DE1900659A1 - Process for the preparation of trichloromethanesulfenyl chloride - Google Patents

Description

Poe. OW 1457

Process for the preparation of TriohlorreethansuXfenylchlorld

Oil substance AO • Wuppertal

The invention relates to a method for Heretei.i- ^ before. TrI chloromethanesulfenyl chloride (Perchlormethy! mercapto r.,

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ili: ser Reektiofj er "tehen ihos": Schwele .. ..i .; .- :, di chlor id nor TetrAahIc ^ raiueKctc. '. \ r * Varblndungefi a.-ö unl. ^ i oh ^ e Lord. πp ~ - volatile ^ ebenpi-oduxU; from left _:
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So far, trichloromethanesulfenyl chloride has been produced in a manner described by catalytically CLü.rr ..ruag of carbon disulfide [Ann. 16? _# Page 1- :, U8? JO]. Almost all of the catalyst was iodine; e,. -r ^ usata »wange 0.1 to 1.0 % used. Below ve- .; J "" vrlauf ■ ;. the reaction according to equations I and 2s

CS ₂ +? CLp - - - ·· '' CCl ^ SCl + SCl-.;. ;

Poe. GW 1457

Trichloromethanesulfenyl chloride and disulphurodichicride can be separated in this way. During the distillation at atmospheric pressure decomposes TrichlormethansulfenyXchlorid InTοige its thermal instability _t For strongly '/ ermince- "n pressure to separate the boiling point. c ", jchlvivt and diachsulfur dichloride only *« ■ ".
Isolation of the Trichlorr.ethfc.

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BATH ORIGINAL

low. In addition, this chlorination process can only be carried out batchwise be performed.

Continuous processes for the preparation of trichlxamefchansulfenyl chloride are also known. According to the process of GDR patent specification No. 36 260, the chlorination is carried out in columns charged with packing in the presence of iodine as a catalyst. In a chlorination zone of the column, in which a temperature of 15-25 ^° C. is maintained, 2 * 23-3 moles of chlorine react per mole of carbon disulfide, the rest of the chlorine remains dissolved in the carbon disulfide. This mixture is transferred to a swelv "column, where in a 15 - afterreacted the dissolved free chlorine with carbon disulfide 25 ⁰ C held after-reaction zone. In this process, long residence times are required, in particular in the post-reaction zone. The chlorination mixture consists of 42 % of low-volatility by-products and 58 % of a sump containing trichloromethaneulfenyl chloride. Trichloromethanesulfenyl chloride can be extracted from this sump by means of steam distillation in a yield of only 60 to 70 % of theory. isolate.

Furthermore, from the German Auslegeschrift No. 1 229 518 a Process known which can also be carried out continuously. According to this procedure, the chlorination takes place in the presence from 5 to 38 # aqueous hydrochloric acid, optionally in a chlorinated one Solvents, e.g. in trichloromethanesulfenyl chloride, at 0 to 46 ° C carried out in reaction »tower. The implementation takes place according to equation 3.

CS ₂ + 5 Cl ₂ + 4 H ₂ O - CCl ₅ SCl + H ₂ SO ₄ + 6 HCl (?)

Although the process gives good yields in addition to relatively few by-products, it also requires chlorine for the conversion of the sulfur carbon dioxide into H ₂ SO ^ and HCl.

The present invention represents a very simple and selective chlorination process which gives trlohloraethanesulfenyl chloride in extremely high yield. By

009839/2186

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Setting of suitable molar ratios and temperature conditions succeeds in the chlorination either almost exclusively in accordance with Equation 1 or almost exclusively according to equation (2) allow.

The present invention relates to a process for the preparation of trichloromethanesulfenyl chloride from carbon disulfide and chlorine, which is characterized in that the reaction is carried out on activated carbon. The process is expediently carried out using a reaction tube filled with granular activated carbon, which carbon disulfide and chlorine are introduced, whereby a temperature of -5 ° to 10O ⁰ C, preferably -5 ° to 40 ⁰ C, is maintained in the reaction zone.

