- CH3OCO2CH3 + 3 Cl2 → CCl3OCO2CCl3 + 6 HCl
Triphosgene is used as a reagent in organic synthesis for a variety of chemical transformations including to bond one carbonyl group to two alcohols, and to convert an amine group into isocyanate.
The toxicity of triphosgene is the same as phosgene since it decomposes to phosgene on heating and upon reaction with nucleophiles. Even trace moisture leads to formation of phosgene. Therefore this reagent can be safely handled if one takes all the precautions as for phosgene.
Structure and basic properties
Industrially, phosgene is produced by passing purified carbon monoxide and chlorine gas through a bed of porous activated carbon, which serves as acatalyst:
- CO + Cl2 → COCl2 (ΔHrxn = −107.6kJ/mol)
Synthesis of carbonates
- HOCR2-X-CR2OH + COCl2 → 1/n [OCR2-X-CR2OC(O)-]n + 2 HCl
Synthesis of isocyanates
- RCO2H + COCl2 → RC(O)Cl + HCl + CO2
- ROH + COCl2 → ROC(O)Cl + HCl
Although it is somewhat hydrophobic, phosgene reacts with water to release hydrogen chloride and carbon dioxide:
- COCl2 + H2O → CO2 + 2 HCl
- COCl2 + 4 NH3 → CO(NH2)2 + 2 NH4Cl
Further information: Use of poison gas in World War I and Second Italo-Abyssinian War
Caitlan E. Ayala, Andres Villalpando, Alex L. Nguyen, Gregory T. McCandless and Rendy Kartika*
*Department of Chemistry, 232 Choppin Hall, Louisiana State University, Baton Rouge, Louisiana 70803, United States, Email: rkartikalsu.edu
Enantiomerically pure hydantoins are prepared from optically pure α-amino amides utilizing triphosgene. A mechanism for the racemization observed with 1,1'-carbonyldiimidazole (CDI) for this type of reaction is proposed.
D. Zhang, X. Xing, G. D. Cuny, J. Org. Chem., 2006, 71, 1750-1753.
Double acylation of a titanaselenide by triphosgene;
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- Mole percent 4 referring to 3 phosgene equivalents of 1 .
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- The weighing error of this procedure mainly comes from icy condensed humidity at the cool glassware of the cooling trap and is less than 0.5 g, determined by a series of weighings under the same conditions, the same equipment, temperature (T = −78 °C), and handling time <10 s, but without 3. Under these conditions evaporation of 3 (bp 8 °C) hardly ever happens and can be ignored.
- Monitox plus gas monitor (COCl2) and phosgene badges from Compurhttp://www.compur.com/gasmessgeraete/front_content.php?idcat=7&changelang=3.
- Davy's account of his discovery of phosgene
- International Chemical Safety Card 0007
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- NIOSH Pocket Guide to Chemical Hazards
- U.S. CDC Emergency Preparedness & Response
- U.S. EPA Acute Exposure Guideline Levels
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- Use of Phosgene in WWII and in modern-day warfare (Refer to Section 4.C of the article)
- An experience with accidental poisoning by heated tetrachlorethylene solvent