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Home , Thionyl chloride

Patented Jan. 22, 1946 2,393,247 UNITED STATES PATENT OFFICE 2,393,247 PROCESS FOR THE PREPARATION OF TONY, CORDE Aban Thomas Ballowel and Gordon Theodore Waala, Wilmington, Del, assignors to E. I. du Pont de Nemours & Company, Wilmington, Del, a corporation of Delaware No Drawing. Application February 3, 1945, Serial No. 576,148 15 Claims. (CI. 23-203) This invention relates to the manufacture of minum , aluminum bromide, ferric chlo thionyl chloride. ride, borontrifluoride, stannic chloride, titanium This application is a continuation-in-part of tetrachloride, antimony pentachloride, zinc chlo our copending application Serial No. 539,378, filed ride, and complexes of Friedel-Crafts' catalysts June 8, 1944. - - with organic compounds. , Thionyl chloride is an important material in The more detailed practice of the invention is the manufacture of many chemicals and chemi illustrated by the following examples, wherein cal intermediates, such as dyestuffs, pharmaceu parts given are by weight. There are, of course, ticals and acid . It is ordinarily pre many forms of the invention other than these pared by the reaction of trioxide with Sul specific embodiments. fur chlorides and has also been prepared by the O reaction of with chlorides of phos Eacample I phorus. These materials are of such a nature Carbon tetrachloride (180 parts), sulfur diox that the manufacture is fraught with special ide (100 parts), and aluminum chloride (65 parts) problems. 5 were heated at 140° C. for six hours in a stain This invention has as an object the provision less steel-lined autoclave. The autogenous pres of a process for the manufacture of thionyl chlo sure developed was 32 atmospheres. After bleed ride. A further object is a process using readily ing the autoclave to atmospheric pressure, 256 available, less corrosive materials. Other objects parts of a dark liquid was obtained. Distillation will appear hereinafter. 20 of the liquid at room temperature and 40 mm. These objects are accomplished by the follow pressure, followed by fractionation of the distill ing invention wherein sulfur dioxide is reacted late at atmospheric pressure, yielded 100 parts of with a chlorinated methanehaving three or four thionyl chloride boiling at 75° to 77° C. A small chlorines, the other valences of the carbon being amount of was found in the low boil satisfied by hydrogen, e. g., or carbon 25 ing fractions. The thionyl chloride was characa tetrachloride, at a temperature of 100 to 300° C. terized by its (reported 78.8° C.), and at a pressure of one to five hundred atmos neutral equivalent of 31 (theory 30), and Con pheres in the presence of a Friedel-Crafts' cata version to boiling at 124 C. and lyst, preferably a polyvalent metal halide hy having a saponification equivalent of 57 (cor drolyzing in water to an acid reaction. 30 responding values for dimethyl sulfite of known In the preferred practice of the invention, the origin being 126° C. and 55, respectively). The reaction is run at 140° to 200° C. for two to eight phosgene was reacted with aniline to yield a de hours in the presence of 0.01 to 1.0 mole of alu rivative melting at 238 to 240° C. and showing minum chloride per mole of carbon tetrachloride no depression in a mixed with Car or chloroform and at a pressure of 15 to 200 at 35 banilide. . . . mospheres. The use of longer reaction times, Ecample II higher pressures or larger amounts of catalyst is not excluded. The reaction can be carried out Carbon tetrachloride (180 parts), sulfur di in the liquid phase or gas phase provided suit (i.60 parts), and aluminum chloride (20 able contact with the catalyst is maintained. In 40 parts) were heated in a stainless steel-lined auto the Carbon tetrachloride-sulfur dioxide reaction, clave at 150° C. for eight hours. The pressure it is desirable, but not necessary, to employ two produced was 40 atmospheres. A small amount moles or more of sulfur dioxide per mole of car of crude phosgene was condensed in dry ice-ace bon tetrachloride. If the amount of sulfur di tone cooled traps during bleeding of the auto oxide is less than two moles per mole of carbon 45 clave. A dark liquid product (260-parts) was re tetrachloride, the yield of thionyl chloride is low moved from the autoclave and distilled as de ered and an undesirable amount of phosgene is scribed in Example I, yielding 140 parts of thi formed. In the chloroform-sulfur dioxide reac onyl chloride. tion, one mole of sulfur dioxide per mole of chlo Eaca772ple III roform gives good results. The reactions are 50 thought to be as follows: Carbon tetrachloride (90 parts), sulfur diox ide (100 parts), and aluminum chloride (10 parts) (1) CC4-2SOa->2SOCla--CO2 were heated in a stainless steel-lined autoclave (2) CHCl3+SOa-SOCI+HC)--Co at 200 C. for eight hours. A dark liquid was Typical Friedel-Crafts' catalysts include au- 55 obtained from the autoclave and was distilled as 2 2,893,247 described in Example I yielding 100 parts thionyl aluminum chloride as a catalyst and recovering chloride. the thionyl chloride. Eacample IW . . . . 