The process according to the invention can be carried out in various ways, both continuously and discontinuously. A device according to FIG. 1 is preferably used. In the upper part of a reaction tube 1 filled with granular activated carbon, carbon disulfide is transferred via line 3 and into the lower part of the reaction tube via line 2 chlorine in a molar ratio of 1: 2 to 1: 4. In this procedure, the reactants are thus fed into the reaction vessel in countercurrent. By means of suitable cooling devices, for example by using a double jacket reaction tube and / or by installing a cooling coil 5 which evenly penetrates the activated carbon layer, it is ensured that a reaction ^{temperature of -5 to 100 °} C. is maintained. The resulting Chlorlerurigsgemlsch is drawn off via line 4.

According to a further Aueführungsform the method may AUOH in the embodiment shown in Figure 2 apparatus performed werden.Die!. Device illustrated only in that the feed line for gaseous chlorine also opens into the upper end of the reaction tube is different from the FIG., The so reactants are in Oleichstrom into the reaction vessel geführt.Bei this procedure, the reaction of chlorine and carbon disulfide Mostly in a relatively short zone at the top of AktivkohlefUllung, eo that AUOH where most of the reaction, "If you were free will" Dl · Väraeregulierune in the reaction *

009839 / 219S " ⁵ ".

Item OW 1457

Zone therefore makes it more difficult for me to use this method than with the former, where the heat of reaction is released in a longer activated carbon zone.

Since, as already described, the work-up of a chlorination mixture which contains disohweed alcohol is technically complex, the chlorination is preferably controlled in such a way that it takes place in accordance with equation 1. It has been found that the best conditions are achieved when the sulfur Molverhältnie carbon * su chlorine 1 ι 3 to 1 t is 4, and the reaction temperature is in the range of "5 to +40 ⁰ C. The carbon disulfide is then mainly chlorinated according to oil solution 1, so that, apart from trlehlornethanaulfenvlohlorld, predominantly only sohweeflohloride is formed. The chlorination mixture contains only very small amounts of disohweediochloride produced in accordance with oil treatment 2 »

The chlorination agent is then worked up in the distillate state a low-boiling fraction, which consists essentially of carbon dioxide, small amounts of unreacted chlorine and carbon disulfide and contains little carbon tetrachloride, and contains a higher boiling fraction, dielrlohlormethanesulfenylchlorld, and very little disohwefeldlohlorld. The proportion of disulfur dioxide is With a suitable reaction flow rate so low that the trloromethanesulfenyl world normally does not require any further purification. It However, it can be cleaned in known catfish, for example by steam distillation.

It has been shown that the content of disohydium chloride in the crude triohlomethane sulphide chloride increases as the reaction temperature rises, depending on the reaction temperature used. When implementing 1 «direct current and using a reaction temperature of 70 ⁰ C, the Hoh-Triohlormethanaulfenylohlorid contains about 6.4 %

Disobwefeldiohloride. Reduces the reaction temperature

• o the disobwefeldlohloride OehaU sinks to approx. 8.5 Jf. In the case of

• 6 -

009839/2196

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tion of reaction temperatures in the range of 0 to 3 ° C contains the crude trichloromethanaulfenyl chloride only 0.8 to 0.5 pounds Dischwefeldlchlorld · In the case of countercurrent reactions, the selectivity of the process according to the invention is even more favorable. Here is a disulfur chloride content of only 0.6 Jf already at 40 ° C reac tion temperature reached.

Apparently, at higher temperatures, disulfur chloride is formed from carbon disulfide and sulfur chloride formed as an intermediate. For this assumption, the fact that are formed in the reaction of carbon disulfide with sulfur on activated carbon at temperatures in the range of 70 to 90 ⁰ C and Trichloruetnansulfenylchlorld Dlschwefeldichlorld. The conversion takes place quickly and in high yield.

However, one can chlorinate carbon disulfide with chlorine also control so that it runs predominantly according to equation 2. In this case a molar ratio of carbon disulfide is used Chlorine as 2: 5 and a reaction temperature in the range from 40 to 100 ° c upright.

