| 摘要 |
Organic compounds containing at least one carbon-to-hydrogen bond and at least one carbon-to-carbon bond are oxidized by heating with (a) sulphuric acid or a water-soluble sulphate, (b) sulphur, and (c) water to above 400 DEG F. and below the critical temperature of water, under pressure sufficient to maintain a part of the water in liquid phase, the mol. ratio of sulphuric acid or sulphate to the organic compound being in excess of 1:1 and the mol. ratio of the organic compound to the sulphur being at least 2:1. The compounds may be hydrocarbons, aldehydes, ketones, esters, ethers, organic acids, amines, amides, or heterocyclic compounds, or partially oxidized hydrocarbons such as alkyl benzene carboxylic acids. The sulphate may be ammonium, alkali metal, alkaline earth metal, or alkali or alkaline earth metal hydrogen sulphate. The temperature may be 400-700 DEG F. and preferably 450-650 DEG F. Pressures may range from 500-5000 p.s.i.g. and commonly 1500-3500 p.s.i.g. The reaction may be batchwise or continuous and a conventional assemblage of apparatus as shown. An example of the oxidation of xylene with ammonium sulphate, sulphur and water is given, the product being a mixture of isophthalic and terephthalic acids and the amides thereof. Reference is also made to the oxidation of acetophenone, benzyl alcohol, n-butane, n-butanol, cumene, cyclohexanone, m-cymene, 2,3-dimethyl butane, diisobutylene, dodecene, ethylene, hemimellitene, n-hexane, mesitylene, sucrose, tetrahydrofurfuryl alcohol, toluene, ammonium toluate, and propylene, giving, besides carbon dioxide, benzoic acid, acetic acid, C2-C4-aliphatic acids, phenol, isophthalic acid, acid, pivalic acid, phthalic acid, trimesic acid, glutaric acid terephthalic acid, propionic and acetic acids. |
