Pernot, Robert published the artcileThe reaction of ethylene with sulfur monochloride (S2Cl2) and with sulfur dichloride (S2Cl2 + Cl2) in the preparation of bis(2-chloroethyl) sulfide (mustard gas), Safety of 1,2-Bis(2-chloroethyl)disulfane, the publication is Ann. chim. [12] (1946), 626-57, database is CAplus.
Crude mustard gas (I) as obtained in the Levinstein process is a clear yellow liquid, m. 10.5°, which does not deposit a trace of S when kept for over a year. On distillation in vacuo I gives 70% pure (ClCH2CH2)2S.(II), m. 13.5°. I is only partially soluble in EtOH or ether. The m.p. is only slightly affected when byproducts are present. When 500 g. I is extracted with 500 cc. EtOH, 208 g. remains undissolved. On cooling the alc. solution, 130 g. II, m. 13.3°, crystallizes. When 500 g. I is cooled with ice-NaCl, 245 g. II, m. 12.5°, crystallizes. Distillation of 323 g. I gives 2 fractions, (a) 185 g., b18 110-15°, m. 13.3°, and (b) 40 g., b18 115-55°, m. 3.8°, the residue decomposing Redistillation of 40 g. of fraction a gives a fraction (c) 25 g., b18 110-15°, and 12 g., b18 120-35°, the latter being chiefly (ClCH2CH2)2S2 (III). Distillation of the EtOH solution gives II, but no III or (ClCH2CH2)2S3 (IV) is present. From the EtOH-insoluble part no definite product can be isolated even on distillation at 1 mm. It still contains a small amount of II which is removed by careful oxidation with H2O2, whereby II is oxidized to the H2O-soluble sulfoxide while III and IV remain unchanged. The elementary composition of the residue after treatment with H2O2 corresponds to (ClCH2CH2)2S8 (V) which may be formed according to the following equation: 7S2Cl2 + 14C2H4 → 6 II + V. Treatment of 86 g. EtOH-insoluble product with moist NH3 according to Felsing and Arenson (C.A. 15, 54) causes the separation of 16.5 g. S. The recovered product, now soluble in ether and C6H6, is free of N and has a composition corresponding to (ClCH2CH2)2S4 (VI). VI does not deposit S even after standing 6 mo. When VI is heated with S, the latter dissolves and seps. again on cooling. In an attempt to hydrolyze VI with alc. KOH no definite compound is formed. When VI is treated with Me2CO, S is deposited with the formation of IV, m. 27°. IV is also formed when VI is treated with steam at 100 mm. An attempt to oxidize IV with BzO2H, to transfer it into the iodine compound by heating it with NaI in a sealed tube, or to condense IV with PhONa or BzONa failed. Distillation of 50 g. IV at 1 mm. gives 40 g. yellow liquid, b1 120-35°. Redistillation of the latter gives 2 fractions, (d) 10 g., b1 up to 120°, and (e) 28 g., b1 120-6°, containing chiefly IV, m. 26.5°. IV prepared according to Mann, et al. (C.A. 15, 2413), m. 25°; the mixed m.p. of the 2 preparations is 26°. When IV is heated with the theor. amount of S to form VI, the S dissolves but seps. again on cooling. IV when distilled at 40 mm. gives a small amount of III, b. 160-5°, which is not attacked by H2O2. When distilled at atm. pressure III gives a very small amount of II. These results show that III has the structure (ClCH2CH2S)2 and not (ClCH2CH2)2S:S, while IV has the structure ClCH2CH2S(:S)SCH2CH2Cl. When 220 g. EtOH-insoluble product is extracted 5 times with 200 cc. pure and dry Me2CO and the Me2CO is evaporated, 80 g. of yellow oil is obtained from which some (ClCH2CH2)2SO crystallizes. The residual oil has a composition corresponding to (ClCH2CH2)2S5 (VII) and is insoluble in EtOH, petr. ether, and AcOH. Pyridine