Formyl Chloride

[2565-30-2]  · CHClO  · Formyl Chloride  · (MW 64.47)

(Gatterman-Koch aldehyde synthesis;1 conversion of alcohols to formate esters2)

Physical Data: unstable at room temperature.

Preparative Methods: prepared by chlorination of Formic Acid at -78 °C3 and by introduction of dry Hydrogen Chloride at -60 °C to a solution of N-Formylimidazole in chloroform.4

The procedure described by Gatterman and Koch1 for the preparation of p-tolualdehyde calls for stirring a suspension of Copper(I) Chloride and Aluminum Chloride in toluene and passing in Carbon Monoxide and Hydrochloric Acid and hydrolyzing the resulting complex with ice. Formyl chloride was regarded as the transient intermediate (eq 1).

Treatment of 4-(1-hydroxyethyl)-3,7,7-trimethylbicyclo[4.1.0]hept-3-ene and its position isomers with Formic Acid and Thionyl Chloride gave in 65% yield the three double bond isomers of 4-(1-formyloxyethyl)-3,7,7-trimethylbicyclo[4.1.0]hept-3-ene (eq 2).2

Related Reagents.

Formyl Fluoride.

1. (a) Gatterman, L.; Koch, J. A. CB 1897, 30, 1622. (b) Coleman, G. H.; Craig, D. OSC 1943, 2, 583.
2. Misra, L. N.; Nigam, M. C. IJC(B) 1983, 22B, 453.
3. Takeo, H.; Matsumura, C. JCP 1976, 64, 4536.
4. Staab, H. A.; Datta, A. P. AG 1963, 75, 1203.

John C. Sih

The Upjohn Co., Kalamazoo, MI, USA

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