| Revision as of 14:25, 10 January 2012 editBeetstra (talk | contribs)Edit filter managers, Administrators172,031 edits Saving copy of the {{chembox}} taken from revid 439632906 of page Triphosgene for the Chem/Drugbox validation project (updated: ''). |
Latest revision as of 11:46, 2 December 2024 edit 2a02:a451:1240:0:5a:ec9b:43e9:cf87 (talk) Fixed mismatched parentheses by adding closing parenthesis. |
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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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| verifiedrevid = 402703781 |
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| ImageFile = Triphosgene-skeletal.png |
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| verifiedrevid = 470617146 |
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| ImageFile1 =Triphosgene-3D-vdW.png |
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| ImageFile = Triphosgen Strukturformel.svg |
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| ImageFile1 =Triphosgene-3D-spacefill.png |
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| ImageSize = |
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| ImageSize = |
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| IUPACName = Bis(trichloromethyl) carbonate |
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| PIN = Bis(trichloromethyl) carbonate |
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| OtherNames = |
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| OtherNames = BTC |
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| Section1 = {{Chembox Identifiers |
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|Section1={{Chembox Identifiers |
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| ChemSpiderID_Ref = {{chemspidercite|correct|chemspider}} |
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| ChemSpiderID_Ref = {{chemspidercite|correct|chemspider}} |
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| ChemSpiderID = 85216 |
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| ChemSpiderID = 85216 |
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| StdInChIKey_Ref = {{stdinchicite|correct|chemspider}} |
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| StdInChIKey_Ref = {{stdinchicite|correct|chemspider}} |
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| StdInChIKey = UCPYLLCMEDAXFR-UHFFFAOYSA-N |
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| StdInChIKey = UCPYLLCMEDAXFR-UHFFFAOYSA-N |
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| CASNo_Ref = {{cascite|correct|CAS}} |
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| CASNo = |
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| CASNo = 32315-10-9 |
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| UNII_Ref = {{fdacite|correct|FDA}} |
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| UNII = 2C0677Q3B2 |
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| PubChem = 94429 |
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| PubChem = 94429 |
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| SMILES = ClC(Cl)(Cl)OC(=O)OC(Cl)(Cl)Cl |
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| SMILES = ClC(Cl)(Cl)OC(=O)OC(Cl)(Cl)Cl |
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| Section2 = {{Chembox Properties |
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|Section2={{Chembox Properties |
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| Formula = C<sub>3</sub>Cl<sub>6</sub>O<sub>3</sub> |
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| Formula = C<sub>3</sub>Cl<sub>6</sub>O<sub>3</sub> |
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| MolarMass = 296.748 g/mol |
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| MolarMass = 296.748 g/mol |
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| Appearance = |
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| Appearance = white solid |
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| Density = |
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| Density = 1.780 g/cm<sup>3</sup> |
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| MeltingPtC = 80 |
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| MeltingPtC = 80 |
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| BoilingPtC = 206 |
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| BoilingPtC = 206 |
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| Solubility = Reacts}} |
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| Solubility = Reacts |
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| Section3 = {{Chembox Hazards |
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*soluble in dichloromethane<ref>{{cite journal | vauthors = Ouimet MA, Stebbins ND, Uhrich KE | title = Biodegradable coumaric acid-based poly(anhydride-ester) synthesis and subsequent controlled release | journal = Macromolecular Rapid Communications | volume = 34 | issue = 15 | pages = 1231–1236 | date = August 2013 | pmid = 23836606 | pmc = 3789234 | doi = 10.1002/marc.201300323 }}</ref> |
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| ExternalMSDS = |
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*soluble in THF<ref>{{cite journal | vauthors = Tang S, Ikai T, Tsuji M, Okamoto Y | title = Immobilization and chiral recognition of 3,5-dimethylphenylcarbamates of cellulose and amylose bearing 4-(trimethoxysilyl)phenylcarbamate groups | journal = Chirality | volume = 22 | issue = 1 | pages = 165–172 | date = January 2010 | pmid = 19455617 | doi = 10.1002/chir.20722 }}</ref> |
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*soluble in toluene<ref>{{Cite journal| vauthors = Zhou Y, Gong R, Miao W |date= September 2006 |title=New Method of Synthesizing N-Alkoxycarbonyl-N-arylamide with Triphosgene |journal=Synthetic Communications |volume=36 |issue=18 |pages=2661–2666 |doi=10.1080/00397910600764675 |s2cid= 98578315 }}</ref>}} |
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|Section3={{Chembox Hazards |
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| FlashPt = |
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| Autoignition = }} |