The activated charcoal used should be free of powder in order to ensure the formation to prevent carbon tetrachloride as a by-product. Technical activated carbon is mostly ferrous. However, it can be used for that Process according to the invention can be prepared in a simple manner: The iron-containing activated carbon is first mixed with dilute aqueous Hydrochloric acid free of acids, then washed free of acid with water and finally dried. It is advisable to use activated carbon types with a grain size of 2.5 to 4 nm that are as abrasion-resistant as possible.

Compared to the known Chloriarungsverfahren on the von Rathk, the method according to the invention is distinguished as a result, if the preferred moXverhaltnlsee is observed as a by-product “only sight” f “ldlehlori £ and r? .ir small

009839 / 219E

Item OW 1457

Amounts of carbon tetrachloride are produced. On the other hand, higher-boiling by-products are formed, so that costly separation processes for isolating the trichloroethanesulfenyl chloride are not necessary required are. In addition, there is no need for iodine to be used, separated or recovered. The chlorination on activated carbon takes place extremely fast «selective and almost quantitative and thus allows high throughputs. The procedure of the GDR patent specification can be operated continuously, but the required device is much more complicated than that for the Proposed implementation of the method according to the invention. In addition, the yields are not nearly as good as with that according to the invention achieved.

The particular advantage of the method according to the invention over the procedure of the German Auslegeschrift No. 1 229 518 exists significantly lower chlorine requirement · In addition, valuable sulfur dichloride is used instead of cheap hydrochloric and sulfuric acid received as a by-product. The activated charcoal filling used in the process according to the invention has the properties even after a long period of use undiminished effectiveness

example 1

There was one in Flg. 1 device shown schematically used

It consists of a 100 cm long double jacket reaction tube (1) with an inner diameter of 25 mm. In the interior of the reaction tube there is a cooling coil (5) which enables to cool the contents of the reaction tube evenly. The reaction tube is provided with feed lines for carbon disulfide (5) and Chlorine (2) and a discharge for the Chlorlergemlsoh (4) equipped.

The reaction tube is filled with 0.4 l of dry, iron-free granulated activated carbon. The activated carbon has a grain size of 2.5 nm and an inner surface of 1200 to 1500 wP / t. Via the line

009839/2195

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2 are etUndlioh 29 g carbon disulfide and over the line

3 hourly 98 β chlorine corresponding to a molar ratio of carbon disulfide ι chlorine * 1 t 3.64 metered in »the amount of cooling water and the temperature is chosen so that it is inside the reaction tube a temperature of 40 ° C is maintained.

A reaction mixture is withdrawn via line 4 as follows is composed ι

Triohlomethane naulfenyl chloride 54.0 % Sohwefeldlohlorid 30.3 % Disulphur dichloride 0.3 % Carbon tetrachloride 1.1 % Carbon disulfide 0.18 %

Chlorine 14.1 %

This results in a carbon disulfide • conversion of 99.2 Jü.Dif yields based on converted carbon disulfide!

Trlohlomethanesulfenylehlorld 96.6 % Sulfur dichloride 97.8 % Dlsohwefeldi chloride 1.4 % Carbon tetrachloride 2.6 %

After the distillate separation of the oleoether-boiling components (chlorine, carbon disulfide, carbon tetrachloride, sulphurous chloride), triohlomethanesulfenylohlorld old 0.55 % Dl

Example 2

The same procedure as described in Example 1 is used. Each dooh etUndlioh 64.2 g of carbon disulfide and 210, og Chlorine corresponding to a molar ratio of carbon disulfide Chlorine - 1 ι 3.5 initiated. This resulted in · reactionsegee Is as follows iiiaazwengesetst ι

-

009839/2195

54.2 * Item OW 1457 31.6 % 1900659 - * - 0.45 % 3 1.2 % Trichloromethaneulfenyl chloride 0.8 % Sulfur dichloride 11.6 % Dlsohwefeldlohlorid Carbon tetrachloride Carbon disulfide chlorine

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

Trlohlormcthansulfenylchlorid 97.5 % Sohwefeldichlorld 98.6 % Dlsohwefeldlchlorld 1.4 % Carbon tetrachloride 8.5 %

After the lelohtersled components have been separated off by means of a detailed separation, triohlonaethanesulfenyl chloride (0.8 % disulfur dichloride) remains.

