全氯甲硫醇
全氯甲硫醇 | |
---|---|
IUPAC名 Trichloromethyl thiohypochlorite | |
别名 | 三氯甲硫基氯 氯硫基三氯甲烷 硫代次氯酸三氯甲酯 Clairsit |
识别 | |
CAS号 | 594-42-3 |
PubChem | 11666 |
ChemSpider | 11176 |
SMILES | |
InChI | |
UN编号 | 1670 |
EINECS | 209-840-4 |
RTECS | PB0370000 |
性质 | |
化学式 | CCl4S |
摩尔质量 | 185.89 g·mol−1 |
外观 | 黄色油状液体[1] |
气味 | 难闻刺鼻[1] |
密度 | 1.69 g/cm3(20 °C)[1] |
熔点 | -78 °C(195 K)([1]) |
沸点 | 147-149 °C(420-422 K)([1]) |
溶解性(水) | 不溶[1]、反应 |
log P | 3.47(预测) |
蒸气压 | 0.4 kPa(20 °C) |
折光度n D |
1.5395[2] |
偶极矩 | 0.65 D[3] |
危险性 | |
GHS危险性符号 | |
GHS提示词 | Danger |
H-术语 | H301, H311, H312, H314, H330, H335 |
P-术语 | P260, P261, P264, P270, P271, P280, P284, P301+310, P301+330+331, P302+352, P303+361+353, P304+340, P305+351+338, P310 |
NFPA 704 | |
PEL | TWA 0.1 ppm(0.8 mg/m3)[4] |
致死量或浓度: | |
LD50(中位剂量)
|
82.6 mg/kg(大鼠,口服)[5] |
LC50(中位浓度)
|
11 ppm(大鼠,1小时) 16 ppm(大鼠,1小时) 9 ppm(小鼠,3小时) 38 ppm(小鼠,2小时) 11 ppm(大鼠,1 hr) |
LCLo(最低)
|
388 ppm(人类,10分钟) 46 ppm(小鼠,10分钟)[5] |
若非注明,所有数据均出自标准状态(25 ℃,100 kPa)下。 |
全氯甲硫醇是化学式 CCl3SCl的有机硫化合物,主要用于合成染料和抗真菌剂盖普丹和灭菌丹。它是无色且难闻刺鼻的油状液体,不过商购的样本呈黄色。它不溶于水,可溶于有机溶剂。全氯甲硫醇其实是一种硫基氯,不是硫醇。[6]
历史
1915年,法国在香槟战役中把全氯甲硫醇用作化学武器,但很快就因为容易被发现、分解和去除而被淘汰。[7]
制备
全氯甲硫醇是由Rathke于1873年[6]通过氯气和二硫化碳反应发现的,此方法至今仍用于生产全氯甲硫醇。这个反应由碘[8]或氯化氢催化。[9]
- CS2 + 3 Cl2 → CCl3SCl + SCl2
- 2 CS2 + 5 Cl2 → 2 CCl3SCl + S2Cl2
它也可以由氯化二甲硫醚[10]或硫光气[11][12]而成。
反应
全氯甲硫醇会缓慢水解:[13]
- CSCl4 + 2 H2O → CO2 + 4 HCl + 1⁄8 S8
它会被硝酸氧化,生成三氯甲磺酰氯(Cl3CSO2Cl),这是一种白色固体。[7]它在140 °C的二甲苯和三氯化铁催化下用锡[14]或9,10-二氢蒽[15]脱氯,可以合成硫光气。[16]
全氯甲硫醇会和氟化汞或氟化银发生卤素交换反应,生成二氯氟甲硫基氯(CCl2FSCl)[17][18],后者可用来合成抗真菌剂苯氟磺胺和对甲抑菌灵。
危险性
全氯甲硫醇可通过呼吸道、皮肤或口服吸收。它会刺激眼睛、喉咙、支气管和肺泡,也会导致肝脏和肾脏损伤。[19]对大鼠[20][21]和小鼠[22][23]的动物实验表明全氯甲硫醇是剧毒,中毒症状有腹泻、皮肤刺激以及呼吸急促。[24]
参考资料
- ^ 跳转到: 1.0 1.1 1.2 1.3 1.4 1.5 Record of Trichlormethylsulfenylchlorid in the GESTIS Substance Database from the IFA
- ^ Douglass, Irwin B.; Martin, Frederic T.; Addor, Roger. Sulfenyl Chloride studies. II. Mono-, Di-, and Tri-Chloromethanesulfenyl Chlorides and Certain of their Derivatives. The Journal of Organic Chemistry (American Chemical Society (ACS)). 1951, 16 (8): 1297–1302. ISSN 0022-3263. doi:10.1021/jo50002a018.
