DE564215C - Process for the preparation of thio derivatives of phenols - Google Patents

Description

Process for the preparation of thio derivatives of phenols According to the process of patent 562 502 , non-coloring thio derivatives of phenols are produced by heating phenol, its homologues or substitution products, such as halophenols or phenol carboxylic acids, with alkalis or alkaline sulfur or alkaline earths and sulfur in the presence of metal compounds or: Metals of the ammonium sulphide and hydrogen sulphide group.

In the further development of this process it was found that similar thio derivatives of the phenols can be obtained if, instead of the phenols mentioned in the main patent, their derivatives of the general formula are used in which R: denotes methylene or sulfur groups, and their substitution products are used.

Such compounds are e.g. B. the effect of formaldehyde Dioxydiphenylmethane that can be represented on phenol or that by the action of chlorosulfur available Dioxydiphenyidisulfid as well as their derivatives, which alkyl, halogen, Contain sulfo or carboxyl groups.

To carry out the method z. B. the phenols first by means Formaldehyde condenses and the resulting condensation products with sulfur, alkali and the metal salts listed in the main patent in the absence or in the presence heated by reflux of water with thorough stirring, with vigorous evolution of hydrogen sulfide entry; The end of the condensation can be recognized by the decrease in the evolution of hydrogen sulfide.

One can also use phenols first with chlorosulfur in the presence or in Treat the absence of a diluent and the sulfur-containing ones obtained Condensation products with alkali in the presence of the metal salts mentioned in the main patent merge. Instead of chlorosulfur treatment one can use a mixture consisting from phenol and sulfur, at a higher temperature in the presence or absence of Treat catalysts with chlorine and the sulfur-containing condensation products obtained further processing. The new compounds are obtained from the melt in their form Alkali salts or free thioacids, the latter being slightly in alkaline solutions are soluble. The new compounds have caustic, tanning properties and reserving properties.

Example i Zoo parts of technical xylenol mixture are made with 2 parts 35% hydrochloric acid and slowly with 80 parts 35% formaldehyde at 35 to 0 ° added with good stirring, then stirred for about 6 hours, i hour to 7o to 8o ' heated and allowed to settle. A light brown paste is obtained, which, from the water separated, with 60 parts of sodium hydroxide, 100 parts of sulfur and 60 parts of tin chloride crystallized and mixed for 24 hours with vigorous stirring to 10 to 10 ° is heated. The melt obtained is dissolved in just enough sodium hydroxide solution and dried up. A green olive powder is obtained, which instead of tannin can be used to fix basic dyes.

Example e 180 parts of phenol are melted and mixed with 20 parts of water, 2 parts hydrochloric acid 35% and 50% formaldehyde with thorough stirring offset at 35 to 40 '. A light yellow-brown "condensation product is obtained which, separated from the water, 60 parts of sodium hydroxide were first added with thorough stirring will. 100 parts of sulfur and q.o parts of tin hydroxide are then added to the solution obtained and heated to 115 to 11.7 'for 20 hours. A thick one is obtained Paste, which, dissolved with sodium hydroxide solution and dried, gives a gray-green powder. This has acidic and glue-precipitating properties. Example 3 100 parts of phenol 100 parts of chlorosulphur are slowly added at 70 to 0 ° and allowed to cool calmly. The mass obtained is carefully mixed with 2o parts of water, 80 parts of sodium hydroxide and q.o parts of tin chloride crystallized out were added. the obtained mixture is now for 24 hours on the reflux condenser to 137 to 140 ' heated. A thick paste is obtained which, when dried, turns into a greenish-gray powder supplies. This is readily soluble in water and is made from dilute solutions with acetic acid not failed. It has the property that treated wool of direct and acid dyes is no longer stained.

Example q.

A mixture consisting of 180 parts of phenol and 60 parts of finely powdered sulfur is heated to 130 ' and treated with dry chlorine gas, the temperature rising to 150 to 16o'. After 60 g of chlorine have been taken up, a further 60 parts of sulfur are added to the melt and the chlorination is continued until about 140 g of chlorine have been consumed. The melt obtained is then cooled, 60 parts of sodium hydroxide and qo parts of tin chloride crystallized and heated for 24 hours to a temperature of 130 to iq.o ° with thorough stirring. After the reaction has ended, the melt is dried in vacuo. A gray powder is obtained which has the property of protecting wool and silk against the absorption of dyes.

Example 5 A mixture consisting of 70 parts of pp'-dioxydiphenyldimethylmethane, 20 parts of sodium hydroxide, 30 parts of sulfur and 15 parts of tin chloride crystallized and 100 parts of water are refluxed with thorough stirring for 40 hours heated to 1o6 °. The brown paste obtained in this way is dissolved in water, the insoluble parts were filtered off and the solution was evaporated in vacuo. Man receives a water-soluble gray-green powder, which is acidic and glue-precipitating Possesses properties.

Claims (1)

PATENT CLAIMS: Modification of the process protected by patent 562 502 for the preparation of thio derivatives of phenols, characterized in that instead of the phenols mentioned in the main patent, their derivatives of the general formula are used where R denotes methylene or sulfur groups, or their homologues and substitution products are used.