DE719059C - Process for the production of sulfur-containing organic compounds - Google Patents

Description

Process for the production of sulfur-containing organic compounds It would be found - that one technically versatile organic sulfur connections are obtained when you use the Effect from. Halogen and sulfur dioxide, possibly under the influence of short-wave towards light, - on aliphatic hydrocarbons - stoffee or halogenated hydrocarbons with at least one not associated with halogen the carbon atom available, acidic sfoff, sulfur and halogen containing zevgmIsse yes presence of ammonia or Reacts amines with phenols. Included. arise connections or mix, ip. which probably sulfonic acid aiyleer 'are present. Mali works for example show that mari in a, mixture of one Phenol and the simultaneous effect of halogen and sulfur dioxide aliphatic hydrocarbons _ or - halo, stoics arising from hydrocarbons gaseous ammonia passes through to saturation. Anhydrous ammonia can also be introduced into the phenol and the sulfohalide-like substances can be introduced at the same time. Besides phenol itself z. B. also the oxytoluenes, oxyxylenes, halophenols and oxynaphthalenes mentioned.

One can also use a mixture of a phenol and the sulfohalide-type Treat the substance with a stream of ammonia, e.g. B. by putting the mixture in a. from Tower cooled on the outside, empty or filled with random packings from top to bottom leads to a stream of ammonia. To mäg-. to obtain the most intact end products, is it appropriate to. not to let the temperature rise too much, so they .z. B. hung by cow to hold about 3o to 40 °. Instead of ammonia you can also, a main, e.g. Methylamine, dimethylamine or ethylamine. use. The solid ammonium halide formed can be extracted from the reaction mixture in a simple manner Way, e.g. B. by Filtriexem. or spinning off. Included. can the This improves the filterability of the precipitating solid ammonium halide be that the mixture to be filtered with an insufficient to dissolve the salt Amount of water, for example 0.5 to 5%, added. This is how you get one Grain coarsening. The water can be used before the implementation as well as the Add reaction mixture containing ammonium salt.

But you can also use the reaction mixture with water or an electrolyte solution, e.g. B. dilute calcium chloride solution, absorb; the ammonium halide dissolves in the process on. The aqueous layer is then separated off and the reaction device is operated on.

The products obtained by the new process are more or few viscous substances. You can z. B. as a plasticizer for polymers or use cellulose derivatives.

Following the procedure of an older proposal, those at, the action from halogen and sulfur dioxide to saturated aliphatic hydrocarbons, Sulfohalide-like products containing oxygen, halogen and sulfur reacted with alcohols or phenols. Often used as an acid-binding agent applied alkali not only favors the desired esterification, but can also directly cause saponification of the sulfohalide-like substances. The resulting saponification products are very effective on the surface, so that at There is a risk of emulsion blooming when processing the water. This danger will avoided according to the present invention, since Ahnmtiniak and amines on the sulfohalide-like- Substances - do not have a saponifying effect. In addition, only the desired esters are formed, without the possible formation of sulfamides: occurring.

The n parts given in the examples below are parts by weight. .: - Example i In. An iron vessel equipped with a stirrer is mixed with 2,000 parts of a product which "contains 100% sulfur and 12 hvdrolyzable chlorine and which by treating an oil obtained by hydrogenation of carbon dioxide" at ordinary pressure between 21b and "- 370 ° boiling oil the density 0.768 (10 °) was prepared with sulfur dioxide according to light, with 83o parts of a phenol mixture consisting of 40 parts of phenol, 40 parts of cresol and 20 parts of xylenol Ammonia a.

The reaction mixture is then stirred with 830 parts of water. Included the ammonium chloride dissolves completely. The saline solution is drawn off and that lag behind; bende oil with o, 2 percent calcium chloride solution and then mix Washed with water and removed from the unchanged phenol mixture and volatile accompanying substances freed by treatment with steam.

One receives a. odorless, yellowish oil that dissolves with polyvinyl chloride can be processed into permanent masses that gelatinize in the heat.

Example z In a tower made of clay you leave in fine distribution a mixture of 100 parts of a halogen and sulfur containing, based on the example i specified product and 29 parts of technical phenolic oil trickle from top to bottom against a circulating ammonia stream. The ammonia used is continuously replaced by fresh gas.

At the lower end of the tower there is a constant stream of fine-grain ammonium chloride mixed reaction product withdrawn as an easily flowing mixture. It will washed with o, 2 percent calcium chloride solution and then with pure water.

Treatment with steam under reduced pressure gives a yellowish oil that can be used, for example, as a plasticizer for polyvinyl chloride.

A similar end product is obtained by adding 100 parts of a product which has been obtained by treating one by the hydrogenation of carbon monoxide. Ordinary pressure produced, unsaturated fractions containing, between 18o and 34o ° boiling oil of .der density 0.763 - (2o °) with hydrogen and reaction. the mixture of saturated hydrocarbons with sulfur dioxide and chlorine thus obtained. Reacts in the manner described with 36 parts of technical phenolic oil.

Befs piel 3-In a mixture of 100 parts of a halogen and sulfur. contain # aden, manufactured in the manner indicated in example i And 32 parts of a tecbniwhen. Phenol mixture ,. the 4o parts phenol ,. 4o parts Contains cresol and 20 parts of xylene, one leaves 24.7 parts piperidine flow in. After the reaction, the precipitated salt is filtered off and washed the liquid several times with twice the volume of 8% methanol; afterward volatile constituents are removed from the product using steam. You get a brownish yellow, thick oil; that z. B. as a plasticizer for polyvinyl chloride suitable.

A similar oil is obtained by taking i oo parts of a product, made by treating a mixture of aliphatic chlorinated hydrocarbons ( by introducing chlorine under irradiation with short-wave light into a hydrocarbon mixture from the boiling range 20o to 36o °, produced by catalytic hydrogenation of carbon monoxide at ordinary pressure) with sulfur dioxide and chlorine under irradiation has been obtained with short-wave light, with 23 parts of said phenol mixture with the addition of 2q. Share: Piperidine converts. Example 4 In, an externally cooled Mixture of i oo parts of a prepared in the manner given in Example i, Product containing chlorine and sulfur and 32 parts of that used in Example i Phenol: -mixed, pass in methylamine while stirring vigorously until nothing of it is taken up; solid hydrochloric acid .Methylamine separates here the end. It is filtered off, the resulting oily product is washed with water and it removes volatile components with steam. That way it gets a light brown, thick oil. It can e.g. B. as a soft = inacher for polyvinyl chloride to serve. . Example 5 100 parts by treating isobutane with sulfur dioxide and Chlorine isobutylmonosulfochlori obtained under exposure to short-wave light, d 86 parts of a technical xylenol mixture are added. Into this mixture ammonia is introduced with cooling until saturation. That from ammonium chloride and xylenyl isobutanesulfonate is obtained by centrifuging separated from ammonium chloride; the filtrate is distilled under 3 mm pressure.

The xylenyl ester obtained is a colorless, easily mobile liquid, which boils at about i 8o 'under 3 mm of pressure.

Claims (1)

PATENT CLAIM: Process for the preparation of sulfur-containing organic compounds, characterized in that the action of halogen and sulfur dioxide, optionally under the influence of short-wave light, on aliphatic hydrocarbons or halogenated hydrocarbons with at least one not. with halogen-bonded carbon atom available oxygen, sulfur and halogen-containing products in the presence of ammonia or amines with phenols.