DE1900659B2 - PROCESS FOR THE PREPARATION OF TRICHLOROMETHANESULFENYL CHLORIDE - Google Patents

Description

CS ₂ + 5 Cl ₂ + 4 H ₂ O CCl ₃ SCl -! - H ₂ SO ₄ + 6 HCl (3) Although the process provides relatively little and selective chlorination process, which in By-products good yields, but requires 65 extremely high yields of trichloromethane sulfide

for the conversion of the sulfur _{chlorides into H 2} SO ₄ nyl chloride provides. By setting suitable MoI

'ind HCl also chlorine. Conditions and temperature conditions succeed

The present invention provides a very simple method of chlorination either almost entirely in accordance with

3 '4

Equation (1) or almost exclusively according to Gle- a higher-boiling fraction, the trichloromeihan-

chung (2) to run. sulfenyl chloride and very little disulfur dichloride

The present invention relates to a V'er- contains. The disulfur dichloride content is hot

drive for the preparation of Trichloromethansuifeinl- suitable reaction procedure so low that the Tn-

chloride of carbon disulfide and chlorine, which 5 chlormeihansull'enylchlorid normally 1 of a white

is characterized in that the implementation requires leren purification. However, it can be known in

on iron-free activated carbon. The process manner, for example by steam distillation,

is conveniently cleaned using a with.

granulated activated carbon filled reaction tube through- It has been shown that the content of disulfur

led, in which carbon disulfide and chlorine a io dichloride in the crude trichloromethanesulfenyl chloride of

are passed, a temperature being dependent on the reaction temperature used in the reaction zone.

Temperature from -5 to 100 ° C, preferably from -5 to It rises with increasing reaction temperature. Be:

40 C. is maintained. Implementation in direct current and application of a

The process according to the invention can be carried out at a reaction temperature of 70 ° C. in the crude tri-dichloride manner, both continuously and continuously with disulfide of about 6.4 ° C. disulfur . Preferably dichloride. If the reaction temperature is lowered, a device according to FIG. 1 is used. 1. 40 C, the sulfur dichloride content falls to about 2.5% in the upper part of a granulated activated carbon. When using reaction temperature, reaction tube 1 is via line 3 doors in the range from 0 to ΎC the crude carbon disulfide and in the lower part of the chloromethanesulfenyl chloride even only 0.8 bi-reaction tube introduced via line 2 chlorine in 0.5% disulfur dichloride in a ratio of 1: 2 to 1: 4 This countercurrent is the selectivity of the procedure according to the invention so the reactants are even more favorable in the process. A di-countercurrent is fed into the reaction vessel. A sulfur dichloride content of only 0.6% is already achieved with suitable cooling devices, for example at 25 40 C reaction temperature Use of a double-jacket reaction tube and / apparently at higher temperatures, or through the installation of a layer of activated carbon, the same is formed Wefeld dichloride from carbon disulfide and intermittently penetrating cooling coil 5 is used for this purpose from medially produced sulfur dichloride. The fact that −5 to 100 ^° C. is maintained speaks for ensuring that a reaction temperature of the correctness of this assumption is made. The resulting from the reaction of carbon disulfide with chlorination mixture is drawn off via line 4 from sulfur dichloride to activated carbon at temperatures. in the range from 70 to 90 C trichloromethanesulfenyl

According to a further embodiment, the chloride and disulfur dichloride can be formed. the Procedure also in the in F i g. 2 shown Vorrich implementation takes place quickly and in high yield, can be carried out. This differs from 35. However, the chlorination of sulfur egg can be seen in FIG. 1 device shown only carbon with chlorine also control so that it precedes that the supply line for gaseous chlorine weighs according to equation (2). In this case A molar ratio of carbon disulfide is also kept in the upper end of the reaction tube opens, the reactants are thus equal to chlorine like 2: 5 and a reaction temperature im current passed into the reaction vessel. With this 40 range from 40 to 100 ° C upright, the implementation of chlorine and the activated carbon used should be iron-free in order Carbon disulfide predominantly in a proportion to prevent the formation of carbon tetrachloride as a secondary short zone at the upper end of the activated carbon product. Technical activated carbon is mostly filling, so that the largest part of the reac- containing iron there too. However, you can for the invention tion heat ft ei. The thermoregulation can be prepared in the 45 procedure in a simple way: The The reaction zone is therefore formed with this iron-containing activated carbon is initially diluted with Driving style more difficult than with the former, where aqueous hydrochloric acid is iron-free, then with water the heat of reaction was washed free of acid in a longer activated carbon zone and finally dried. It becomes free. It is advisable to use activated charcoals that are as resistant to abrasion as possible