precipitates 8.5 g. S from 43 g. VII. Evaporation of the pyridine leaves an oil which on distillation at 3 mm. gives a mixture of III and IV. The Me2CO-insoluble part (140 g.), when cooled, deposits 16 g. S. The filtrate consists of a polysulfide or a mixture of polysulfides high in S content (75.7-6.7%). The hypothesis that II is formed according to the equation S2Cl2 + 2C2H4 → II + S is not substantiated by the action of C2H4 upon S5Cl2. When 580 g. S5Cl2 is treated with C2H4, 733 g. reaction product is obtained from which 207 g. S deposits, giving 526 g. reaction product. From 342 g. S2Cl2, which equals 580 g. S5Cl2, and 142 g. C2H4, 484 g. reaction product is calculated while 526 g. is obtained. These results indicate that S5Cl2 reacts in the same way as S2Cl2. The following reaction mechanism is proposed: S2Cl2 + 3C2H4 gives a sesquimustard gas, (CH2SCH2CH2Cl)2 (VIII). VIII reacts with S2Cl2 to give 1 mol. II and ClSS2CH2CH2Cl (IX); IX + C2H4 → IV. IV + S2Cl2 → Cl.S.CH2CH2Cl (X) + ClS4CH2CH2Cl (XI); XI + C2H4 → II + VI, etc. SCl2 + C2H4 gives 85% crude reaction product (XII), m. 5-8°. Distillation of 109.5 g. XII, m. 5.5°, gives 3 fractions: (f) 97.5 g., b10 93-6°, m. 10°; (g) 4.5 g., b10 96-105°; and 3.5 g. residue. Redistillation of 90 g. f gives a fraction, 76.5 g., b12 97-8°, m. 10°, which on redistillation gives 62.3 g., b13 101-2°, m. 10.2°, and 11.4 g., b15 102-4°, m. 11.8°. This indicates that with II other products come over. Because under the conditions used, SCl2 can be considered to be a solution of Cl in a mixture of SCl2 and S2Cl2, byproducts containing α-chlorinated compounds are formed which split off HCl with formation of ClCH:CHSCH2CH2Cl (XIII). II containing 8.8% XIII m. 9.9°. When SCl2 in a 10% CCl4 solution and C2H4 are allowed to react and the reaction product is distilled after the CCl4 has been removed at 120°, II, b10 93.5-4°, m. 10.8°, is obtained. When 800 g. of the reaction product is extracted with EtOH only 31 g. insoluble product (XIV) is obtained. When Cl is passed into 250 g. XIV, the temperature rises to 45-50°. As soon as the temperature drops to room temperature the Cl current is stopped and the reaction product distilled in vacuo. Up to 70°/15 mm. the S-Cl compounds distill, and between 98° and 100° a few cc. of a turbid liquid distills. When C2H4 is passed at 30-40° into the residue, a vigorous reaction takes place. After the active Cl in the residue has disappeared, 303 g. of a clear red solution is obtained. Distillation of 238 g. of this solution gives 3 fractions: (h) 12.6 g., b13 40-97°; (i) 76.6 g., b13 97-107°; (j) 8.2 g., b13 107-25°. Redistillation of i gives a product, b13 98-101°, m. 8.6°. Oxidation of 4.3 g. of this product with H2O2 at 50° in AcOH gives 1.2 g. of a sulfoxide, m. 108°, which when mixed with the sulfoxide of II, m. 108°. These results indicate that the Cl splits the polysulfides, ClCH2CH2S(:Sx)S(:Sy)CH2CH2Cl, to give 2 mols. X, while the S is converted into SCl2 which again reacts with C2H4 with excess formation of a certain amount of II. On the other hand, the Cl also reacts with X, giving rise to the formation of XIV.
Ann. chim. [12] published new progress about 1002-41-1. 1002-41-1 belongs to chlorides-buliding-blocks, auxiliary class Aliphatic Chain, name is 1,2-Bis(2-chloroethyl)disulfane, and the molecular formula is C4H8Cl2S2, Safety of 1,2-Bis(2-chloroethyl)disulfane.
Referemce:
https://en.wikipedia.org/wiki/Chloride,
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