diphosgene

Diphosgene
IUPAC name	Diphosgene
Other names	trichloromethyl chloroformate
Identifiers
CAS number	503-38-8
RTECS number	LQ7350000
Properties
Molecular formula	C2Cl4O2
Molar mass	197.82 g/mol
Appearance	liquid at room temperature
Density	1.65 g/cm3
Melting point	-57 °C
Boiling point	128 °C
Solubility in water	insol.
Hazards
R-phrases	26/28-34
S-phrases	26-28-36/37/39-45
Related compounds
Related compounds	COCl2, Cl2
Except where noted otherwise, data are given for materials in their standard state (at 25 °C, 100 kPa)
Infobox references

Diphosgene is a chemical compound with the formula ClCO₂CCl₃. This colorless liquid is a valuable reagent in the synthesis of organic compounds. Diphosgene is related to phosgene but is more conveniently handled because it is a liquid, whereas phosgene is a gas.

Production and uses

Diphosgene is prepared by radical chlorination of methyl chloroformate under UV light.^[1]:

Cl-CO-OCH₃ + 3 Cl₂ —(hv)→ Cl-CO-OCCl₃ + 3 HCl

Another method is the radical chlorination of methyl formate^[2]:

H-CO-OCH₃ + 4 Cl₂ —(hv)→ Cl-CO-OCCl₃ + 4 HCl

Diphosgene converts to phosgene upon heating or upon catalysis with charcoal. It is thus useful for reactions traditionally relying on phosgene. For example, it convert amines into isocyanates, secondary amines into carbamoyl chlorides, carboxylic acids into acid chlorides, and formamides into isocyanides. Diphosgene serves as a source of two equivalents of phosgene:

2 RNH₂ + ClCO₂CCl₃ → 2 RNCO + 4 HCl

With α-amino acids diphosgene gives the acid chloride-isocyanates, OCNCHRCOCl, or N-carboxy-amino acid anhydrides depending on the conditions.^[3]

It hydrolyzes to release HCl in humid air.

Diphosgene has supplanted phosgene in some large scale industrial reactions such as the production of (di-)isocyanates from amines because it is safer to handle than phosgene.

Role in warfare

Diphosgene was originally developed as a pulmonary agent for chemical warfare, a few months after the first use of phosgene. It was used as a poison gas in artillery shells by Germany during World War I. The first recorded battlefield use was in May 1916.^[4] Diphosgene was developed because the vapors could destroy the filters in gas masks in use at the time.

Safety

Diphosgene has a relatively high vapor pressure of 10 mmHg (1.3 kPa) at 20 °C and decomposes to phosgene around 300 °C. Exposure to diphosgene is similar in hazard to phosgene and the MSDS should be consulted.

See also

• phosgene
• triphosgene

References

1. ^ Keisuke Kurita1 and Yoshio Iwakura (1979), "TRICHLOROMETHYL CHLOROFORMATE AS A PHOSGENE EQUIVALENT: 3-ISOCYANATOPROPANOYL CHLORIDE", Org. Synth. 59: 195, http://www.orgsyn.org/orgsyn/orgsyn/prepContent.asp?prep=cv6p0715 ; Coll. Vol. 6: 715 
2. ^ Lohs, KH.: Synthetische Gifte; Berlin (east), 1974 (german)
3. ^ Kurita, K. "Trichloromethyl Chloroformate" in Encyclopedia of Reagents for Organic Synthesis (Ed: L. Paquette) 2004, J. Wiley & Sons, New York. DOI: 10.1002/047084289.
4. ^ Jones, Simon; Hook, Richard (2007). World War I Gas Warfare Tactics and Equipment. Osprey Publishing. ISBN 1846031516. 

External links

• medical care guide.
• NATO guide, includes treatment advice
• material safety data sheet (PDF, for phosgene and diphosgene treated as one).