Its many different reactions makes phosgene an important starting compound in the production of

intermediates and end products in many branches of large-scale industrial chemistry.

Diisocyanates. Mostphosgeneisusedforthe production of diisocyanates as starting materials of

polyurethane chemistry. The most important compounds are toluene diisocyanate (TDI) [1321-38-6]
as well as monomeric [101-68-8] (MDI) and polymeric methylenediphenyl diisocyanate [9016-87-9]
(PMDI) (→Isocyanates, Organic, Chap. 3.).

The production of toluene diisocyanate (TDI) starts from toluene, which is converted in a continuous
process to a mixture of 2,4and 2,6-dinitrotoluene. This mixture is hydrogenated with hydrogen to
give 2,4- and 2,6toluenediamine(TDA).Thereactionwithphosgene is usually carried out in a
continuous process, using e.g., toluene, chlorobenzene, or 1,2dichlorobenzene as solvents, at 65–
180◦C and at excess pressure. In the course of this process hydrogen chloride (reaction product),
phosgene (excessreactant),andfinallythesolventaresuccessively separated. The end product TDI is
purified by distillation.

For the production of methylenediphenyl diisocyanate (MDI), aniline is used as the starting material.
It is condensed with formaldehyde to form a mixture of isomeric methylenediphenyldiamines
(MDA). The subsequent reaction of this amine mixture with phosgene is
similartothatdescribedaboveforTDI.Theend product is a mixture of isomeric MDI and various PMDI
types. Distillative purification is not carried out.

Thehightoxicityofphosgenehasresultedin intensiveworkonthedevelopmentofphosgenefree processes

for diisocyanate manufacture. These processes start from the corresponding dinitro compounds,
which react with CO to form diisocyanates [57–62]. The reaction of the amines with compounds
other than phosgene such as dimethyl carbonate [63] or methanol and carbon monoxide with
oxygen [64], is another line of development. The development of phosgene-
freeprocesseshasbeensuccessfulfor only a few aliphatic diisocyanates; the production of other
diisocyanates by this route suffers from a lack of profitability or process engineering difficulties
(→Isocyanates, Organic, Chap. 4.3.) [65], [66].

Aliphatic diisocyanates are important starting materials for polyurethanes used in coatings.
Monoisocyanates, such as isopropyl isocyanate, phenyl isocyanate, and chlorophenyl isocyanates,
are important intermediates in the manufacture of herbicides and insecticides.

Polycarbonates. The next largest phosgene consumers are polycarbonate plastics

(→Polycarbonates). They are produced by reaction of 2,2-bis(4-hydroxyphenyl)propane (bisphenolA)
with phosgene, either directly or indirectly via diphenyl carbonate.

Chloroformic Esters. The reaction of phosgenewithalcoholstoformchloroformicestersis

veryimportantforindustrialapplications.These esters are exceptionally versatile intermediates, e.g.,
for the production of carbonic esters, polycarbonates, and polyurethanes, and for many other
applications (→Chloroformic Esters).

Urea Azo Dyes. The treatment of aminoazo dyes with phosgene in aqueous solution to produce
symmetrical urea azo dyes, has been practiced since the end of the 19th century (→Azo Dyes, Chap.
4.1.6.).

Carbonate Esters. Among the carbonate esters,dimethylanddiethylcarbonatesinparticular are used in

the pharmaceutical industry and in the production of pesticides. Diphenyl carbonate is an
intermediate in the production of polycarbonates.
Friedel–Crafts Acylations. Friedel–Crafts acylations with phosgene are important reactions, e.g., for
the dye industry, yielding importantketonessuchasbenzophenone(→Ketones, Chap. 7.3.) or 4,4-
bis(dimethylamino)benzophenone (Michler’s ketone) (→ Acylation and Alkylation, Chap. 2.2.).
Benzoyl chloride can also be obtained in this way from benzene. The production of 2,5-
dichlorobenzoic acid from 1,4-dichlorobenzeneandphosgeneinanAlCl3 – sodium formate melt is
described in [67].

Other Uses. Phosgene undergoes commercially important cyclization reactions with aminocarboxylic
acids, aminophenols, and diamines. Acid chlorides are often prepared by reaction of carboxylic acids
with phosgene (for suitable catalysts see [68]). Examples are the production of isophthaloyl
dichloride and terephthaloyl dichloride on the large industrial scale.

Phosgene disproportionates to form carbon tetrachloride and carbon dioxide at high temperatures
(→Chlorinated Hydrocarbons).

In inorganic chemistry, phosgene is used as anintermediateforthelarge-scaleproductionof

aluminumchloride(→AluminumCompounds, Inorganic, Chap. 4.1.2.). The production of zirconium
chloride is described in [69].