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| AutoignitionPt = |
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| GHSPictograms = {{GHS06}}{{GHS05}}<ref name="sigma">{{Sigma-Aldrich|id=330752|name=Triphosgene|access-date=2018-06-12}}</ref> |
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| GHSSignalWord = Danger |
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| HPhrases = {{H-phrases|314|330}}<ref name="sigma" /> |
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| PPhrases = {{P-phrases|260|280|284|305+351+338|310}}<ref name="sigma" />}} |
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'''Triphosgene''' ('''bis(trichloromethyl) carbonate''' ('''BTC''')) is a chemical compound with the formula OC(OCCl<sub>3</sub>)<sub>2</sub>. It is used as a solid substitute for ], which is a gas and ], which is a liquid.<ref>{{cite book |doi=10.1002/047084289X.rb200 |chapter=Bis(trichloromethyl) Carbonate |title=Encyclopedia of Reagents for Organic Synthesis |date=2001 |last1=Roestamadji |first1=Juliatiek |last2=Mobashery |first2=Shahriar |isbn=0471936235 }}</ref><ref name="eckert">{{cite journal |author1=Heiner Eckert |author2=Barbara Forster |year=1987 |title=Triphosgene, a Crystalline Phosgene Substitute |journal=Angew. Chem. Int. Ed. Engl. |volume=26 |issue=9 |pages=894–895 |doi=10.1002/anie.198708941}}</ref> Triphosgene is stable up to 200 °C.<ref name=":0" /> Triphosgene is used in a variety of halogenation reactions.<ref name=":2" /> |
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==Preparation== |
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This compound is commercially available. It is prepared by exhaustive free radical chlorination of ]:<ref name = eckert/> |
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:CH<sub>3</sub>OCO<sub>2</sub>CH<sub>3</sub> + 6 Cl<sub>2</sub> → CCl<sub>3</sub>OCO<sub>2</sub>CCl<sub>3</sub> + 6 HCl |
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Triphosgene can be easily recrystallized from hot hexanes. |
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==Uses== |
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Triphosgene is used as a ] in ] as a source of CO<sup>2+</sup>. It behaves like phosgene, to which it cracks thermally: |
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:{{chem2|OC(OCCl3)2 <-> 3 OCCl2}} |
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Alcohols are converted to carbonates. Primary and secondary amines are converted to ureas and ]s.<ref name = eckert/><ref name=":0">{{cite journal| vauthors = Akiba T, Tamura O, Terashima S |doi=10.15227/orgsyn.075.0045 |title=(4R,5S)-4,5-Diphenyl-3-Vinyl-2-Oxazolidinone |journal=Organic Syntheses |volume=75 |pages=45 |year=1998 }}</ref><ref name=":1">{{cite journal| vauthors = Tsai JH, Takaoka LR, Powell NA, Nowick JS |doi=10.15227/orgsyn.078.0220|title=Synthesis of Amino Acid Ester Isocyanates: Methyl (S)-2-Isocyanato-3-Phenylpropanoate|journal=Organic Syntheses|volume=78|pages=220|year=2002}}</ref><ref>{{cite journal| vauthors = Du H, Zhao B, Shi Y |doi=10.15227/orgsyn.086.0315|title=Pd(0)-Catalyzed Diamination of Trans-1-Phenyl-1,3-Butadiene with Di-tert-Butyldiaziridinone as Nitrogen Source|journal=Organic Syntheses|volume=86|pages=315|year=2009|doi-access=free}}</ref> |
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Triphosgene has been used to synthesize chlorides.<ref name=":2">{{cite journal | vauthors = Ganiu MO, Nepal B, Van Houten JP, Kartika R | title = A decade review of triphosgene and its applications in organic reactions | journal = Tetrahedron | volume = 76 | issue = 47 | pages = 131553 | date = November 2020 | pmid = 33883783 | pmc = 8054975 | doi = 10.1016/j.tet.2020.131553 }}</ref> Some ] are prepared by treating alcohols with a mixture of triphosgene and ]. Alkyl dichlorides and trichlorides can similarly be synthesized using triphosgene. ] are synthesized from ]s using triphosgene and ] to form a ], followed by a ring opening by chloride ions. ] can also be produced using a Vilsmeier reagent from triphosgene and DMF. |
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==Safety== |
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The vapor pressure of Triphosgene is sufficiently high for it to reach concentrations that are considered toxicologically unsafe.<ref name=":3">{{Cite journal | vauthors = Cotarca L, Geller T, Répási J |date=2017-09-15 |title=Bis(trichloromethyl)carbonate (BTC, Triphosgene): A Safer Alternative to Phosgene? |journal=Organic Process Research & Development |language=en |volume=21 |issue=9 |pages=1439–1446 |doi=10.1021/acs.oprd.7b00220 |doi-access=free }}</ref> While several properties of triphosgene are not yet readily available, it is known that it is very toxic if inhaled. A toxic gas is emitted if it comes in contact with water.<ref>{{Cite web |date=2009 |title=Material Safety Data Sheet: Triphosgene |url=https://ehslegacy.unr.edu/msdsfiles/26588.pdf |access-date=February 17, 2022 |website=Acros Organics}}</ref> There is a lack of information and variability regarding the proper handling of triphosgene. It is assumed to have the same risks as phosgene.<ref>{{cite journal | vauthors = Damle SB | title = Safe handling of diphosgene, triphosgene. | journal = Chemical & Engineering News | date = February 1993 | volume = 71 | issue = 6 | pages = 4 | url = http://pubsapp.acs.org/cen/safety/19930208.html? }}</ref><ref>{{cite journal | vauthors = Pauluhn J | title = Phosgene inhalation toxicity: Update on mechanisms and mechanism-based treatment strategies | journal = Toxicology | volume = 450 | pages = 152682 | date = February 2021 | pmid = 33484734 | doi = 10.1016/j.tox.2021.152682 | s2cid = 231693591 | doi-access = free | bibcode = 2021Toxgy.45052682P }}</ref> |
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== See also == |
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* ] |
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* ] |
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== References == |
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{{reflist}} |
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== External links == |
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