Diphosgene
Encyclopedia
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.
chlorination of methyl chloroformate
under UV light
.:
Another method is the radical chlorination of methyl formate:
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 amine
s into isocyanate
s, secondary amines into carbamoyl chlorides, carboxylic acid
s into acid chlorides, and formamide
s into isocyanide
s. Diphosgene serves as a source of two equivalents of phosgene:
With α-amino acid
s diphosgene gives the acid chloride-isocyanates, OCNCHRCOCl, or N-carboxy-amino acid anhydrides depending on the conditions.
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.
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. Diphosgene was developed because the vapors could destroy the filters in gas mask
s in use at the time.
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.
Chemical compound
A chemical compound is a pure chemical substance consisting of two or more different chemical elements that can be separated into simpler substances by chemical reactions. Chemical compounds have a unique and defined chemical structure; they consist of a fixed ratio of atoms that are held together...
with the formula ClCO2CCl3. This colorless liquid is a valuable reagent in the synthesis
Organic synthesis
Organic synthesis is a special branch of chemical synthesis and is concerned with the construction of organic compounds via organic reactions. Organic molecules can often contain a higher level of complexity compared to purely inorganic compounds, so the synthesis of organic compounds has...
of organic compounds. Diphosgene is related to phosgene
Phosgene
Phosgene is the chemical compound with the formula COCl2. This colorless gas gained infamy as a chemical weapon during World War I. It is also a valued industrial reagent and building block in synthesis of pharmaceuticals and other organic compounds. In low concentrations, its odor resembles...
but is more conveniently handled because it is a liquid, whereas phosgene is a gas.
Production and uses
Diphosgene is prepared by radicalRadical (chemistry)
Radicals are atoms, molecules, or ions with unpaired electrons on an open shell configuration. Free radicals may have positive, negative, or zero charge...
chlorination of methyl chloroformate
Methyl chloroformate
Methyl chloroformate is the methyl ester of chloroformic acid. It is also known as methyl chlorocarbonate, and is an oily liquid with a colour that is anywhere from yellow to colorless. It is also known for its pungent odour...
under UV light
Ultraviolet
Ultraviolet light is electromagnetic radiation with a wavelength shorter than that of visible light, but longer than X-rays, in the range 10 nm to 400 nm, and energies from 3 eV to 124 eV...
.:
- Cl-CO-OCH3 + 3 Cl2 —(hv)→ Cl-CO-OCCl3 + 3 HCl
Another method is the radical chlorination of methyl formate:
- H-CO-OCH3 + 4 Cl2 —(hv)→ Cl-CO-OCCl3 + 4 HCl
Diphosgene converts to phosgene upon heating or upon catalysis
Catalysis
Catalysis is the change in rate of a chemical reaction due to the participation of a substance called a catalyst. Unlike other reagents that participate in the chemical reaction, a catalyst is not consumed by the reaction itself. A catalyst may participate in multiple chemical transformations....
with charcoal
Charcoal
Charcoal is the dark grey residue consisting of carbon, and any remaining ash, obtained by removing water and other volatile constituents from animal and vegetation substances. Charcoal is usually produced by slow pyrolysis, the heating of wood or other substances in the absence of oxygen...
. It is thus useful for reactions traditionally relying on phosgene. For example, it convert amine
Amine
Amines are organic compounds and functional groups that contain a basic nitrogen atom with a lone pair. Amines are derivatives of ammonia, wherein one or more hydrogen atoms have been replaced by a substituent such as an alkyl or aryl group. Important amines include amino acids, biogenic amines,...
s into isocyanate
Isocyanate
Isocyanate is the functional group of elements –N=C=O , not to be confused with the cyanate functional group which is arranged as –O–C≡N or with isocyanide, R-N≡C. Any organic compound which contains an isocyanate group may also be referred to in brief as an isocyanate. An isocyanate may have more...
s, secondary amines into carbamoyl chlorides, carboxylic acid
Carboxylic acid
Carboxylic acids are organic acids characterized by the presence of at least one carboxyl group. The general formula of a carboxylic acid is R-COOH, where R is some monovalent functional group...
s into acid chlorides, and formamide
Formamide
Formamide, also known as methanamide, is an amide derived from formic acid. It is a clear liquid which is miscible with water and has an ammonia-like odor. It is used primarily for manufacturing sulfa drugs and synthesizing vitamins and as a softener for paper and fiber...
s into isocyanide
Isocyanide
An isocyanide is an organic compound with the functional group -N≡C. It is the isomer of the related cyanide , hence the prefix iso....
s. Diphosgene serves as a source of two equivalents of phosgene:
- 2 RNH2 + ClCO2CCl3 → 2 RNCO + 4 HCl
With α-amino acid
Amino acid
Amino acids are molecules containing an amine group, a carboxylic acid group and a side-chain that varies between different amino acids. The key elements of an amino acid are carbon, hydrogen, oxygen, and nitrogen...
s diphosgene gives the acid chloride-isocyanates, OCNCHRCOCl, or N-carboxy-amino acid anhydrides depending on the conditions.
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 agentPulmonary agent
A pulmonary agent is a chemical weapon agent designed to impede a victim's ability to breathe. They operate by causing a build-up of fluids in the lungs which then leads to...
for chemical warfare
Chemical warfare
Chemical warfare involves using the toxic properties of chemical substances as weapons. This type of warfare is distinct from Nuclear warfare and Biological warfare, which together make up NBC, the military acronym for Nuclear, Biological, and Chemical...
, a few months after the first use of phosgene. It was used as a poison gas in artillery
Artillery
Originally applied to any group of infantry primarily armed with projectile weapons, artillery has over time become limited in meaning to refer only to those engines of war that operate by projection of munitions far beyond the range of effect of personal weapons...
shells by Germany
Germany
Germany , officially the Federal Republic of Germany , is a federal parliamentary republic in Europe. The country consists of 16 states while the capital and largest city is Berlin. Germany covers an area of 357,021 km2 and has a largely temperate seasonal climate...
during World War I
World War I
World War I , which was predominantly called the World War or the Great War from its occurrence until 1939, and the First World War or World War I thereafter, was a major war centred in Europe that began on 28 July 1914 and lasted until 11 November 1918...
. The first recorded battlefield use was in May 1916. Diphosgene was developed because the vapors could destroy the filters in gas mask
Gas mask
A gas mask is a mask put on over the face to protect the wearer from inhaling airborne pollutants and toxic gases. The mask forms a sealed cover over the nose and mouth, but may also cover the eyes and other vulnerable soft tissues of the face. Some gas masks are also respirators, though the word...
s in use at the time.
Safety
Diphosgene has a relatively high vapor pressureVapor pressure
Vapor pressure or equilibrium vapor pressure is the pressure of a vapor in thermodynamic equilibrium with its condensed phases in a closed system. All liquids have a tendency to evaporate, and some solids can sublimate into a gaseous form...
of 10 mmHg (1.3 kPa) at 20 °C and decomposes to phosgene
Phosgene
Phosgene is the chemical compound with the formula COCl2. This colorless gas gained infamy as a chemical weapon during World War I. It is also a valued industrial reagent and building block in synthesis of pharmaceuticals and other organic compounds. In low concentrations, its odor resembles...
around 300 °C. Exposure to diphosgene is similar in hazard to phosgene and the MSDS should be consulted.
External links
- medical care guide.
- NATO guide, includes treatment advice
- material safety data sheet (PDF, for phosgene and diphosgene treated as one).