Browse history interactively

Page 1

Page 1Revision 1

Page 2

Page 2Revision 2

← Previous editContent deleted Content addedVisualWikitext

Revision as of 04:42, 16 August 2011 edit200.144.75.5 (talk) →Synthesis of CSCl2← Previous edit		Latest revision as of 04:28, 24 December 2024 edit undoBeland (talk | contribs)Autopatrolled, Administrators236,629 editsm convert special characters found by Misplaced Pages:Typo Team/moss (via WP:JWB)
(76 intermediate revisions by 41 users not shown)
Line 1:		Line 1:
	{{chembox		{{chembox
			| Watchedfields = changed
	| verifiedrevid = 444226056		| verifiedrevid = 445098555
⚫	| Name = Thiophosgene
	| ImageFile_Ref = {{chemboximage|correct|??}}		| Name = Thiophosgene
			| ImageFile_Ref = {{chemboximage|correct|??}}
	| ImageFileL1_Ref = {{chemboximage|correct|??}}		| ImageFileL1_Ref = {{chemboximage|correct|??}}
			| ImageFile =
	| ImageFileL1 = Thiophosgene-2D.png		| ImageFileL1 = Thiophosgene-2D.png
	| ImageSizeL1 = 120px		| ImageSizeL1 = 126px
	| ImageNameL1 = Thiophosgene		| ImageNameL1 = Thiophosgene
	| ImageFileR1 = Thiophosgene-3D-vdW.png		| ImageFileR1 = Thiophosgene-3D-vdW.png
	| ImageSizeR1 = 100px		| ImageSizeR1 = 116px
	| ImageNameR1 = Thiophosgene		| ImageNameR1 = Thiophosgene
		⚫	| ImageFile2 = Thiophosgene.png
	| IUPACName = Carbonothioyl dichloride
	| OtherNames = Thiophosgene; Thiocarbonyl chloride; Carbonothioic dichloride		| IUPACName = Carbonothioyl dichloride
			| OtherNames = Thiophosgene; Thiocarbonyl chloride; Carbonothioic dichloride
			| SystematicName =
	| Section1 = {{Chembox Identifiers		| Section1 = {{Chembox Identifiers
	| UNII_Ref = {{fdacite|correct|FDA}}		| UNII_Ref = {{fdacite|correct|FDA}}
	| UNII = 067FQP576P		| UNII = 067FQP576P
	| ChEBI_Ref = {{ebicite|correct|EBI}}		| ChEBI_Ref = {{ebicite|correct|EBI}}
	| ChEBI = 29366		| ChEBI = 29366
	| SMILES = ClC(Cl)=S		| SMILES = ClC(Cl)=S
	| ChemSpiderID_Ref = {{chemspidercite|correct|chemspider}}		| ChemSpiderID_Ref = {{chemspidercite|correct|chemspider}}
	| ChemSpiderID = 9645		| ChemSpiderID = 9645
	| PubChem = 10040		| PubChem = 10040
Line 28:		Line 32:
	| StdInChIKey = ZWZVWGITAAIFPS-UHFFFAOYSA-N		| StdInChIKey = ZWZVWGITAAIFPS-UHFFFAOYSA-N
	| CASNo = 463-71-8		| CASNo = 463-71-8
	| CASNo_Ref = {{cascite|correct|CAS}}		| CASNo_Ref = {{cascite|correct|CAS}}
	| RTECS = XN2450000		| RTECS = XN2450000
	}}		}}
	| Section2 = {{Chembox Properties		| Section2 = {{Chembox Properties
	| Formula = CSCl<sub>2</sub>		| Formula = {{chem2|CSCl2}}
			| C=1|S=1|Cl=2
	| MolarMass = 114.98 g/mol
	| Appearance = Red liquid		| Appearance = Red liquid
			| Odor = Persistent, choking odor
	| Density = 1.50 g/cm<sup>3</sup>		| Density = 1.50 g/cm<sup>3</sup>
	| Solubility = Decomp.		| Solubility = Decomposes
	| Solvent = other solvents		| Solvent = other solvents
	| SolubleOther = polar organic solvents<br />rxn with amines and alcohols
			| SolubleOther = Reacts with amines and alcohols, soluble in polar organic solvents
	| MeltingPt =		| MeltingPt =
	| BoilingPt = 70–75 °C
			| BoilingPtC = 70 to 75
⚫	| Viscosity =
			| BoilingPt_notes =
⚫	| RefractIndex = 1.548
		⚫	| Viscosity =
		⚫	| RefractIndex = 1.558
			| MagSus = -50.6·10<sup>−6</sup> cm<sup>3</sup>/mol
	}}		}}
