With the increasing availability in recent years of a purer and more stable hydrogen peroxide, new means have been sought for its utilization. The reaction of an ethylenic compound with hydrogen peroxide and tungstic acid catalyst in alcohol solution led directly to glycol monoalkyl ether; the same catalyst, after partial neutralization, was found to be effective for the production of epoxy compounds from allylic aleohols and from &,@-unsaturated carboxylic acids. Selenium dioxide catalyzed the oxidation of acrolein to acrylic acid as well as the oxidative ring contraction of cycloalkanones to to cycloalkanecarboxylic acids. Acrolein was smoothly oxidized to glyceraldehyde by means of hydrogen peroxide with osmium tetroxide as catalyst. By carefully controlling the pH of the solution, it was found possible to carry out a base-catalyzed epoxidation of acrolein to give glycidaldehyde, a new epoxy aldehyde; other (y$-unsaturated aldehydes reacted similarly. Mesityl oxide peroxide, obtained in only 3% yield as by-product from the alkaline epoxidation of mesityl oxide at high pH, could be secured in 20% yield by carrying out the epoxidation at pH 7.5-8. A cyclic cy-diketone, 3,5,5-trimethyl-1,2-eyclohexanedione, underwent normal cleavage by hydrogen peroxide to the substituted adipic acid at high pH, while at pH 9 a completely different product, 3,3-dimethyl-5-ketohexanoic acid, was obtained. The substitution of sodium carbonate for sodium hydroxide in the preparation of monoperphthalic acid from phthalic anhydride and hydrogen peroxide led to a simplified procedure and a higher yield. Treatment of mesityl oxide with peroxyacetie acid gave the epoxy ester, 3'3-dimethyl-2- acetoxyoxirane. Finally, the reaction of the hexanoic acid radical (prepared from hydrogen peroxide, cyclohexanone and ferrous ion) with dimethyl maleate and other conjugated unsaturated materials led to a variety of monobasic and polybasic acids.
Le peroxyde d'hydrogène étant devenu récemment de plus en plus disponible sous une formé pure et stable, on a dû rechercher des débouchés nouveaux pour son utilisation. La réaction d'un composé éthylénique avec du péroxyde d'hydrogène et de l'acide tungstique comme catalyseur, dans une solution d'alcool, produit directement de l'oxyde de glycol monoalkylé; on a découvert que ce même catalyseur, après avoir subi un neutralisation partielle, est effectif pour la production des eomposéa époxy, provenant des alcools allyliques et des acides carboxyliques non-saturés en positions a- et p-. On se sert du dioxyde de sélénium comme catalyseur pour former de l'acide acrylique par l'oxydation d'acroléine, aussi bien que pour former des acides carboxyliques cyelaniques par contraction oxydative des noyaux de cycloalcanones. L'acroléine est facilement oxydée à l'aldéh