Since, as already described, the processing of a 50 with a grain size of 2.5 to 4 mm is to be used. Chlorination mixture, which disulfur dichloride Compared to the known chlorination process,

contains, is technically complex, the chlorination based on the method of R a t h k e is characterized

preferably controlled so that, according to equation (1), the method according to the invention is characterized in that

expires. It has been shown that the most favorable conditions when adhering to the preferred molar ratios as

can be achieved if the molar ratio of 55 by-products only sulfur dichloride and only

Carbon disulfide to chlorine 1: 3 to 1: 4 is small amounts of carbon tetrachloride. There-

and the reaction temperature in the range from -5 to against, no higher-boiling by-products are

+40 ⁰ C. The carbon disulfide is then pre-

mainly chlorinated according to equation (1), so that apart from the addition of trichloromethanesulfenyl chloride,

Trichloromethanesulfenyl chloride are predominantly only Swedish. In addition, there is no need to

field dichloride is formed. The chlorination mixture separation and recovery of iodine. The CoIo-

contains only very small amounts of activated carbon according to equation (2).

Amounts of disulfur dichloride left. selective and almost quantitative and thus allows high

The chlorine ling mixture is made up by distillation. The procedure of the patent specification of the

is working. You get a low-boiling fraction, 65 Office for Inventions and Patents in East Berlin

which essentially sulfur dichloride, small ones can be operated continuously, _the to do so

Amounts of unreacted chlorine and carbon disulfide- required equipment is however essentially com-

contains substance and little carbon tetrachloride, and more complicated than that for the implementation of the invention

proposed according to the procedure. In addition, the yields are not nearly as good as with that Achieved method according to the invention.

The particular advantage of the method according to the invention over the method of the German patent application 1,229,518 has a much lower chlorine requirement. In addition, it will be cheaper in place of Hydrochloric and sulfuric acid obtained valuable sulfur dichloride as a by-product. The in the invention The activated carbon filling used in the process has undiminished effectiveness even after long periods of use.

example 1

Molar ratio of carbon disulfide to chlorine = 1: 3.5 initiated. The resulting reaction mixture is composed as follows:

Trichloromethanesulfenyl chloride 54.2%

Sulfur dichloride 31.6%

Monochloride 0.45 ° / ₀

Carbon tetrachloride 1.2%

Carbon disulfide 0.8%

Chlorine 118 ° /

Chloromethanesulfenyl chloride 97.5%

Sulfur dichloride 98.6%

Disulfur dichlond 1.4%

Carbon tetrachloride 2.5%

This results in a carbon disulfide conversion of 96.6%. The yields based on converted

A carbon disulfide, shown schematically in FIG. 1, would be: Device used.

It consists of a 100 cm long jacketed reaction tube 1 with an internal diameter of 25mm. In the interior of the reaction tube there is a cooling coil 5, which enables the in ao keep the reaction tube to cool evenly. The reaction tube is equipped with feed lines for carbon disulfide 3 and chlorine 2 and a derivation for the distillative separation of the lower boiling Chlorination mixture 4 equipped. Components remains trichloromethanesulfenylchlo-

The reaction tube is filled with 0.4 l dry iron aside with 0.8% disulfur dichloride. free, granular activated carbon filled. The activated carbon

has a grain size of 2.5 mm and an inner example 3

Surface from i2ö0 to i50G mVg. over line 2

29 g of carbon disulfide are added per hour and over one in FIG. 2 shown schematically line 3 uses 98 g of chlorine per hour, corresponding to a 30 meter period.

