| Revision as of 07:14, 9 April 2012 editBeetstra (talk | contribs)Edit filter managers, Administrators172,084 edits Saving copy of the {{chembox}} taken from revid 485473070 of page Perchloromethyl_mercaptan for the Chem/Drugbox validation project (updated: 'StdInChI', 'StdInChIKey'). |
Latest revision as of 07:14, 25 April 2024 edit WOSlinker (talk | contribs)Administrators858,548 editsm update table header |
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{{ambox | text = This page contains a copy of the infobox ({{tl|chembox}}) taken from revid of page ] with values updated to verified values.}} |
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{{Chembox |
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{{Chembox |
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| Verifiedfields = changed |
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| ImageFile1 = 3Drotatingstuctureofperchloromethylmercaptan.gif |
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| Watchedfields = changed |
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| ImageSize1 =180px |
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| verifiedrevid = 477004453 |
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| verifiedrevid = 486388910 |
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| ImageFile2 = Perchloromethyl mercaptan.svg |
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| ImageFile = Perchloromethyl mercaptan.svg |
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| ImageSize2 = 100px |
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| ImageSize = 140px |
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| ImageAlt = Skeletal formula of perchloromethyl mercaptan |
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| ImageName = |
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| PIN = Perchloromethyl mercaptan |
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| ImageFile1 = Perchloromethyl mercaptan molecule spacefill.png |
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| ImageSize1 = 140 |
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| OtherNames = Trichloromethane sulfenyl chloride<br /> |
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| ImageAlt1 = Space-filling model of the perchloromethyl mercaptan molecule |
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| PIN = Trichloromethyl thiohypochlorite |
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| OtherNames = Trichloromethane sulfenyl chloride<br /> |
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Trichloromethyl sulfur chloride <br /> |
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Trichloromethyl sulfur chloride <br /> |
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Clairsit |
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Clairsit |
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| Section1 = {{Chembox Identifiers |
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|Section1={{Chembox Identifiers |
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| CASNo_Ref = {{cascite|correct|CAS}} |
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| SMILES = ClC(Cl)(Cl)SCl |
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| InChI = 1S/CCl4S/c2-1(3,4)6-5 |
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| CASNo = 594-42-3 |
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| CAS = 594-42-3 |
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| ChEMBL = 3188766 |
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| ChemSpiderID_Ref = {{chemspidercite|correct|chemspider}} |
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| EINECS = 209-840-4 |
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| ChemSpiderID = 11176 |
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| StdInChI = 1S/CCl4S/c2-1(3,4)6-5 |
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| EINECS = 209-840-4 |
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| StdInChIKey = RYFZYYUIAZYQLC-UHFFFAOYSA-N |
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| PubChem = 11666 |
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| PubChem = 11666 |
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| RTECS = PB0370000 |
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| ChemSpiderID = 11176 |
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| UNNumber = 1670 |
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| UNII_Ref = {{fdacite|correct|FDA}} |
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| UNII = KK489OII9M |
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| SMILES = ClC(Cl)(Cl)SCl |
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| InChI = 1S/CCl4S/c2-1(3,4)6-5 |
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| StdInChI_Ref = {{stdinchicite|correct|chemspider}} |
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| StdInChI = 1S/CCl4S/c2-1(3,4)6-5 |
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| StdInChIKey_Ref = {{stdinchicite|correct|chemspider}} |
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| StdInChIKey = RYFZYYUIAZYQLC-UHFFFAOYSA-N |
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}} |
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}} |
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| Section2 = {{Chembox Properties |
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|Section2={{Chembox Properties |
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| C = 1 | S = 1 | Cl = 4 |
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| C=1 | S=1 | Cl=4 |
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| Appearance = Oily, yellow liquid |
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| Molecular weight = 185.87 |