- ^ Rogers, Max T.; Gross, K. J. The Electric Moments of Some Sulfur and Selenium Compounds. Journal of the American Chemical Society (American Chemical Society (ACS)). 1952, 74 (21): 5294–5296. ISSN 0002-7863. doi:10.1021/ja01141a018.
- ^ NIOSH Pocket Guide to Chemical Hazards. #0489. NIOSH.
- ^ 跳转到: 5.0 5.1 Perchloromethyl mercaptan. Immediately Dangerous to Life and Health Concentrations (IDLH). National Institute for Occupational Safety and Health (NIOSH).
- ^ 跳转到: 6.0 6.1 Committee on Acute Exposure Guideline Levels, Committee on Toxicology, National Research Council, (2011), Acute Exposure Guideline Levels for Selected Airborne Chemicals.
- ^ 跳转到: 7.0 7.1 Sosnovsky, George. The Chemistry Of Trichloromethanesulfenyl Chloride. Chemical Reviews (American Chemical Society (ACS)). 1958, 58 (3): 509–540. ISSN 0009-2665. doi:10.1021/cr50021a003.
- ^ Autenrieth, W.; Hefner, Heinrich. Über Versuche mit Thiophosgen. Berichte der deutschen chemischen Gesellschaft (A and B Series) (Wiley). 1925-10-14, 58 (9): 2151–2156. ISSN 0365-9488. doi:10.1002/cber.19250580935.
- ^ Prakash, G.K.Surya; Hu, Jinbo; Simon, Jurgen; Bellew, Donald R.; Olah, George A. Preparation of α,α-difluoroalkanesulfonic acids. Journal of Fluorine Chemistry (Elsevier BV). 2004, 125 (4): 595–601. ISSN 0022-1139. doi:10.1016/j.jfluchem.2003.11.031.
- ^ Patent Schering DE 416603.
- ^ James, J. William. XXIX.—The action of chlorine on organic thiocyanates. Part I. Methyl thiocyanate. J. Chem. Soc., Trans. (Royal Society of Chemistry (RSC)). 1887, 51 (0): 268–274. ISSN 0368-1645. doi:10.1039/ct8875100268.
- ^ Klason, Peter. Ueber einige schwefelhaltige Derivate des Kohlensäureesters. Berichte der deutschen chemischen Gesellschaft (Wiley). 1887, 20 (2): 2384–2385. ISSN 0365-9496. doi:10.1002/cber.18870200256.
- ^ Greco, C., (1978), Production of perchloromethyl mercaptan, Stauffer ChemicalCompany, Westport, Conn.
- ^ Dyson, G. M. (1926). "Thiophosgene". Org. Synth. 6: 86.
- ^ K. T. Potts, C. Sapino. Thiocarbonyl halides. S. Patai (编). Acyl Halides. PATAI'S Chemistry of Functional Groups. 1972: 349–380. ISBN 9780470771273. doi:10.1002/9780470771273.ch11.
- ^ E. F. Orwoll, US-Patent 2668853.
- ^ Kober, E.: A New Class of Sulfenyl Derivatives; Perhalogenated Aliphatic Sulfenyl Fluorides in J. Am. Chem. Soc. 81 (1959) 4810–4812, doi:10.1021/ja01527a016.
- ^ Ham, N.S.: Dichlorofluoromethanesulfenyl chloride in J. Am. Chem. Soc. 83 (1961) 751–752, doi:10.1021/ja01464a052.
- ^ Fritze, Jürgen. Die ärztliche Begutachtung Rechtsfragen, Funktionsprüfungen, Beurteilungen ; mit 208 Tabellen. Darmstadt. 2008: 296. ISBN 978-3-7985-1563-5. OCLC 199205123 (德语).
- ^ Toxicology and Applied Pharmacology. Vol. 42, S. 417, 1977.
- ^ Sbornik Vysledku Toxixologickeho Vysetreni Latek A Pripravku, Marhold, J.V., Institut Pro Vychovu Vedoucicn Pracovniku Chemickeho Prumyclu Praha, Czechoslovakia, S. 13, 1972.
- ^ Toxicometric Parameters of Industrial Toxic Chemicals Under Single Exposure, Izmerov, N.F., et al., Moscow, Centre of International Projects, GKNT, S. 97, 1982.
- ^ National Technical Information Service. Vol. OTS0533569.
- ^ CID 11666 from PubChem