| 摘要 |
1,154,038. Oxidation. IMPERIAL CHEMICAL INDUSTRIES Ltd. 9 Dec., 1966 [24 Dec., 1965; 5 May, 1966; 23 June, 1966], Nos. 54840/65; 19853/66 and 28201/66. Heading C2C. Unsaturated organic compounds are oxidized by contacting with a nucleophilic compound HA where A is a nucleophilic element or group, in the presence of a salt or co-ordination compound of palladium and an oxime. The unsaturated compound may be an olefine preferably α-olefine, e.g. ethylene cracked wax olefines, aryl substituted α-olefine, n-hexene-1, n-octene-1, 3 : 5 : 5-trimethyl hexene-1, propylene, n-butene-1 or isobutenes, a non-terminal olefine, e.g. n-octene-2, butadiene and piperylene, allyl acetate or allyl alcohol, and the products are ethers, acetals, aldehydes, ketones acids or saturated or unsaturated esters. In a modification the unsaturated compound is contacted with molecular oxygen in a solution comprising a palladous salt, a carboxylic acid, carboxylate ions, a redox system, up to 20 : 1 by weight of water, and halide ions, at the most up to 0À05 gm ions per litre, to which solution is added a nitrate, nitrite, nitrosyl, nitro- or nitrosocompound. Many examples of these compounds are listed. Examples of the process describe the oxidation of propylene to allyl acetate, acetone and isopropenyl acetate; of ethylene to vinyl acetate and acetaldehyde; of allyl alcohol to acrolein and allyl acetate; of allyl acetate to allylidene diacetate, acrolein, cis-1:3 diacetoxypropene and trans 1 : 3 diacetoxy propene; and of octene-1 to octenyl acetate. |
