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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	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
氣味	难闻刺鼻
密度	1.69 g/cm3（20 °C）
熔点	-78 °C（195 K）（）
沸点	147-149 °C（420-422 K）（）
溶解性（水）	不溶、反应
log P	3.47（预测）
蒸氣壓	0.4 kPa（20 °C）
折光度n; D	1.5395
偶极矩	0.65 D
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	0 3 2
PEL	TWA 0.1 ppm（0.8 mg/m3）
	致死量或浓度：
LD50（中位剂量）	82.6 mg/kg（大鼠，口服）
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）
	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（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

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（德语：Dichlofluanid）和对甲抑菌灵（德语：Tolylfluanid）。

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

^ ^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）
^ 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.
^ ^5.0 ^5.1 Perchloromethyl mercaptan. Immediately Dangerous to Life and Health Concentrations (IDLH). National Institute for Occupational Safety and Health (NIOSH).
^ ^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.
^ ^7.0 ^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

外部链接

CDC - NIOSH Pocket Guide to Chemical Hazards （页面存档备份，存于互联网档案馆）

[GESTIS-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.

[PGCH-4] NIOSH Pocket Guide to Chemical Hazards. #0489. NIOSH.

[IDLH-5] 5.0 ^5.1 Perchloromethyl mercaptan. Immediately Dangerous to Life and Health Concentrations (IDLH). National Institute for Occupational Safety and Health (NIOSH).

[Committeeon-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.

[Sosnovxky-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.

[Greco-13] Greco, C., (1978), Production of perchloromethyl mercaptan, Stauffer ChemicalCompany, Westport, Conn.

[14] Dyson, G. M. (1926). "Thiophosgene". Org. Synth. 6: 86.

[Patai-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）.

[tox3-20] Toxicology and Applied Pharmacology. Vol. 42, S. 417, 1977.

[tox4-21] Sbornik Vysledku Toxixologickeho Vysetreni Latek A Pripravku, Marhold, J.V., Institut Pro Vychovu Vedoucicn Pracovniku Chemickeho Prumyclu Praha, Czechoslovakia, S. 13, 1972.

[tox1-22] Toxicometric Parameters of Industrial Toxic Chemicals Under Single Exposure, Izmerov, N.F., et al., Moscow, Centre of International Projects, GKNT, S. 97, 1982.

[tox2-23] National Technical Information Service. Vol. OTS0533569.

[chemid-24] CID 11666 from PubChem

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PROFILPELAJAR.COM

全氯甲硫醇

历史

制备

反应

危险性

参考资料

外部链接

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