	| Section3 = {{Chembox Structure		| Section3 = {{Chembox Structure
	| MolShape = planar, sp<sup>2</sup>, C<sub>2v</sub>		| MolShape = planar, sp<sup>2</sup>, C<sub>2v</sub>
	| Dipole =		| Dipole =
	}}		}}
			| Section4 =
			| Section5 =
			| Section6 =
	| Section7 = {{Chembox Hazards		| Section7 = {{Chembox Hazards
	| ExternalMSDS =		| ExternalSDS =
	| EUIndex = Not listed		| MainHazards = Highly toxic
			| FlashPtC = 62
	| MainHazards = Highly toxic
	| FlashPt = 62 °C		| HPhrases =
	| RPhrases =		| PPhrases =
	| SPhrases =		| GHS_ref =
	}}		}}
	| Section8 = {{Chembox Related		| Section8 = {{Chembox Related
	| OtherCpds = ]<br/>]<br/>]		| OtherCompounds = {{ubl|]|]|]|]|]}}
	}}		}}
	}}		}}
		⚫	'''Thiophosgene''' is a red liquid with the formula {{chem2|CSCl2}}. It is a molecule with trigonal planar geometry. There are two reactive C–Cl bonds that allow it to be used in diverse ].<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.
			{{doi|10.1002/14356007.a05_185}}</ref>
			== Preparation ==
⚫	'''Thiophosgene''' is a red liquid with the formula CSCl<sub>2</sub>. It is a molecule with trigonal planar geometry. There are two reactive C–Cl bonds that allow it to be used in diverse ].
		⚫	Typically, {{chem2|CSCl2}} is prepared in a two-step process from ]. In the first step, carbon disulfide is ] to give ] ({{chem2|CCl3SCl}}), a rare ]:
			:{{chem2|CS2 + 3 Cl2 → CCl3SCl + ]}}
			The chlorination must be controlled as excess chlorine converts trichloromethanesulfenyl chloride into ]. Steam distillation separates the trichloromethanesulfenyl chloride and hydrolyzes the disulfur dichloride. Reduction of trichloromethanesulfenyl chloride with, e.g., ]<ref>{{OrgSyn|last = Dyson|first = G. M.|year = 1926|title = Thiophosgene|volume = 6|pages = 86|doi = 10.15227/orgsyn.006.0086}}</ref> or ]<ref name=Patai>{{cite book|title= Acyl Halides|editor=S. Patai|year=1972|doi=10.1002/9780470771273.ch11|series=PATAI'S Chemistry of Functional Groups|chapter=Thiocarbonyl halides|author=K. T. Potts, C. Sapino|pages=349–380|isbn=978-0-470-77127-3}}</ref> produces thiophosgene:
			:{{chem2|CCl3SCl + M → CSCl2 + MCl2}}
			An alternative one-step reaction is<ref>Graham-Otto's ''Ausführliches Lehrbuch der Chemie'' (in German; 1881). Germany: Vieweg.</ref>
	==Synthesis of CSCl<sub>2</sub>==
		⚫	:CCl<sub>4</sub>&nbsp;+ H<sub>2</sub>S&nbsp;→ SCCl<sub>2</sub>&nbsp;+ 2&nbsp;HCl
⚫	CSCl<sub>2</sub> is prepared in a two-step process from ]. In the first step, carbon disulfide is chlorinated to give trichloromethanesulfenyl chloride, CCl<sub>3</sub>SCl:
	::CS<sub>2</sub> + 3 Cl<sub>2</sub> → CCl<sub>3</sub>SCl + ]
	The chlorination must be controlled as excess chlorine converts trichloromethanesulfenyl chloride into ]. Steam distillation separates the trichloromethanesulfenyl chloride, a rare sulfenyl chloride, and hydrolyzes the sulfur monochloride. Reduction of trichloromethanesulfenyl chloride produces thiophosgene:
⚫	:: CCl<sub>3</sub>SCl + M → CSCl<sub>2</sub> + MCl<sub>2</sub>
	Typically, ] is used for the reducing agent M.
			== Reactions ==
	==Uses of CSCl<sub>2</sub>==
