Copper(I) Acetate1

CuOAc

[598-54-9]  · C2H3CuO2  · Copper(I) Acetate  · (MW 122.58)

(acetoxylation;4 oxidation of phenols;6 hydrogenation3)

Alternate Name: cuprous acetate.

Physical Data: dec 285 °C.

Solubility: sol water (hydrolyzes to form Cu2O), pyridine, HOAc; dissolves slowly in ether.

Form Supplied in: tan or white powder; commercially available.

Preparative Methods: obtained as a sublimate by heating copper(II) acetate in vacuo to temperatures above 220 °C.2 Prepared from Copper(I) Oxide and Acetic Acid-Acetic Anhydride;3 also, from a reaction involving Copper(II) Acetate and Copper foil in anhydrous acetonitrile with acetic acid-acetic anhydride. The mixture is stirred under nitrogen for 48 h after excess copper is removed, and precipitation of copper(I) acetate in ether occurs.4,5 Obtained by slow addition of a solution of hydroxylamine hydrogen sulfate to a hot mixture of ammoniacal copper(II) acetate solution buffered with a large amount of ammonium acetate; addition of excess acetic acid precipitates the copper(I) acetate.1

Handling, Storage, and Precautions: stable when dry, but decomposes with moisture or strong heating.

Acetoxylation.

Vinyl acetates are often very hard to prepare from vinyl halides. They can be synthesized either by reacting cyclic vinylic bromides with excess copper(I) acetate in acetonitrile at 80-110 °C for 2-10 h (eq 1),4,6 or by reacting acyclic vinyl iodides with copper(I) acetate in refluxing pyridine. However, the latter method produces poor yields of vinyl acetates (eq 2). When copper(II) acetate in refluxing N-methylpyrrolidone (NMP) is utilized instead, vinyl acetates are obtained in higher yields (eq 2).7

Oxidation of Phenols.

Copper(I) acetate functions as a catalyst in the oxidation of phenols to the corresponding poly(phenylene) ethers and diphenoquinones in the presence of tertiary amines.8

Hydrogenation.

A dimer of the copper(I) acetate-Quinoline complex activates molecular hydrogen in the homogeneous catalytic hydrogenation of quinone in solution.3

Related Reagents.

Copper(II) Acetate, Sodium Tetracarbonylcobaltate.


1. Tuddenham, W.; Dougall, P. In Kirk-Othmer Encyclopedia of Chemical Technology, 3rd ed.; Wiley: New York, 1979; Vol. 7, p 97.
2. Angel, A.; Scholar, D.; Harcourt, A. V. JCS 1902, 81, 1385.
3. Calvin, M. JACS 1939, 61, 2230.
4. Edwards, D. A.; Richards, R. JCS(D) 1973, 2463.
5. Kochi, J. K.; Bemis, A. T 1968, 24, 5099.
6. Klumpp, G. W.; Bos, H.; Schmitz, R. F.; Vrielink, J. J. TL 1975, 3429.
7. Commercon, A.; Normant, J.; Villieras, J. JOM 1975, 93, 415.
8. Hay, A. Fr. Patent 1 322 152, 1963 (CA 1964, 60, 685b).

Edward J. Parish & Stephen A. Kizito

Auburn University, AL, USA



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