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| Odor = disagreeable, acrid odor |
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| Appearance = Oily, yellow liquid |
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| Density = 1.72 g/cm<sup>3</sup> |
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| Odor = disagreeable, acrid odor |
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| Solubility = Insoluble, reacts |
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| Density = 1.72 g/cm<sup>3</sup> |
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| SolubleOther = |
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| Solubility in water = insoluble |
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| MeltingPtC = -44 |
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| SolubleOther = |
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| BoilingPtC = 147 to 148 |
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| MeltingPtC = -44 |
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| VaporPressure = 0.4 kPa (at 20 °C) |
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| BoilingPtC = 147-148 |
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| VaporPressure = 0.4 kPa (at 20 °C) |
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| LogP = 3.47 (estimated) |
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| Dipole = |
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| LogP = 3.47 (estimated) |
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| Dipole = |
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| RefractIndex = |
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| RefractIndex = |
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| HenryConstant = |
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| HenrysConstant = |
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}} |
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}} |
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| Section7 = {{Chembox Hazards |
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|Section7={{Chembox Hazards |
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| ExternalMSDS = |
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| ExternalSDS = |
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| NFPA-H = 3 |
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| EUIndex = |
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| NFPA-F = 0 |
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| EUClass = {{Hazchem T}} {{Hazchem N}} |
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| NFPA-H = 3 |
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| NFPA-R = 2 |
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| GHSPictograms = {{GHS05}}{{GHS06}}{{GHS07}} |
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| NFPA-F = 0 |
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| NFPA-R = 2 |
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| GHSSignalWord = Danger |
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| HPhrases = {{H-phrases|301|311|312|314|330|335}} |
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| RPhrases = {{R21}} {{R25}} {{R26}} {{R34}} |
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| PPhrases = {{P-phrases|260|261|264|270|271|280|284|301+310|301+330+331|302+352|303+361+353|304+340|305+351+338|310|312|320|321|322|330|361|363|403+233|405|501}} |
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| SPhrases = {{S25}} {{S28}} {{S36/37/39}} {{S45}} |
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| FlashPt = |
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| FlashPt = |
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| Autoignition = |
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| AutoignitionPt = |
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| IDLH = 10 ppm<ref name=PGCH>{{PGCH|0489}}</ref> |
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| LC50 = 11 ppm (rat, 1 hr)<br/>16 ppm (rat, 1 hr)<br/>9 ppm (mouse, 3 hr)<br/>38 ppm (mouse, 2 hr)<br/>11 ppm (rat, 1 hr)<ref name=IDLH>{{IDLH|594423|Perchloromethyl mercaptan}}</ref> |
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| LD50 = 82.6 mg/kg (rat, oral)<ref name=IDLH/> |
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| REL = TWA 0.1 ppm (0.8 mg/m<sup>3</sup>)<ref name=PGCH/> |
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| PEL = TWA 0.1 ppm (0.8 mg/m<sup>3</sup>)<ref name=PGCH/> |
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| LCLo = 388 ppm (human, 10 min)<br/>46 ppm (mouse, 10 min)<ref name=IDLH/> |
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}} |
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| Section8 = {{Chembox Related |
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|Section8={{Chembox Related |
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| OtherFunction_label = |
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| Function = |
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| OtherFunctn = |
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'''Perchloromethyl mercaptan''' is the organosulfur compound with the formula '''CCl<sub>3</sub>SCl'''. It is mainly used as an intermediate for the synthesis of dyes and fungicides (], ]). It is a colorless oil, although commercial samples are yellowish. It is insoluble in water but soluble in organic solvents. It has a foul, unbearable, acrid odor. Perchloromethyl mercaptan is the original name. The systematic name is trichloromethanesulfenyl chloride, because the compound is a ], not a ].<ref name="Committeeon" /> |
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==History== |
