Oxidation of p, p'-dimethylbenzophenone (1) with peracid in glacial acetic acid or acetic anhydride gave p-cresol ester (2) of p-toluic acid, which was hydrolyzed to yield p-toluic acid and p-cresol simultaneously. Amount of solvent and hydrogen peroxide, concentration of sulfuric acid catalyst and reaction temperature have been investigated and the optimum reaction conditions were found as follows: To 0.03 mole of (1) in 0.22 mole of glacial acetic acid, was added 4.8ml. of concn sulfuric acid. 0.05 mole of 30% hydrogen peroxide was added dropwise to the above mixture during 30 mins. and farther stirring was continued for 11 hrs. at the same temperature. Hydrolysis of the product (2) with sodium hydroxide solution yielded 94.4% toluic acid and 94.9% p-cresol respectivery.
In the polymerizaton of chlorcyan to cyanulic chloride in chloroform by passing of hydrogen chloride it was found that the product was contaminated with by-product (the other polymerized chlorcyan). Then, after this by-product was separated in a purified form, chemical and physical properties were measured for determinaton of its structure and it was confirmed that this byproduct was a tetramer of chlorcyan, 2, 4-dichloro-6-isocyanodichlorotriazine. This being a new compound, its properties have been investigated.
The reaction of preparing dodecanthiol by catalytic hydrogenation (reductive thiolation reaction) of dodecanoic acid with sulfur, in cyclohexane under pressure has been investigated by using MoS3 catalyst.The reaction was proceeded above 200°c and gave dodecanthiol as the main product with a small amount of di-dodecyl disulfide as a by-product. It was advantageous to heat at about 250°c for this reaction and the amount of sulfur had great effect on the velocity of reaction. In case of 3.0 molar ratio of surfur with the reaction time of 240 min at 250°c, 90% yield of the thiol was obtained. It, was indicated from the result of similar reaction on dodecanoic anhydride and hydrogenation of thiododecanoic acid that the reducive thiolation reaction of dodecanoic acid consisted of the formation of thionic acid from reaction of H2S with dodecanoic acid and its rapid cleavage into the thiol.
Reactivities of xylenes in the liquid phase air oxidation at 135°c with cobalt naphthenate catalyst was in order of o->m-≅p-xylene. The velocity of oxidation with cobalt bromide catalyst without solvent in a stationary chainpropagation period was in the order of o-<in-≅p-xylene. The presence of bromine in cobalt catalyst increased the oxidation velocity in the propagation period (with the exception of o-xylene, no solvent system in which the oxidation was decreased). The ratio of the reaction velocity coefficient, k2/k1, in the twostep oxidation of xylenes toluic acids benzenedicaroxylic acids was not much dependent on the kind of xylenes in case of using cobalt naphthenate catalyst. The ratio k2/k1 became smaller with cobalt bromide catalyst than with cobalt naphthenate catalyst. In the liquid phase oxidation of toluic acids at 150°c to benzenedicarboxylic acids, it was found that the reaction was proceeded smoothly in case of m-or p-toluic acids but not in case of o-toluic acid. This may be attributed mainly to inactivation of catalyst by the o-phthalic acid. This kind of inactivation is found commonly in organic acids having a large dissociation constant and was found in case of oxidation of easily oxidizable xylenes too, though the tendency is smoll.