N-Methyl-N-phenylcarbamoyl Chloride1

[4285-42-1]  · C8H8ClNO  · N-Methyl-N-phenylcarbamoyl Chloride  · (MW 169.62)

(reagent for formylation of arenes2)

Physical Data: mp 87-90 °C; bp 280 °C.

Form Supplied in: solid; commercially available.

Purification: recrystallize from dry ether.3

Handling, Storage, and Precautions: a corrosive lachrymator. Store under dry nitrogen. Use in a fume hood.

Formylation Reagent.

N-Methyl-N-phenylcarbamoyl chloride saw early use for the formation of aromatic aldehydes, through the two-step procedure of a Friedel-Crafts acylation of an arene, followed by reduction of the resultant N-methylbenzanilide with Lithium Aluminum Hydride.2 Yields in both steps are generally only moderate (eq 1).2 The mechanism of the reduction has been studied.3 Other reagents for arene formylation have been developed that have greater utility1 (see Bis(1,3-diphenyl-2-imidazolidinylidene) and N-Ethoxymethyleneaniline).

Vinyl and Aryl Amides.

The reagent undergoes reasonably efficient palladium-catalyzed cross coupling with a variety of vinyl- and arylstannanes to give the corresponding amides (eq 2).4

1. Carnduff, J. QR 1966, 20, 169.
2. Weygand, F.; Mitgau, R. CB 1955, 88, 301.
3. Fox, B. L.; Doll, R. J. JOC 1973, 38, 1136.
4. Balas, L.; Jousseaume, B.; Shin, H. A.; Verlhac, J.-B.; Wallian, F. OM 1991, 10, 366.

Steven J. Brickner

The Upjohn Company, Kalamazoo, MI, USA

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