit.26 mp 132°) and the semicarbazone melted at 183-185°(lit.26 mp 186-187°).3,3-Dimethyl[3.2.1]bicyclooctanone-2 (7): bp 30-40°(0.3 mm); ir 1710, 3050, and 1610 cm-1 (the latter indicated olefinic contamination); vpc (200°)18 indicated three compounds present. The distillate, dissolved in petroleum ether (bp 30-60°), was placed upon a column containing 30 g of neutral alumina. Elution with petroleum ether yielded an unidentified olefin, ir 3050 and 1610 cm-1, no carbonyl or hydroxyl absorptions present.Elution with 50% (v/v) benzene-petroleum ether yielded 2 g of 7 (25) O.

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Photochemically initiated HO radical oxidations of 0.2-3.0 M isopropyl methylphosphonic acid (IPA) and methylphosphonic acid (MPA) (as sodium salts) have been carried out at 25 °C in water solution using 0.01-3.0 M hydrogen peroxide and oxygen to effect complete oxidations of both compounds to phosphoric acid, carbon dioxide, and water. No intermediate oxidation products were found from oxidation of MPA, whereas acetone, acetic acid, and methylphosphonic acid were found in the oxidation of IPA. From the relative proportions of these intermediates, the relative and absolute rate constants for reactions of HO radical with IPA and MPA were calculated. The experiments suggest that rapid and complete oxidation of alkyl phosphorus compounds to simple products may be possible but careful control of reaction variables is necessary to achieve efficient use of H2O2.

Aqueous emulsions of a variety of hydrocarbons under cobalt-60 irradiation have been allowed to react with molecular oxygen at pressures of 1-4 atm at 50°. Unlike the effect observed in polymerization, emulsification of styrene had no significant effect on the oxidation rate or products as compared to that observed in hydrocarbon solution. With emulsions of styrene and -methylstyrene, dependency on the rate of initiation and temperature is consistent with the bulk mechanism, and the product distribution qualitatively parallels bulk oxidations. Other hydrocarbons investigated include cyclohexene, cyclopentene, tetramethylethylene, tetralin, and cumene.