6. Process according to claim 5 wherein the aluminum chloride is used in the amount of 0.01 Carbon tetrachloride (80 parts), sulfur diox to 10 mole per mole of carbon tetrachloride. ide (90 parts), and ferric chloride (30 parts) 7. Process for the preparation of thionyl chlo wereat 200 heated c. for in twelve a stainless hours. steel-linedA dark liquid autoclave prod ride which comprises reacting sulfur dioxide and uct was removed from the autoclave and distilled chloroform in the presence of a Friedel-Crafts' as described in Example I yielding 85 parts thi catalyst and recovering the thionyl chloride. onyl chloride. 8. Process for the preparation of thionyl chlo Eacample V ride which comprises reacting sulfur dioxide and chloroform at 100 to 300 C. and at. a pressure Chloroform (80 parts), sulfur dioxide (100 of one to five hundred atmospheres in the pres parts), and aluminum chloride (20 parts) were ence of a Friedel-Crafts' catalyst and recovering heated in a stainless steel-lined autoclave at 150 the thionyl chloride. C. for eight hours. After bleeding the autoclave 9. Process for the preparation of thionyl chlo to atmospheric pressure, 95 parts of a liquid. ride which comprises reacting sulfur dioxide and product was obtained. The product was dis chloroform at 100 to 300 C. and at a pressure tilled as in Example I and 32 parts of thionyl of one to five hundred atmospheres in the pres chloride, boiling at 75° to 76° C. and having a ense of a Friedel-Crafts' metal halide catalyst neutral equivalent of 33, was obtained. and recovering the thionyl chloride. When the reaction conditions found suitable for 10. Process for the preparation of thionyl chlo the preparation of thionyl chloride from sulfur ride which comprises reacting sulfur dioxide and dioxide and chloroform or carbon tetrachloride were applied to sulfur dioxide and methylene di chloroform at a temperature of 140 to 200' C. chloride, no thionyl chloride was obtained. and a pressure of fifteen to two hundred atmos

pheres in the presence of a Friedel-Crafts' metal The above description and examples are in halide catalyst and recovering the thionyl chlo tended to be illustrative only. Any modification ride. thereof or variation therefrom which conforms 11. Process for the preparation of thionyl chlo to the spirit of the invention is intended to be ride which comprises reacting chloroform with included within the scope of the claims. at least one mole, per mole of chloroform, of What is claimed: sulfur dioxide at 140' to 200 C. in the liquid 1. Process for the preparation of thionyl chlo phase and at a pressure of fifteen to two hundred ride which comprises reacting sulfur dioxide and atmospheres in the presence of aluminum chlo carbon tetrachloride in the presence of a Friedel ride as a catalyst and recovering the thiony Crafts' catalyst and recovering the thionyl chlo chloride. ride, 12. Process according to claim 11 wherein the 2. Process for the preparation of thionyl chlo aluminum chloride is used in the amount of 0.01 ride which comprises reacting sulfur dioxide and to 10 mole permole of chloroform. carbon tetrachloride at 100 to 300 C. and at 13. Process for the preparation of thionyl chlo a pressure of one to five hundred atmospheres ride which comprises reacting sulfur dioxide and in the presence of a Friedel-Crafts' catalyst and a chlorinated methane of the formula CH-Cla, recovering the thionyl chloride. where ac is three to four, in the presence of a 3. Process for the preparation of thionyl chlo Friedel-Crafts' catalyst and recovering the thi ride which comprises reacting sulfur dioxide and onyl chloride. carbon tetrachloride at 100 to 300 C. and at a 14. Process for the preparation of thionyl chlo pressure of one to five hundred atmospheres in ride which comprises reacting sulfur dioxide and the presence of a Friedel-Crafts' metal halide a chlorinated methane of the formula CH4-Cle, catalyst and recovering the thionyl chloride. where at is three to four, at 100' to 300' C. and a 4. Process for the preparation of thionyl chlo O pressure of one to five hundred atmospheres in ride which comprises reacting sulfur dioxide and the presence of a Friedel-Crafts' catalyst and carbon tetrachloride at a temperature of 140 to recovering the thionyl chloride. 200° C. and a pressure of fifteen to two hundred 15. Process for the preparation of thionyl chlo atmospheres in the presence of a Friedel-Crafts ride which comprises reacting sulfur dioxide and metalhalide catalyst and recovering the thionyl a chlorinated methane of the formula CH-Cls, chloride. where ac is three to four, at 100 to 300° C. and a 5. Process for the preparation of thionyl chlo pressure of one to five hundred atmospheres in ride which comprises reacting carbon tetrachlo the presence of a Friedel-Crafts' metal halide ride with at least two moles, per mole of carbon catalyst and recovering the thionyl chloride. tetrachloride, of sulfur dioxide at 140 to 200 C. 60 in the liquid phase and at a pressure of fifteen ALBAN THOMAS HALLOWELL, to two hundred atmospheres in the presence of GORDON THEODORE WAALA.