全氯甲硫醇

全氯甲硫醇
Skeletal formula of perchloromethyl mercaptan
Space-filling model of the perchloromethyl mercaptan molecule
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  checkY
PubChem 11666
ChemSpider 11176
SMILES
 
  • ClC(Cl)(Cl)SCl
InChI
 
  • 1S/CCl4S/c2-1(3,4)6-5
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]
氣味 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 不溶[1]、反应
log P 3.47(预测)
蒸氣壓 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
《全球化学品统一分类和标签制度》(简称“GHS”)中腐蚀性物质的标签图案《全球化学品统一分类和标签制度》(简称“GHS”)中有毒物质的标签图案《全球化学品统一分类和标签制度》(简称“GHS”)中有害物质的标签图案
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
0
3
2
 
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灭菌丹英语folpet。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英语sulfenyl chloride,不是硫醇[6]

历史

[编辑]

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

[编辑]

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[8]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]硫光气[11][12]而成。

反应

[编辑]

全氯甲硫醇会缓慢水解:[13]

CSCl4 + 2 H2O → CO2 + 4 HCl + 18 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的二甲苯三氯化铁催化下用[14]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德语Dichlofluanid对甲抑菌灵德语Tolylfluanid

危险性

[编辑]

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

[编辑]
  1. ^ 1.0 1.1 1.2 1.3 1.4 1.5 Record of Trichlormethylsulfenylchlorid in the GESTIS Substance Database from the IFA英语Institute for Occupational Safety and Health
  2. ^ 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. 
  3. ^ 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. 
  4. ^ NIOSH Pocket Guide to Chemical Hazards. #0489. NIOSH. 
  5. ^ 5.0 5.1 Perchloromethyl mercaptan. Immediately Dangerous to Life and Health Concentrations (IDLH). National Institute for Occupational Safety and Health (NIOSH). 
  6. ^ 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.
  7. ^ 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. 
  8. ^ 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. 
  9. ^ 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. 
  10. ^ Patent Schering DE 416603.
  11. ^ 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. 
  12. ^ 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. 
  13. ^ Greco, C., (1978), Production of perchloromethyl mercaptan, Stauffer ChemicalCompany, Westport, Conn.
  14. ^ Dyson, G. M. (1926). "Thiophosgene". Org. Synth. 6: 86. 
  15. ^ 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. 
  16. ^ E. F. Orwoll, US-Patent 2668853.
  17. ^ 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.
  18. ^ Ham, N.S.: Dichlorofluoromethanesulfenyl chloride in J. Am. Chem. Soc. 83 (1961) 751–752, doi:10.1021/ja01464a052.
  19. ^ Fritze, Jürgen. Die ärztliche Begutachtung Rechtsfragen, Funktionsprüfungen, Beurteilungen ; mit 208 Tabellen. Darmstadt. 2008: 296. ISBN 978-3-7985-1563-5. OCLC 199205123 (德语). 
  20. ^ Toxicology and Applied Pharmacology. Vol. 42, S. 417, 1977.
  21. ^ Sbornik Vysledku Toxixologickeho Vysetreni Latek A Pripravku, Marhold, J.V., Institut Pro Vychovu Vedoucicn Pracovniku Chemickeho Prumyclu Praha, Czechoslovakia, S. 13, 1972.
  22. ^ Toxicometric Parameters of Industrial Toxic Chemicals Under Single Exposure, Izmerov, N.F., et al., Moscow, Centre of International Projects, GKNT, S. 97, 1982.
  23. ^ National Technical Information Service. Vol. OTS0533569.
  24. ^ CID 11666 from PubChem

外部链接

[编辑]