Fuson, Reynold C. published the artcileLevinstein mustard gas. IV. The bis(2-chloroethyl)polysulfides, Recommanded Product: 1,2-Bis(2-chloroethyl)disulfane, the publication is Journal of Organic Chemistry (1946), 487-98, database is CAplus and MEDLINE.
In the preparation of II according to the L. process, a considerable amount of products with a high S content is formed. These products are considered to consist of bis(2-chloroethyl) polysulfides (XXVII) (cf. Conant, et al., loc. cit.). XXVII are identified and synthesized. H2O2 (503 g., 30%) is slowly added over a period of 2 hrs. to 624 g. XX with stirring and cooling to maintain a temperature of 50-60°. The mixture is kept 2 hrs. and the H2O distilled off in vacuo. Heating the crude (HOCH2CH2)2S2 (XXVIII) with 2800 cc. concentrated HCl on a steam bath for 0.5 hr. gives 94% III, b0.4 97-8°, nD20 1.5656. An apparatus for a continuous process for the preparation of III is described. When to Na2S3, prepared by dissolving 256 g. S and 960 g. Na2S.9II2O in 1300 cc. H2O, 644 g. HOCH2CH2Cl (XXIX) is added over a period of 0.5 hr. with cooling with ice-H2O, the mixture stirred an addnl. 4 hrs., the oily layer separated, and the H2O and excess XXIX are distilled off in vacuo, 80% (HOCH2CH2)2S3 is obtained and is converted with SOCl2 into crude IV which is purified by distillation at 0.01 mm. The fractions with nD 1.59-1.62 are crystallized from absolute EtOH, giving pure IV, m. 30.5-1.5°, nD20 1.6110. When 120 g. II from the Levinstein process is stirred with H2O for 11 days and the H2O frequently changed until the H ion concentration becomes negligible, 29.1% unhydrolyzed XXVII is obtained and dissolved in Cellosolve (XXX). S (77.5 g.) and a small amount of viscous oil are filtered off and the XXX is washed out with H2O, leaving crude (ClCH2CH2)2S5 (XXXI), nD20 1.6763. Calculated on the S recovered, the original XXVII has the composition (ClCH2 CH2)2S7.5. XXXI is further purified by steam distillation to remove any III and IV. The residual XXXI is treated again with XXX, washed with H2O, taken up in ether, and the ether solution dried and evaporated, giving 70% pure XXXI, nD20 1.6853, dD20 1.5013. When IV is treated 6-36 hrs. at temps, ranging from 115-40° with various mol. amounts of S, homogeneous products are obtained. These compounds, when kept in the refrigerator for several days, deposit S in amounts equal to the amount used in excess of that required to form XXXI. Treatment of the products with XXX gives XXXI. III and S at 145-50° for 20-30 hrs. also give XXXI. On treatment of the hydrolysis products of II with XXX, a small amount of alc.-insoluble oil (the analysis of which agrees with C4H8Cl2S11), which slowly deposits S on standing, is obtained. Me2S4, b1.5 68-70°, nD20 1.6621, d420 1.3008, is prepared according to the method of Levi and Baroni (C.A. 23, 4927) in 25% yield. An attempt to sulfurize III with Me2S4 failed. When 0.14 mol. Me2S4 and 0.06 mol. IV are heated at 35-40° and 3-4 mm., Me2S3, nD20 1.5999, slowly distills, and, on raising the temperature to 120° for 2 hrs., 50% XXXI, nD20 1.6850, is obtained. Sulfurization of XXXI with Me2S4 4 hrs. at 75° in a N atm. and finally at 130° several hrs., gives 97% (ClCH2CH2)2S7 (XXXII), nD20 > 1.74, which deposits S upon standing. When treated with NH3, XXXII is reconverted into XXXI. When the sulfurization is carried out by using a large amount of Me2S4, higher polysulfides are formed which lose S rapidly upon standing. When XXXI is subjected to a steam distillation and the residue is allowed to stand for 1 week, no S is deposited. The residue, nD20 1.702, has the composition (ClCH2CH2)2S5.5. When 10 g. XXXI is heated with 9 g. S at 110° for 3 days, (ClCH2CH2)2S12, red viscous oil, is obtained. IV, when shaken with finely divided S, dissolves 4.4% S, while XXXI dissolves 7.4%. In lieu of XXX, moist NH3 can be used for the stripping of XXVII, resulting in the formation of XXXI. When the stripping is carried out with NH3 in the presence of XXX or ether, IV is obtained. When XXXI is refluxed with Me2CO for 2 days, a XXVII is obtained, corresponding approx. to a tetrasulfide, nD20 1.6545. Steam distillation of XXXI gives an impure IV, m. 13°, nD20 1.611. On heating of IV at 145-60° and 0.5 mm., III, nD20 1.5690, distills, leaving a mixture of S and XXVII from which no IV can be isolated. III and IV are quite stable to hydrolysis with H2O. By exhaustive hydrolysis of II from the L. process and stripping the residue with XXX, a mixture of III and XXXI, nD20 1.6740, is obtained. From this nD and on the basis of nD20 1.6835 for XXXI and 1.5656 for III, a content of 1.8% III is calculated for the original II. When 3.1 g. III is slowly added to 5.5 g. com. 90% thiosalicylic acid and 2.6 g. NaOH in 150 cc. 95% EtOH, the mixture refluxed h 1 hr., and poured into 400 cc. H2O, acidification of the solution with dilute HCl precipitates 5.1 g. of a compound, C18H18O4S4, crystals from EtOH, m. 185-6°. Heating 7 g. III in 50 cc. MeOH with 165 g. XXII in 125 cc. MeOH and 15 cc. H2O 2 hrs. on a steam bath gives 92% of a compound, C14H24N2O2S6, fine needles from 95% EtOH, m. 109-10°. III and piperidine give 53% bis[2-(1-piperidyl)ethyl] disulfide, oil, nD20 1.5478 (di-HCl salt, crystals, m. 236°). The structure of XXVII is discussed and it is concluded that III and IV possess a linear structure rather than an angular one. Structure XXXIa is proposed for XXXI.
Journal of Organic Chemistry 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, Recommanded Product: 1,2-Bis(2-chloroethyl)disulfane.
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