Triphosgene

Last updated
Triphosgene
Triphosgen Strukturformel.svg
Triphosgene-3D-spacefill.png
Names
Preferred IUPAC name
Bis(trichloromethyl) carbonate
Other names
BTC
Identifiers
3D model (JSmol)
ChemSpider
ECHA InfoCard 100.046.336 OOjs UI icon edit-ltr-progressive.svg
PubChem CID
UNII
  • InChI=1S/C3Cl6O3/c4-2(5,6)11-1(10)12-3(7,8)9 Yes check.svgY
    Key: UCPYLLCMEDAXFR-UHFFFAOYSA-N Yes check.svgY
  • InChI=1/C3Cl6O3/c4-2(5,6)11-1(10)12-3(7,8)9
    Key: UCPYLLCMEDAXFR-UHFFFAOYAA
  • ClC(Cl)(Cl)OC(=O)OC(Cl)(Cl)Cl
Properties
C3Cl6O3
Molar mass 296.748 g/mol
Appearancewhite solid
Density 1.780 g/cm3
Melting point 80 °C (176 °F; 353 K)
Boiling point 206 °C (403 °F; 479 K)
Reacts
Solubility *soluble in dichloromethane [1]
  • soluble in THF [2]
  • soluble in toluene [3]
Hazards
GHS labelling:
GHS-pictogram-skull.svg GHS-pictogram-acid.svg [4]
Danger
H314, H330 [4]
P260, P280, P284, P305+P351+P338, P310 [4]
Safety data sheet (SDS) SDS Triphosgene
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
X mark.svgN  verify  (what is  Yes check.svgYX mark.svgN ?)

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 liquid

Contents

and diphosgene, which is a liquid. [5]  [6]  Triphosgene is stable up to 200 °C. [7]  Triphosgene is used in a variety of halogenation reactions. [8]

Preparation

This compound is commercially available. It is prepared by exhaustive free radical chlorination of dimethyl carbonate: [6]

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:

OC(OCCl3)2 ⇌ 3 OCCl2

Alcohols are converted to carbonates. Primary and secondary amines are converted to ureas and isocyanates. [6] [7] [9] [10]

Triphosgene has been used to synthesize chlorides. [8] 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. [11] 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. [12] There is a lack of information and variability regarding the proper handling of triphosgene. It is assumed to have the same risks as phosgene. [13] [14]

See also

References

  1. ↑ Ouimet MA, Stebbins ND, Uhrich KE (August 2013). "Biodegradable coumaric acid-based poly(anhydride-ester) synthesis and subsequent controlled release". Macromolecular Rapid Communications. 34 (15): 1231–1236. doi:10.1002/marc.201300323. PMC   3789234 . PMID   23836606.
  2. ↑ Tang S, Ikai T, Tsuji M, Okamoto Y (January 2010). "Immobilization and chiral recognition of 3,5-dimethylphenylcarbamates of cellulose and amylose bearing 4-(trimethoxysilyl)phenylcarbamate groups". Chirality. 22 (1): 165–172. doi:10.1002/chir.20722. PMID   19455617.
  3. ↑ Zhou Y, Gong R, Miao W (September 2006). "New Method of Synthesizing N-Alkoxycarbonyl-N-arylamide with Triphosgene". Synthetic Communications. 36 (18): 2661–2666. doi:10.1080/00397910600764675. S2CID   98578315.
  4. 1 2 3 Sigma-Aldrich Co., Triphosgene.
  5. ↑ Roestamadji, Juliatiek; Mobashery, Shahriar (2001). "Bis(trichloromethyl) Carbonate". Encyclopedia of Reagents for Organic Synthesis. doi:10.1002/047084289X.rb200. ISBN   0-471-93623-5.
  6. 1 2 3 Heiner Eckert; Barbara Forster (1987). "Triphosgene, a Crystalline Phosgene Substitute". Angew. Chem. Int. Ed. Engl. 26 (9): 894–895. doi:10.1002/anie.198708941.
  7. 1 2 Akiba T, Tamura O, Terashima S (1998). "(4R,5S)-4,5-Diphenyl-3-Vinyl-2-Oxazolidinone". Organic Syntheses. 75: 45. doi:10.15227/orgsyn.075.0045.
  8. 1 2 Ganiu MO, Nepal B, Van Houten JP, Kartika R (November 2020). "A decade review of triphosgene and its applications in organic reactions". Tetrahedron. 76 (47) 131553. doi:10.1016/j.tet.2020.131553. PMC   8054975 . PMID   33883783.
  9. ↑ Tsai JH, Takaoka LR, Powell NA, Nowick JS (2002). "Synthesis of Amino Acid Ester Isocyanates: Methyl (S)-2-Isocyanato-3-Phenylpropanoate". Organic Syntheses. 78: 220. doi:10.15227/orgsyn.078.0220.
  10. ↑ Du H, Zhao B, Shi Y (2009). "Pd(0)-Catalyzed Diamination of Trans-1-Phenyl-1,3-Butadiene with Di-tert-Butyldiaziridinone as Nitrogen Source". Organic Syntheses. 86: 315. doi: 10.15227/orgsyn.086.0315 .
  11. ↑ Cotarca L, Geller T, Répási J (2017-09-15). "Bis(trichloromethyl)carbonate (BTC, Triphosgene): A Safer Alternative to Phosgene?". Organic Process Research & Development. 21 (9): 1439–1446. doi: 10.1021/acs.oprd.7b00220 .
  12. ↑ "Material Safety Data Sheet: Triphosgene" (PDF). Acros Organics. 2009. Retrieved February 17, 2022.
  13. ↑ Damle SB (February 1993). "Safe handling of diphosgene, triphosgene". Chemical & Engineering News. 71 (6): 4.
  14. ↑ Pauluhn J (February 2021). "Phosgene inhalation toxicity: Update on mechanisms and mechanism-based treatment strategies". Toxicology. 450 152682. Bibcode:2021Toxgy.45052682P. doi: 10.1016/j.tox.2021.152682 . PMID   33484734. S2CID   231693591.
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