Example 3 Ee became a device as schematically shown in Fig. 2

used·

It is proceeded in the catfish described in example 1, depending

but every hour 29.8 g carbon disulfide and 88.0 g chlorine, corresponding to a »MolverhJQtnla carbon disulfide 1 chlorine - 1 t 3i23 t * i IT ⁹ Q reaction temperature initiated.

The resulting action ratio is Hi · follows additionally1

y 61.2 %

Sohwefeldif * a «iri4 Disohwefeldiqhlorid _{0 # 8} ^ Carbon tetrachloride _{0 # 2} %

carbon disulfide 0 * 02 4

^CU 5.6 %

009839/2196. i ₀ -

«** - Poa. GW 1457

This results in a carbon disulfide conversion of 99 * 9 %. The yields, based on the converted carbon disulfide, are

Triohiormethanesulfenyl Chloride 99 * 6 % Sulfur dichloride 97 * 6 % Dlsohwefeldiohlorid 2.4 % Carbon tetrachloride 0.4 %

After separating off the Ie loht boiling components, triohloraethanesulfenyl chloride with 1.33 % sulfur dichloride remains.

Example 4

Ea is moved in the manner described in Example 3 catfish "However, hourly 29,0g carbon disulfide and 67,6g chlorine, corresponding to a molar ratio of carbon disulfide ι chloro - 1 ι 2.5 at 90 ⁰ C Reaktlonatemperatur initiated · Pas 1st resulting Reaktionsgemlsoh as follows composed »

TriohlormothansulfenylQhlorld 66.2 % Sulfur dichloride ^! 2.8 % Diöohwefeldiohlorid 87.3 % Carbon tetrachloride 3.3 % Carbon disulfide ■ $ 0.4

This results in a carbon disulfide conversion of 98.7 The yields based on converted carbon disulfide are!

Trlohlomethanesulfenyl chloride 93.0 % Sohwefeldiohlorid 3.4 % Disulfur dichloride 95.2 % Carbon tetrachloride 5.6 %

009839/2195

Poe. OW 1457

After the detachment of the components which are contained in the loan, crude trichloromethanaulfenylohlorld with 29O % Dlaohwefeldiohlorld remains.

009839/2195

Claims (5)

Po «. OW 1457 claim 1. Process for the production of Trlchlormethaneulfenylohlorld by converting carbon disulfide old chlorine, daduroh characterized in that the reaction is carried out on activated charcoal. 2. The method of claim 1, daduroh in that durchfuhrt the reaction in a tank filled with granular activated carbon reaction tube, are introduced in that carbon disulphide and chlorine, wherein in the reaction zone a temperature of -5 ° to 100 ⁰ C, preferably -5 ° up to 40 ° C. 3 · Process according to claims 1 and 2, characterized in that in the upper part of a granulated active · carbon-filled reaction tube and carbon disulfide Chlorine in a molar ratio of 1 ι 2 to 1 ι 4 initiates and on The Oemisoh formed from trichloromethanesulfenyl chloride and chlorides of sulfur is withdrawn from the lower end of the reaction tube. 4. The method according to claims 1 and 2, characterized in that one in the upper part of a reaction tube filled with granular activated carbon and carbon disulfide in the lower part of the reaction tube introduces chlorine, the molar ratio of carbon disulfide and chlorine being 1 to 2 to 1 ι 4 and at the lower end of the reaction tube · the resulting mixture of triohlomethanesulfenyl chloride and chlorides of sulfur · subtracts. 5. The method according to claims 1 bin 4, daduroh gekennzeiohnefe, that the molar ratio of carbon disulfide to chlorine is 1 t bi · 1 ι 4 is. 009839/2195