94 COFFEY THE ACTION OF THE CHLORIDES OE’ X.-The Action of the Chlorides of Sulphur on Substituted Ethylenes. T h e Action of Propylene on Sulphur &lonochloride and the Synth esiv o j Pp’- DicILIoyodi-n-propyl Sulphide. By SAMUEL COFFEY. GUTHRIE (Quart. Journ. Chem. SOC. 1859 12 116) by the action of ethylene on sulphur dichloride obtained impure @PI-dichlorodi-ethyl sulphide. Later (ibid. 1860 13 134) he obtained the disul-phide by the action of ethylene on sulphur monochloride at looo, but higher chlorinated products and tar were also formed in large quantity. In a recent communication Gibson and Pope (T. 1920, 117 271) have shown that sulphur monochloride and ethylene between the ordinary temperature and 70° give /3/3/-dichlorodiethyl sulphide whereas above 70° the liquid darkens and hydrogen chloride is evolved as in Guthrie’s reaction.Apart from the work mentioned above nothing is known of the reactions involved when sulphur chlorides act on olefines although the action of “ sulphur chloride ” on oils etc. has long been used as a “thermal” test for unsaturation. The aim of these investigations of which this is only a preli-minary communication is to study the action of sulphur chlorides on substituted ethylenes to find the effect of the substituent on the course of the reaction with a view to elucidate the complex changes which doubtless are involved in the thermal test mentioned above. Considering the mono-substituted ethylenes the compounds most likely to be produced are of the types: CHRCl*CH,*S*S-CH,*C€IRCl CH,Cl*CHR*S S - CHR*CH,Cl (1.1 (11.) (CHRCl*CH,),S (111.) (CH,Cl* CHR),S (IV.SULPHUR ON SUBSTITUTED ETHYLENES 95 The course of the reaction will no doubt depend on the temperature and the electrochemical character of the substituent group. In the case of a monoalkyl-ethylene such as propylene for example the electropositive methyl group should cause the second-ary chloride to be produced as the main product as in the case of iodine chloride (Michael J . p r . Ckem. 1892 [ii] 46 345) and theref ore the probable products wiIl be /3B’-dichlorodi-n-propyl disulphide (type I) and @B/-dichlorodi-n-propyl sulphide (type 111). Attempts to prepare these substances by the action of propylene on sulphur monochloride were not very successful but a small quantity of /3/3/-dichlorodi-n-propyl disulphide was obtained from which a barium chloropropa.nes~lphonate was produced on oxida-tion.BP’-Dichlorodi-n-pro~~l sulphide which was not formed in this reaction was prepared from propylene chlorohydrin by Clarke’s modification of V. Meyer’s method (T. 1912 101 1583) for the production of BP/-dichlorodiethyl sulphide : CH,*CH (OH) *CH,Cl+ (C Ht-CH[OH]*CH2)2S + (V.) (CH,*CHCl*CH,),S. (VI.) E X P E R I M E N T A L . Action of Yropylene on Sulphur Monochloride. The sulphur monochloride was repeatedly distilled from sulphur and finally fractionated in a vacuum over charcoal; 2.5 per cent. of sulphur was dissolved in the amber-coloured liquid. The propylene was prepared by the action of phosphoric acid on isopropyl alcohol (Newth T.1901 79 915). The dried propylene was passed into the sulphur monochloride (40 grams) a t a rate of about a litre per hour the absorption vessels being kept a t constant temperature. A t 60° the sulphur monochloride soon became brown and gela-tinous and finally changed into a viscid black product through which the gas would not pass. During the whole time much hydro-gen chloride was evolved. When distilled in a current of steam the product furnished only about 1 gram of volatile oil. In the next experiment the absorption was started a t 40° and the temperature was never allowed to rise above 50°. Ten litres of gas (approximately 20 grams) were passed through three tubes each of which contained 15 grams of sulphur monochloride before all the chloride had become dark brown and semi-solid.The product was extracted with chloroform and then distilled (18-25 mm.) when a small quautity (5 grams) of a red oil ( A ) passed over a t 113-120° 96 COFBEY THE ACTION OF THE CHLORIDES OF The residue was a black tar (more than 25 grams). During the distillation much hydrogen chloride was evolved. The distillate a t first pale yellow gradually became red as it passed over. It was vigorously oxidised by concentrated nitric acid (D 1.4) in the cold but nothing but a little sulphur separated on dilution. Thus the reaction was totally different from that of nitric acid on PB'-dichlorodi-n-propyl sulphide (p. 97). The filtered solution was evaporated until free from nitric acid, when a pale yellow viscous strongly acid liquid was left.This was diluted wfih water boiled with barium carbonate and the filtrate evaporated to incipient crystallisation when a barium salt separated on cooling. 