	CSCl<sub>2</sub> is mainly used to prepare compounds with the connectivity CSX<sub>2</sub> where X = OR, ]. Such reactions proceed via intermediate such as CSClX. Under certain conditions, one can convert primary amines into ]s.		{{chem2|CSCl2}} is mainly used to prepare compounds with the connectivity {{chem2|CSX2}} where X = OR, ].<ref>Pascual, Roxana Martinez "Thiophosgene" Synlett 2015, vol. 26, pp. 1776-1777.{{doi|10.1055/s-0034-1380659}}</ref> Such reactions proceed via intermediate such as CSClX. Under certain conditions, one can convert primary amines into ]s.
	CSCl<sub>2</sub> also serves as a ] to give, after reduction 5-thiacyclohexene derivatives. Thiophosgene is also known as the appropriate reagent in ] synthesis for stereospecific converting 1,2-diols into olefins.		{{chem2|CSCl2}} also serves as a ] to give, after reduction 5-thiacyclohexene derivatives. Thiophosgene is also known as the appropriate reagent in ] synthesis for stereospecific conversion of 1,2-diols into ]s.<ref>{{Cite journal|last1 = Sharma|first1 = S.|title = Thiophosgene in Organic Synthesis|doi = 10.1055/s-1978-24896|journal = Synthesis|volume = 1978|issue = 11|pages = 803–820|year = 1978}}</ref>
			It forms a head-to-tail dimer upon irradiation with UV light:
	==Safety considerations==
			:{{chem2|2 CSCl2 → S2(CCl2)2}}
	CSCl<sub>2</sub> is considered highly toxic.
			Unlike thiophosgene monomer, a red liquid, the photodimer, an example of a 1,3-], is a colourless solid.<ref>{{cite journal|title=Die Kristall- und Molekelstruktur des dimeren Thiophosgens|author=B. Krebs H. Beyer |journal=Z. Anorg. Allg. Chem.|volume=365|pages=199–210
			|year=1969|issue=3–4|doi=10.1002/zaac.19693650315}}</ref> ] of the dimer and then cracking is the principal route to ].<ref>{{cite book|doi=10.1002/9780470771273.ch11|title=The Chemistry of Acyl Halides|editor-first=Saul|editor-last=Patai|series=The Chemistry of Functional Groups|year=1972|publisher=Wiley|chapter=Thiocarbonyl halides|first1=K.&nbsp;T.|last1=Potts|first2=C.|last2=Sapino|pages=354–355|isbn=978-0-471-66936-4 }}</ref>
			Thiophosgene decomposes at 200 °C or above to form carbon disulfide and carbon tetrachloride.<ref>], Department of Transportation (1999). ''CHRIS - Hazardous Chemical Data''. Commandant Instruction 16465.12C. Washington, D.C.: ]&nbsp;&mdash; ]. As in "Thiophosgene" ] compound record.</ref> It has also been observed decomposing to ], ], and ] gases via contact with ].<ref name=pubchem>{{Cite web|url=https://pubchem.ncbi.nlm.nih.gov/compound/Thiophosgene|title=Thiophosgene}}</ref>{{failed verification|date=March 2024}}
⚫	==References==
	{{Citation style|date=September 2007}}
			== Toxicology and safety ==
			{{chem2|CSCl2}} is considered highly toxic. Inhalation of the substance can cause irritation of ], burns, delayed ] and ].<ref>] (2020). ] entry, as on "Thiophosgene" ] compound record.</ref>
			== See also ==
			{{Div col}}
			*]
			*]
			*]
			{{Div col end}}
		⚫	== References ==
	{{reflist}}		{{reflist}}
	*Dyson, G. M. "Thiophosgene" Organic Syntheses, Coll. Vol. 1, p.&nbsp;506; Vol. 6, p.&nbsp;86.
			== Further reading ==
	*{{Holleman&Wiberg}}		*{{Holleman&Wiberg}}
	*Sharma, S. "Thiophosgene in Organic Synthesis" Synthesis, 1978, pages 804-820.
			{{Authority control}}
			{{Chemical agents}}
	]		]
	]		]
	]		]
			]
	]
	]
	]
	]
	]