| 摘要 |
Mono- and di-esters of glycols are, among other esters, products of the reaction of an olefinic hydrocarbon with at least one hydrogen atom attached to one of the carbon atoms forming part of the double bond, at a partial pressure of at most 10 atmospheres with a solution containing a carboxylic acid, an ionized carboxylate and a palladous salt, and in the presence of a redox system, molecular oxygen, less than 15% of water, and an alkali-metal halide so that the halide: palladous gram-ion ratio is greater than 6: 1, and the halide-carboxylate gram-ion ratio is at least 6: 10. Ethylene, propylene, butene-1, and octene-1, styrene, a -methyl styrene, butene-2, octene-2 and 3: 5-dimethyl hexene-2 are specified and palladous chloride and lithium chloride are the preferred salts and the palladium salt may be made in situ. The redox system may be organic, e.g. p-benzoquinone, duroquinone and 2-ethyl anthraquinone or inorganic, e.g. cupric or ferric salts, or cupric and ferric salts, copper and manganese acetates, ferric and manganese chloride, and copper and cobalt acetate. The carboxylic acid corresponds to the ester required and alkali metal carboxylates are preferred, and acids mentioned are acetic, propionic, n-hexanoic, adipic, benzoic and terephthalic. Examples describe reactions which produce mixed products, ethylene glycol diacetate, ethylidene diacetate and acetaldehyde; ethylene glycol diacetate, ethylidene diacetate, paraldehyde, acetaldehyde and vinyl acetate; ethylene glycol monoacetate, diacetoxyethane, ethylidene diacetate and acetaldehyde; di-acetoxy propane, 1-hydroxy-2-acetoxy propane, 1-acetoxy 2-hydroxy propane, propene esters and acetone; ethylene glycol monopropionate, dipropioxyethane, ethylidene dipropionate, and acetaldehyde; 1-hydroxy 2-acetoxypropane, 1: 3, 1: 2 and 1: 1 diacetoxypropanes, allyl acetate, n-propenyl and isopropenyl acetates and acetone; butene esters and butane diesters. The glycol esters may be hydrolysed to the free glycols. |