Molar ratio of carbon disulfide to chlorine = 1: 3.64 It is in the manner described in Example 1

fh jdh d dli 2 f

dosed. The amount and temperature of cooling water are chosen so that a temperature of 40 ^° C. is maintained inside the reaction tube.

A reaction mixture is drawn off via line 4, which is composed as follows:

Trichloromethanesulfenyl chloride 54.0%

Sulfur dichloride 30.3%

Disulfur dichloride 0.3%

Carbon tetrachloride 1.1%

Carbon disulfide 0.18%

Chlorine 14.1%

proceed, but 29.8 g of carbon disulfide and 88.0 g of chlorine per hour, corresponding to a molar ratio Carbon disulfide to chlorine = 1: 3.22 introduced at 17 ° C reaction temperature.

The resulting reaction mixture is composed as follows:

Trichloromethanesulfenyl chloride 61.2%

Sulfur dichloride 34.1%

Disulfur dichloride 0.8%

Carbon tetrachloride 0.2%

Carbon disulfide 0, ^ 2%

Chlorine 3.6%

This results in a carbon disulfide conversion. This results in a carbon disulfide conversion

of 99.2%. Dk yields, based on converted 99.9%. The yields, based on converted "carbon disulfide, are: 5" carbon disulfide, are:

Trichloromethanesulfenyl chloride 96.6% Sulfur dichloride 97.8% Disulfur dichloride 1.4% Carbon tetrachloride 2.6%

After the lower-boiling components (chlorine, carbon disulfide, tetra-chlorine carbon, sulfur dichloride) have been separated off by distillation, trichloromethanesulfenyl chloride with 0.55% disulfur dichloride remains.

B ei s ρ i e 1 2

The procedure is as described in Example 1, but every hour 64.2 g of carbon disulfide and 210.0 g of chlorine, corresponding to one

Tricblomethanesulfen) '. Chloride 99.6% Sulfur dichloride 97.6% Disulfur dichloride 2.4% Carbon tetrachloride 0.4%

After the lower boiling components have been separated off by distillation Components remains Trichloromethansotfenylchlo rid with 1.35% disulfur dichloride.

Example 4

It is vei in the way described in Example 3

Drive for 6s, but 29.0 g of sulfur per hour are added

carbon and 67.7 g chlorine, corresponding to one mole

ratio of carbon disulfide to chlorine = 1: 2.5 tx

90 ° C reaction temperature initiated.

7 8

The resulting reaction mixture is 98.7% as follows. The yields based on converted

composed: carbon disulfide, amount to:

Trichloromethanesulfenyl chloride 66.2% trichloromethanesulfenyl chloride 93.0 »/,

Sulfur dichloride 2.8% ⁵ sulfur dichloride 3.4 «/

Disulfur dichloride 27.3 · /. Disulfur dichloride 95.2 /,

Carbon tetrachloride 3.3% carbon tetrachloride 5.6 · /.

Carbon disulfide 0.4% ₁₀ Na ₀ I ₁ distillative separation of the lower boiling

Components are left with raw trichloromethanesulfenyl-Darfrom the result is a carbon disulfide conversion chloride with 29.3% disulfur dichloride.

1 sheet of drawings

Claims (2)

