Triphosgene
{{chembox
| Verifiedfields = changed
| Watchedfields = changed
| verifiedrevid = 470617146
| ImageFile = Triphosgen Strukturformel.svg
| ImageFile1 =Triphosgene-3D-spacefill.png
| ImageSize =
| PIN = Bis(trichloromethyl) carbonate
| OtherNames = BTC
|Section1={{Chembox Identifiers
| ChemSpiderID_Ref = {{chemspidercite|correct|chemspider}}
| ChemSpiderID = 85216
| InChI = 1/C3Cl6O3/c4-2(5,6)11-1(10)12-3(7,8)9
| InChIKey = UCPYLLCMEDAXFR-UHFFFAOYAA
| StdInChI_Ref = {{stdinchicite|correct|chemspider}}
| StdInChI = 1S/C3Cl6O3/c4-2(5,6)11-1(10)12-3(7,8)9
| StdInChIKey_Ref = {{stdinchicite|correct|chemspider}}
| StdInChIKey = UCPYLLCMEDAXFR-UHFFFAOYSA-N
| CASNo_Ref = {{cascite|correct|CAS}}
| CASNo = 32315-10-9
| UNII_Ref = {{fdacite|correct|FDA}}
| UNII = 2C0677Q3B2
| PubChem = 94429
| SMILES = ClC(Cl)(Cl)OC(=O)OC(Cl)(Cl)Cl
}}
|Section2={{Chembox Properties
| Formula = C3Cl6O3
| MolarMass = 296.748 g/mol
| Appearance = white solid
| Density = 1.780 g/cm3
| MeltingPtC = 80
| BoilingPtC = 206
| Solubility = Reacts
| SolubleOther =
- soluble in dichloromethane{{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 }}
- soluble in THF{{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 }}
- soluble in toluene{{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 }}}}
|Section3={{Chembox Hazards
| ExternalSDS =[https://www.sigmaaldrich.com/MSDS/MSDS/DisplayMSDSPage.do?country=PL&language=EN-generic&productNumber=330752&brand=ALDRICH&PageToGoToURL=https%3A%2F%2Fwww.sigmaaldrich.com%2Fcatalog%2Fsearch%3Finterface%3DAll%26term%3Dtriphosgene%26N%3D0%26mode%3Dmode%2520matchpartialmax%26focus%3Dproduct%26lang%3Dpl%26region%3DPL%26cm_re%3DDid%2520You%2520Mean-_-triphosgene-_-trifosgen SDS Triphosgene]
| FlashPt =
| AutoignitionPt =
| GHSPictograms = {{GHS06}}{{GHS05}}{{Sigma-Aldrich|id=330752|name=Triphosgene|access-date=2018-06-12}}
| GHSSignalWord = Danger
| HPhrases = {{H-phrases|314|330}}
| PPhrases = {{P-phrases|260|280|284|305+351+338|310}}}}
}}
Triphosgene (bis(trichloromethyl) carbonate (BTC)) is a chemical compound with the formula OC(OCCl3)2. It is used as a solid substitute for phosgene, which is a gas and diphosgene, which is a liquid.{{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 }}{{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}} Triphosgene is stable up to 200 °C. Triphosgene is used in a variety of halogenation reactions.
Preparation
This compound is commercially available. It is prepared by exhaustive free radical chlorination of dimethyl carbonate:
:CH3OCO2CH3 + 6 Cl2 → CCl3OCO2CCl3 + 6 HCl
Triphosgene can be easily recrystallized from hot hexanes.
Uses
Triphosgene is used as a reagent in organic synthesis as a source of CO2+. It behaves like phosgene, to which it cracks thermally:
:{{chem2|OC(OCCl3)2 <-> 3 OCCl2}}
Alcohols are converted to carbonates. Primary and secondary amines are converted to ureas and isocyanates.{{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 }}{{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}}{{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}}
Triphosgene has been used to synthesize chlorides.{{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 }} Some Alkyl chlorides are prepared by treating alcohols with a mixture of triphosgene and pyridine. Alkyl dichlorides and trichlorides can similarly be synthesized using triphosgene. Vinyl chlorides are synthesized from ketones using triphosgene and DMF to form a Vilsmeier reagent, followed by a ring opening by chloride ions. Aryl chlorides can also be produced using a Vilsmeier reagent from triphosgene and DMF.
Safety
The vapor pressure of Triphosgene is sufficiently high for it to reach concentrations that are considered toxicologically unsafe.{{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 }} 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.{{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}} There is a lack of information and variability regarding the proper handling of triphosgene. It is assumed to have the same risks as phosgene.{{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? }}{{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 }}
See also
References
{{reflist}}
External links
- [https://www.sigmaaldrich.com/content/dam/sigma-aldrich/docs/Aldrich/Bulletin/al_techbull_al176.pdf Bulletin about Triphosgene]
- [https://fscimage.fishersci.com/msds/97949.htm Material Safety Data Sheet]
Category:Reagents for organic chemistry