Hydroxylation of Monounsaturated Fatty Materials with Hydrogen Peroxide

395

141

It was discovered that olefinic double bonds are readily oxidized in an aqueous solution of periodate which contains only catalytic amounts of permanganate. The data suggest that in the effective pH range of 7 to 10 the permanganate is not reduced at once beyond the manganate state and that it is regenerated from this state by periodate action. Evidence was obtained that the main course of the oxidation of an olefin of type —CH=CH— involves first permanganate oxidation to hydroxyketones which are then rapidly cleaved by periodate to products which may subsequently be oxidized by the permanganate.

“…83-85°C.) prepared by the method of Swern et al (14). The high and low melting forms could be readily iilterconverted by crystallization and both gave a P-bromophenacyl ester of m.p.…”

Section: Experimental Imethodsmentioning

confidence: 99%

Periodate–permanganate Oxidations: I. Oxidation of Olefins

Lemieux¹,

Rudloff²

1955

395

141

“…T h e hydroxylation of the 3-acetoxycyclol~exene was carried out by three methocls, the first of which emplojied tertiary-butyl peroxide with selenium dioxide a s a catalyst (33); the second, hydrogen peroxide in sulphuric and glacial acetic acids (25), and the third, hydrogen peroxide in formic acid (35). I n each instance acyl groups were removed from the distilled but uncrystallized product by saponification, and the resulting mixture of crude triols was separated by fractional crystallization of the tribenzoates.…”

Section: Introductionmentioning

confidence: 99%

AN IMPROVED SYNTHESIS OF CIS-CIS-TRANS-CYCLOHEXANE-1,2,3-TRIOL

Gogek¹,

Moir²,

McRae³

et al. 1951

“…(20). The amount oi hydrogen peroxide employed was calculated on the basis of 1.2 moles per mole of unsaturation.…”

Section: Peracetic Acid Oxidationmentioning

confidence: 99%

Hydroxylation and Epoxidation of Rapeseed Oil Derivatives With Subsequent Pyrolysis and Ammonolysis

Mageli¹,

Patteson²,

Spencer³

1953

A method was developed to follow the hydroxylation of rapeseed oil and erucic acid derivatives with peracetic acid. Peracetic acid prepared insitu was found to be equally as effective as the preformed acid in hydroxylation of methyl erucate. Among the compounds synthesized were ethyl 13,14-dihydroxybehenate, methyl 13,14-oxidoerucate, ethyl 13,14-diacetoxybehenate, and methyl 13,14(14,13)-hydroxyacetoxybehenate which were subsequently pyrolyzed at approximately 300 °C with p-toluenesulphonic acid as catalyst. The first compound yielded mainly the corresponding ketone with a small amount of the oxido derivative, the chief product of the second compound was also the ketone with some unsaturated material, the third compound yielded 43% of the diene, while the last one yielded 60%. Ammonolysis of the oxido compound or the bromohydrin to yield the corresponding aminohydroxy derivative under pressure with liquid ammonia and ammonium bromide was unsuccessful. A new compound oxidoerucamide, m.p.101.5°, was synthesized.