gas (HCl, SOo) and sulfur quantities. The hydro claims: lytic destruction can also be done in the presence of an oxidizing agent, e.g. B. in the presence of 1. Process for the production of trichloro-chlorine, to be carried out (German methar.sulfenylchlorid by reaction of Schwe- 5 patent specification 915 335). Thereby arise from the Carboniferous carbon 'with chlorine, characterized by sulfuric chlorides, sulfuric acid and hydrochloric acid. This draws that one is the implementation of iron separation process because of the additional effortless Carries out activated carbon. "The large amount of chlorine is uneconomical. Also 2. The method according to claim 1, characterized in that the reaction is carried out in a reaction tube filled with sulfur chlorides by reacting the activated carbon with a mixture of sulfur dioxide, neutral or acidic -5 to 10 ³ C performs. Sulphites into polythionates, thiosulphate, chlorides, etc. are transferred, is complex and expensive (German Patent 910 297). Furthermore were 15 separation processes known according to which, the sulfur chlorides under the action of sulfur trioxide into sulfur, thionyl chloride and sulfur dioxide (US Pat. No. 2,664,442) or under the action The invention relates to a process for the production of aliphatic ethers or alcohols in hydrochloric acid, by trichloromethanesulfenyl chloride (perch'ormethyl-20 sulfur dioxide and sulfur mercaptan). (U.S. Patent 2,545,285). So far, trichloromethanesulfenyl chloride has been used in a for the first time by Rathke in a manner that was flat by agile processing of what is known after the well-known catalytic chlorination of carbon disulfide produced process is chlorination mixture. Of the (Ann., 167, p. 195 [1873]). As a catalyst, the proportion of by-products is high, the yield and the purity of the trichloromethanesulfenyl chloride was almost exclusively iodine in an additional amount from 0.1 to 1.0 ° / ₀ used. Below 30 ⁰ C is comparatively low. In addition, this chlorination If the reaction runs according to equations 1 and 2: the process can only be carried out discontinuously. .. _Λ There are also continuous processes for CS ₂ + 3 CL ₂ ----> CCLSCl + SCl ₂ (1) 3 ° position of trichloromethanesulfenyl chloride known. According to the method of patent specification 36 260 des "Office for Inventions and Patents in East Berlin 2 CS ₂ -t- 5 Cl ₂ ^ 4- 2 CCl ₃ SCl + S ₂ Cl ₂ (2) the chlorination is charged in with packing Columns in the presence of iodine as a catalyst In addition to sulfur, this reaction is carried out. In a chlorination zone of the codichloride and disulfur dichloride or tetrachloride, in which a temperature of 15 to 25 ° C is maintained for carbon, thiophosgene and other compounds, 2.25 to 3 mol of chlorine react per as undesirable by-products. The lighter curse-mole carbon disulfide that the rest of the chlorine remains term by-products such as carbon tetrachloride and dissolved in carbon disulfide. This mixture will Sulfur dichloride can be transferred by distillation from the 40 to a second column, where in a 15 The reaction mixture is separated off, but the post-reaction zone maintained at up to 25 ° C. is the dissolved extremely difficult, trichloromethanesulfenyl-free chlorine reacts with carbon disulfide. at Chloride and disulfur dichloride in this way for this process are particularly in the night. Long residence times are required during the distillation at normal pressure in the reaction zone. That trichloromethanesulfenyl chloride decomposes because of the chlorination mixture, 42% consists of low thermal instability. With greatly reduced volatile by-products and 58% from one Pressure differ from the boiling point of trichloromethanesulfenyl chloride-containing sump. From the chloromethanesulfenyl chloride and disulphur dichloride the sump can only be slightly removed by means of steam. There were therefore to isolate the distillation trichloromethanesulfenyl chloride in a Isolate trichloromethanesulfenyl chloride from the chlorination 50 yield of only 60 to 70% of theory, A mixture of procedures is proposed, which is based on a marriage mix conversion of the sulfur chlorides in easily 1,229,518 a process known, which are also based on continuously separable compounds. can be carried out naturally. After this For example, the sulfur chlorides can be hydrolytically destroyed in the chlorination process in the presence of a 5- aqueous medium, especially in the case of the aqueous 55 to 38% aqueous hydrochloric acid, optionally in steam distillation (organic a chlorinated solvent, e.g. in trichloro synthesis, coil. Vol. 1, p. 502 [1962]; Authenrieth methansulfenylchlorid, at 0 to 46 ° C in Reaiktions- und H ef η er, Ber., 58, p. 2151 [1925]). De-piling carried out in the process. The implementation takes place in accordance with the enormous, technically difficult to master equation (3).