| 摘要 |
Organic sulphur compounds are manufactured by causing hydrogen sulphide or gaseous mixtures containing it, or substances yielding hydrogen sulphide under the reaction conditions, to act on compounds of the general formul R.CH = CH2 where R is hydrogen, an alkyl group containing up to five carbon atoms, an alkenyl, cycloaliphatic, aliphaticaromatic or aromatic radicle, an esterified carboxylic group or a cyano group, or RO.CH = CH2, where R is an alkyl, alkenyl, cycloaliphatic, aliphatic-aromatic or aromatic radicle, in the presence of a diluent or solvent, e.g. hydrocarbons or mono- or polyhydric alcohols, and of a basic substance as catalyst. The reaction is effected at ordinary or elevated temperature, e.g. 100--300 DEG C., if desired under superatmospheric pressure, and may be rendered continuous. Suitable catalysts, of which small amounts are sufficient, are the oxides, hydroxides, alcoholates, carbonates, acetates, oxalates, sulphides, sulphydrates and mercaptides of the alkali and alkaline-earth metals, also ammonia and organic bases, e.g. pyridine or piperidine. If initial materials which split off small amounts of basic substances under the reaction conditions are employed, the addition of catalysts is unnecessary. The products may be employed as solvents, or in some cases as intermediates for the preparation of dyestuffs, artificial materials or medicines. On oxidation they yield sulphoxides and sulphones. In examples: (1) ethylene and hydrogen sulphide are heated in a pressure-tight vessel in a solution of sodium in alcohol, producing diethyl sulphide ; propylene similarly yields diisopropyl sulphide; (2) acrylic nitrile and hydrogen sulphide are heated in moist butanol (which partially saponifies the acrylic nitrile with liberation of ammonia, which, in the form of its salt with hydrogen sulphide, acts as catalyst); the product is mainly thiodihydracrylic nitrile, which on saponification yields the free acid, which may be oxidized to its sulphone; (3) styrene and hydrogen sulphide are heated in ethanol in the presence of ammonia to yield a -a <1>-diphenyldiethyl sulphide; (4) p-vinylanisol and hydrogen sulphide are heated in a solution of sodium in ethanol, yielding a -a <1>-di-(p-methoxyphenyl)-diethyl sulphide; (5) p-divinylbenzene is similarly treated; (6) hydrogen sulphide is led into a mixture of styrene and a solution of sodium in butanol, producing diphenyldiethyl sulphide; (7) the reaction of (3) is carried out with excess of hydrogen sulphide. Other starting materials specified are: a -butylene, hexylene, acrylic alkyl esters (e.g. the methyl, ethyl and butyl esters), vinylnaphthalene, and vinyl ethers (e.g. vinyl methyl, ethyl, butyl, isobutyl, octodecyl, phenyl, benzyl, o- and p-chlorobenzyl and naphthyl ethers, vinyl phenyl glycol ether, diglycol mono- and divinyl ether, the mono- and divinyl ethers of di- and triethanolamine, and N-methylvinylhydroxy-ethyl-m-toluidine). |
