Patented Feb. 16,1954 " . 2,669,587 UNITED sures PATENT“ OFFICE

PROCESS OF MAKING BIS (BETA CHLOR~ ETHYL) George E. Miller, Edgewood Arsenal, Edgar M. Faber, Baltimore, and Arthur-7M.- Reeves, Havre de Grace, Md, assignors» to the 'United'states of‘ Americaas represented by the Secretary of War - No Drawing. Application June 19, 1937, serial No. 149,233 6 Claims. (Cl. 260--609) (Granted under Title 35, U. 8. Code (1952), see. 266) l a The invention described herein may be manu- not limitedto the precise details herein set forth factured and used by or for the Government for by way of illustration, governmental purposes, without the payment to Theoretically, the formation .of his (beta chlor them of any royalty thereon. ethyl) sul?de from. and dichlor This invention relates to an improved process 5 ide is. the ideal method. However, the strong for the manufacture of bis (beta chlorethyl) sul- tendency of the sulfur dichloride to chlorinate ?de commonly known as . the mustard gas had not been overcome prior Mustard gas, which is to our invention. These reactions may be ex 610E201}, pressed by the following. equations:

5 1° . ClOHiQEi CICHZCQ modem + set =- ‘5' was used during the World War as a war gas, (31032611! and was manufactured for the German army by women, CICHZCIOH reacting ethylene ch'lorhydrin with sodium sul- 15 g S l _ s S HG] ?de, with subsequent treatment with hydro- ‘ + C “ _ ‘I’ + chloric acid. Later developments showed that 0101520112 0101120112 mustard gas could be produced by the action of Prior to the present invention, sulfur dichlor ethylene upon sulfur monochloride. 20 ide containing one per cent of absorbent char The Levinstein process for mustard gas manu- coal had been treated with dry ethylene. How~ facture consists essentially in bringing together ever, the yield was only about 50% mustard gas sulfur mono-chloride and Very pure ethylene gas which was also very impure. Another method in the presence of crude mustard gas as a Solvent tried was to spray ethylene with mixtures of sul at a temperature ranging from 30—35° C- A Sllp- I, vfur dichloride and sulfur monochloride into a ply of unchanged mono-chloride is constantly globular ?ask at atmospheric pressure. The mus maintained in the reacting liquid until a su?i- tar-c1 gas thus Obtained contained a, large per Ciently large batch is built up- Then the Sulfur centage of S2C'L2 which will gradually chlorinate mono-chloride feed is discontinued and the eth- the mustard gas, ylene feed continued until further abSOI‘DtiOII According to the present invention the reaction ceases- During the reaction the charge is me- to of sulfur dichloride and ethylene is carried out chanically agitated. under pressure with an excess of ethylene. Due This Levinstein process is acwmpanied by 9» to the increase in pressure, the concentration deposition of Sulfur in the reactor, pipe lines and of ethylene is increased, with a resultant increase valves. causing serious clogging. Since a oer- in the rapidity of the reaction and a decrease in tain amount of mustard gas remains with this 35 the chlorination of the mustard gas by unre sulfur, the removal of the sulfur is accompanied acted sulfur dichloride. It has been found that by hazards to the personnel- pressures of the order of 40‘ to 75 pounds or The principal object of this invention is to upward, per square inch in the reaction cham develop an e?‘loient continuous process for the her may be used satisfactorily. In a number of manufacture of his (beta chlorethyl) sul?de in 40 runs, a pressure of about 50 pounds per square quantity production. inch has been used with good results. Gener Another Object of this invention is to develop ally the reaction is more rapid and there is less a process for the manufacture of his (beta chlor- chlorination of the mustard gas as the pressure ethyl) sul?de in which the difficulties occasioned is raised. by the deposition of sulfur in the pipes and valves 45 In order to get a rapid and intimate mixture of are materially reduced. the S012 and ethylene, the spray method is used Another object of this invention is to develop and preferably the sulfur dichloride is sprayed a process for the manufacture of bis (beta chlor- into an atmosphere of ethylene. One speci?c ethyl) sul?de from ethylene and sulfur dichloride example of our process is as follows: A lead-lined which eliminates the strong tendency of sulfur 50 reactor is ?lled with ethylene maintained at a dichloride to chlorinate the mustard gas in the pressure of 50 pounds per square inch. Sulfur reaction chamber. dichloride is sprayed into the reactor and the These and other objects of the invention will resultant mustard gas is withdrawn. be apparent from the following description and By the above method, a yield of about 92% claims, it being understood that the invention is 55 mustard gas having a purity of about 85% may 2,669,587 4 3 pounds to about 60 pounds per square inch and be obtained. The temperature in the reaction spraying sulfur dichloride thereinto. chamber is generally from 50° to 80° C. 5. The process of making his (beta chlor For quantity production, the reactor will be ethyl) sul?de which comprises spraying sulfur di continuously supplied with ethylene to maintain chloride into ethylene maintained at a pressure the pressure thereof, and means will be provided of substantially 50 pounds per square inch. to continuously withdraw the lique?ed gas. 6. The process of making bis (beta chlor The invention herein described is not limited ethyl) sul?de which comprises spraying sulphur to the precise details herein disclosed, since vari dichloride into ethylene maintained under a pres ations therein may be made by those skilled in 10 sure of from about 40 pounds to about 75 pounds the art without exceeding the scope of the ap per square inch, maintaining a reaction tempera pended claims. ture of from about 50° C. to about 80° C., con We claim: tinuously supplying additional ethylene to main 1. The process of making his (beta chlor ' tain the pressure, and withdrawing the lique?ed ethyl) sul?de which comprises intimately con— bis (beta chlorethyl) sul?de. tacting sulfur dichloride and ethylene at a pres 15' sure of from about 40 pounds to about 75 pounds GEORGE E. MILLER. per square inch. EDGAR M. FABER. 2. The process of making bis (beta chlor ARTHUR M. REEVES. ethyl) sul?de which comprises intimately con tacting sulfur dichloride and ethylene by spray 20 References Cited in the ?le of this patent ing under a pressure of from about 40 pounds to FOREIGN PATENTS about 75 pounds per square inch. 3. The process of making his (beta chlor Number Country Date ethyl) sul?de which comprises maintaining an 142,875 Great Britain ______June 10, 1920 excess of ethylene under pressure, and introduc 25 504,814 France ______July 17, 1920 ing therein and intimately contacting therewith OTHER REFERENCES sulfur dichloride at pressure of from about 40 “Journal Soc. Chem. Ind.” vol. 39, page 65. pounds to about 75 pounds per square inch. (Copy in Patent O?ice Library.) 4. The process of making his (beta chlorethyl) , (Copy 30 “Chem. Reviews,” vol. 15 pages 426-62. sul?de which comprises maintaining an excess of in Patent Oflice Library.) ethylene under a pressure of from about 40