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Triphosgene
Chemical compound

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. Triphosgene is stable up to 200 °C. Triphosgene is used in a variety of halogenation reactions.

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Preparation

This compound is commercially available. It is prepared by exhaustive free radical chlorination of dimethyl carbonate:5

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.6789

Triphosgene has been used to synthesize chlorides.10 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.1314

See also

References

  1. Roestamadji, Juliatiek; Mobashery, Shahriar (2001). "Bis(trichloromethyl) Carbonate". Encyclopedia of Reagents for Organic Synthesis. doi:10.1002/047084289X.rb200. ISBN 0471936235. 0471936235 ↩

  2. Heiner Eckert; Barbara Forster (1987). "Triphosgene, a Crystalline Phosgene Substitute". Angew. Chem. Int. Ed. Engl. 26 (9): 894–895. doi:10.1002/anie.198708941. /wiki/Doi_(identifier) ↩

  3. 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. /wiki/Doi_(identifier) ↩

  4. 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. https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8054975 ↩

  5. Heiner Eckert; Barbara Forster (1987). "Triphosgene, a Crystalline Phosgene Substitute". Angew. Chem. Int. Ed. Engl. 26 (9): 894–895. doi:10.1002/anie.198708941. /wiki/Doi_(identifier) ↩

  6. Heiner Eckert; Barbara Forster (1987). "Triphosgene, a Crystalline Phosgene Substitute". Angew. Chem. Int. Ed. Engl. 26 (9): 894–895. doi:10.1002/anie.198708941. /wiki/Doi_(identifier) ↩

  7. 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. /wiki/Doi_(identifier) ↩

  8. 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. /wiki/Doi_(identifier) ↩

  9. 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. https://doi.org/10.15227%2Forgsyn.086.0315 ↩

  10. 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. https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8054975 ↩

  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. https://doi.org/10.1021%2Facs.oprd.7b00220 ↩

  12. "Material Safety Data Sheet: Triphosgene" (PDF). Acros Organics. 2009. Retrieved February 17, 2022. https://ehslegacy.unr.edu/msdsfiles/26588.pdf ↩

  13. Damle SB (February 1993). "Safe handling of diphosgene, triphosgene". Chemical & Engineering News. 71 (6): 4. http://pubsapp.acs.org/cen/safety/19930208.html? ↩

  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. https://doi.org/10.1016%2Fj.tox.2021.152682 ↩