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Carbamoyl chloride

A carbamoyl chloride is the functional group with the formula R<sub>2</sub>NC(O)Cl. The parent carbamoyl chloride, H<sub>2</sub>NCOCl, is unstable, but many N-substituted analogues are known. Most examples are moisture sensitive, colourless, and soluble in nonpolar organic solvents. An example is dimethylcarbamoyl chloride (m.p. −90 °C and b.p. 93 °C). Carbamoyl chlorides are used to prepare a number of pesticides, e.g. carbofuran and aldicarb.

Production and examples

Carbamoyl chlorides are prepared by the reaction of an amine with phosgene:

2 R<sub>2</sub>NH + COCl<sub>2</sub> → R<sub>2</sub>NCOCl + [R<sub>2</sub>NH<sub>2</sub>]Cl

They also arise by the addition of hydrogen chloride to isocyanates:

RNCO + HCl → RNHCOCl

In this way, carbamoyl chlorides can be prepared with N-H functionality.

Reactions

In a reaction that is typically avoided, hydrolysis of carbamoyl chlorides gives carbamic acids:

R<sub>2</sub>NCOCl + H<sub>2</sub>O → R<sub>2</sub>NC(O)OH + HCl

Owing to the influence of the amino group, these compounds are less hydrolytically sensitive than the usual acid chlorides. A related but more useful reaction is the analogous reaction with alcohols:

R<sub>2</sub>NCOCl + R'OH + C<sub>5</sub>H<sub>5</sub>N → R<sub>2</sub>NC(O)OR' + C<sub>5</sub>H<sub>5</sub>NHCl

References