Patent GB-776757-A (GB)
Title: Method for carrying out the oxidation of olefinically unsaturated compounds
IPC: C07D303/40
Filed: 1954-12-02
Abstract: A method of oxidizing olefinically unsaturated compounds comprises contacting a liquid mixture of hydrogen peroxide and the compound to be oxidized with a cation-exchange resin in its hydrogen form. Preferably also a carboxylic acid is present in the mixture.  The olefinic compounds undergo epoxidation and/or hydroxylation.  Among compounds to which the process is applicable are (a) olefinic hydrocarbons such as amylenes, hexylenes, tetradecenes and octadecenes; (b) olefinic fatty acids such as oleic, ricinoleic, undecylenic and erucic acids; (c) nitrites, amides and esters of such acids including their esters with mono-, di- and trihydric alcohols, such as methyl oleate, methyl ricinoleate, diethylene glycol dioleate, glycerol mono-oleate, glycerol trioleate, soybean oil, castor oil, olive oil, tall oil, peanut oil and cottonseed oil; (d) olefinic alcohols such as decenols, tetradecenols, hexadecenols and oleyl alcohol; and (e) derivatives of such alcohols, e.g. oleyl acetate and oleyl oleate. Suitable resins are those having sulphonic, carboxylic and phosphonic acid groups, particularly sulphonated polymers of polyvinyl aryl compounds and sulphonated copolymers of poly- and mono-vinyl aryl compounds such as those described in Specification 571,029, [Group IV].  The nature of the oxidation is partly dependent on the resin.  For example sulphonated copolymers of styrene with more than about 6 per cent polyvinyl benzene are primarily epoxidation catalysts.  Resins cross linked to a less extent yield hydroxylated compounds as the major product.  Higher temperatures also favour hydroxylation.  With olefins such as amylenes, octene-2 and decene-1, peroxides are also found in the products.  Suitable reaction temperatures are 25 DEG  to 100 DEG  C. The hydrogen peroxide is generally used in amount 0.85 to 1.1 mols. for each oxidizable olefinic linkage.  In Example (1) a sulphonated copolymer of styrene with 8 per cent divinyl benzene and containing about one -SO3H group per benzene ring is stirred with glacial acetic acid and then with methyl oleate, hydrogen peroxide of 50 per cent strength then being added.  After keeping such mixtures at 60 DEG and 82 DEG  C. respectively, the amount of epoxystearate is determined.  In Example (2) hydrogen peroxide of 70 per cent strength and a resin which has not been acid-pretreated are used.  Examples (3) to (8) describe generally similar processes to that of Example (1).  In Example (12), butylacetoxyricinoleate is similarly epoxidized.  In Example (10), hydroxylation is the main reaction when methyl oleate is treated at 60 DEG  C. with 10 per cent excess hydrogen peroxide in the presence of a sulphonated copolymer of styrene with 4 per cent divinyl benzene and of a half molecular proportion of acetic acid. A process similar to Example (1) but performed continuously is described in Examples (11) and (12). Alkali refined soybean oil is also treated in this way.  Other compounds yielding epoxides as the major product are soybean oil acids.  Specification 776,758 also is referred to.