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It was used as a ] agent by the French in the 1915 battle of Champagne. Shortly thereafter, wartime use was abandoned due to the clear warning properties, the decomposition in the presence of iron and steel, and the easy removal of the vapor by charcoal.<ref name="Sosnovxky">Sosnovsky, George "The chemistry of trichloromethanesulfenyl chloride" Chemical Reviews 1958, volume 58, 509-40. {{doi|10.1021/cr50021a003}}</ref> |
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==Preparation== |
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The method to prepare perchloromethyl mercaptan was first described by Rathke in 1873<ref name="Committeeon" /> and is still used. ] is chlorinated using an iodine catalyst. The following equations operate most efficiently at temperatures below about 30 °C |
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:CS<sub>2</sub> + 3 Cl<sub>2</sub> → CCl<sub>3</sub>SCl + SCl<sub>2</sub> |
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:2 CS<sub>2</sub> + 5 Cl<sub>2</sub> → 2 CCl<sub>3</sub>SCl + S<sub>2</sub>Cl<sub>2</sub> |
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At higher temperatures, the chlorination gives ] and additional sulfur chlorides.<ref>Manchiu D. S. Lay, Mitchell W. Sauerhoff And Donald R. Saunders "Carbon Disulfide" in Ullmann's Encyclopedia Of Industrial Chemistry, 2000, Wiley-VCH, Weinheim. |
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{{doi|10.1002/14356007.a05_185}}</ref> The formation of byproducts can be suppressed by performing the reaction in the presence of ]s.<ref name="Greco">Greco, C., (1978), Production of perchloromethyl mercaptan, Stauffer ChemicalCompany, Westport, Conn.</ref> Another byproduct is ]. The more volatile byproducts such as carbon tetrachloride and ] can be removed by ]. The separation of perchloromethyl mercaptan from ] by distillation is challenging since their ] are very close. Another byproduct that forms is ]. Innovations in the basic Rathke method have been reported.<ref name="Greco" /> |
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==Reactivity== |
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The compound slowly hydrolyzes:<ref name="Greco" /> |
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:CSCl<sub>4</sub> + 2 H<sub>2</sub>O → CO<sub>2</sub> + 4 HCl + {{frac|1|8}} S<sub>8</sub> |
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The compound is corrosive to most metals. It reacts with iron, evolving carbon tetrachloride. Perchloromethyl mercaptan is oxidized by nitric acid to trichloromethanesulfonyl chloride (Cl<sub>3</sub>CSO<sub>2</sub>Cl), a white solid.<ref name="Sosnovxky" /> |
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==Toxicity== |
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{| class="wikitable" |
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!Animal |
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!Oral |
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!Inhalation |
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!Intraperitoneal |
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!Intravenous |
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!Skin |
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!Eyes |
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|- bgcolor="moccasin" |
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| Rat |
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| 82,6 mg/kg |
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| 11 ppm/1h |
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| 25 mg/kg |
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| Mouse |
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| 40 mg/kg |
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| 296 g/m<sup>3</sup>/2h |
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| 10 mg/kg |
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| 56 mg/kg |
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| Rabbit |
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| 1410 mg/kg |
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| Guinea Pig |
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| 500 μL/kg |
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| 50 μg/24h<ref>Catalog of Chemical Suppliers, Custom Synthesis Companies and Equipment |
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Manufactures.</ref> |
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When it is heated or in a fire, it will emit toxic and corrosive gases. It is also very toxic by inhalation or skin absorption.<ref name="Committeeon">Committee on Acute Exposure Guideline Levels, Committee on Toxicology, National Research Council, (2011), Acute Exposure Guideline Levels for Selected Airborne Chemicals.</ref> |
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At least two mechanisms could account for the toxicity of perchloromethyl mercaptan, as hypothesized by Althoff (1973). The first mechanism is a reaction between perchloromethyl mercaptan and biological functional groups such as hydroxyl, sulfhydryl, amino and carboxyl groups. This results in an inactivation of key enzymes. A second general pathway reaction is the hydrolysis to give hydrochloric acid.<ref name="Committeeon" /> |
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==References== |
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{{Reflist}} |
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==External links== |
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* |
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{{Chemical agents}} |
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] |
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] |
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] |