'The barium salt was only sparingly soluble in alcohol but readily s3 in cold water or hot 75 per cent. alcohol from which it crystal-lised in colourless nacreous plates. It contained sulphur and chlorine and on treatment with phosphorus pentachloride gave a very easily hydrolysable sulphonyl chloride (Found in air-dried salt H20 = 5-25 (C3H,03C1S),Ba,l~&0 requires H20 = 5.6 per cent. Found in anhydrous salt Ba = 30-7. (C,H,O&lS),Ba requires Ba = 30.4 per cent.). This was theref ore the barium salt of a chloropropanesulphonic acid and the original substance was in all probability BPI-dichloro-di-n-propyl disulphide.A little barium sulphate was also obtained. BP'-l)ihydroxydi-n-propyl Sdphide (V) . Propplene chlorohydrin was prepared from ally1 chloride by Oppenheim's method (Annalen Suppl. 1868 6 367) for as Smith (Zeitsch. physikal. Chem. 1918 93 59) has shown recently this is the only method which does not give a mixture of a- and j3-chloro-hydrins. Twelve grams of propylene chlorohydrin were gradually added to 37 grams of crystallised sodium sulphide dissolved in an equal weight of water. The mixture became warm and was cooled in water but after a short time the development of heat ceased. The mixture was heated on a water-bath for one and a-half hours; a pale brown oil gradually separated but partly redissolved on cool-ing.The product was then just acidified with hydrochloric acid. The slightly turbid solution was distilled in a vacuum when a yellow oil gradually separated along with sodium chloride. The residue was shaken with alcohol and the extract evaporated in a vacuum until no more distilled. The pB'-clTihydroxydi-n-propyl sul-phi& was left as a non-volatile pale yellow viscous liquid soluble in water or alcohol and heavier than water. The product was no SULPliUR O N SUBSTITUTED ETHYLENES. 97 purified further but used for the preparation of P@’-dichlorodi-n-propyl sulphide. The yield was 80 per cent. of $he theoretical. PB’-DichloroJ.i-n-propy~ Sulphide (VI). The preceding compound (9 grams) was added to Concentrated hydrochloric acid (70 c.c.) when a pale pink turbid solution was produced.This was then heated on a water-bath for one and a-half hours when it gradually became more and more turbid and a heavy dark brown oil gradually separated. It was extracted with chloroform and distilled in a vacuum when a colourless oil, boiling a t 122O/23 mm. passed over. When the temperature quickly rose Lo 126O/23 mm. bhe distillation was stopped. The yield of BP’-dichlorodi-n-propgl sulphide was 7 grams and the residue amounted to less than 1 gram. PPt-Uichlorodi-n-propyl sidphide is a colourless oil boiling a t 122O/23 mm. which does not freeze on cooling to -8O for half an hour. It has properties very similar to its lower homologue “ mus-tard gas,” except that apparently it has no vesicant action (Found, C1= 38.10.C,H,,Cl,S requires C1= 37.90 per cent.). When heated with alcoholic potassium hydroxide solution the chlorine is displaced quantitatively with the production of the dihydroxy-compound. Oxidation of P13f-DichZorodCn-propyl Sulphide. When added to an excess of nitric acid (D 1-4) oxidation took place smoothly and a clear solution was obtained. On leaving for twenty-four hours and diluting a heavy viscid oil separated which from its solubility in concentrated acid and insolubility on dilution appeared to be the sulphoxide (compare Davies T. 1920 117, 299). In the hope t,hat some crystalline compound might be obtained this oil was heated for some time a t 100° with more con-centrated nitric acid. A rather vigorous oxidation took place and on dilution a little oil ssparated; on concentrating the clear solu-tion a solid melting at.10Q-102° crystallised which was in all probability the corresponding sulphone. Another product of the reaction was sulphuric acid showing that under these conditions BPI-dichlorodi-n-propyl sulphide is corn-pletely decomposed. ADDENDUM. Since these results were obtained a paper by Conant Hartshorn, and Richardson ( J . -47nw. Chent. Soc. 1920 42 485) has appearzd, VOL. CXIX. i n which it is shown that t,he production of PB’-dichlorodiethyl sul-phide involves two reactions. An intermediate product, CH,Cl=CH,*SCl has been obtained from ethylene and sulphur dichloride which evolves hydrogen chloride very easily and when warmed with sulphur gives a black tar. In the case of sulphur monochloride a similar product is obtained and unless the sulphur is crystallised from the colloidal solution after the reaction a black tar (CH,Cl*CH,),S, is formed. The results given in this paper are in agreement with those described above and probabIy a similar series of reactions takes place in. the case of propylene to some extent but flD’-dichlorodi-n-propyl sulphide has not yet been detected. The author desires to express his indebtedness to Professor F. 5. THE CHEMICAL DEPARTMENT, Kipping F.R.X. for his interest in and criticisms of this work. UNIVERSITY COLLEGE, NOTTINUHAM. [Received December 9th 1920.