Copper(I) Phenoxide

PhOCu

[34046-55-4]  · C6H5CuO  · Copper(I) Phenoxide  · (MW 156.65)

(phenoxylating agent for organic halides,1 organosulfur compounds,2 and carbon tetrachloride;3 undergoes carbon-carbon bond cleavage by oxygen4)

Solubility: sol DMF, diglyme; insol ether and benzene.

Preparative Methods: metathesis reaction between Copper(I) Chloride and alkali metal phenoxide in MeCN or THF produces a solution of CuI phenoxide complexed with alkali metal chloride,1,2 which can be used for synthetic purposes. CuI phenoxide without alkali metal chloride can be prepared by phenolysis of Methylcopper,1 Phenylcopper,5 and Copper(I) t-Butoxide4 or by metathesis between [Cu(MeCN)4]PF6 and sodium phenoxide.6

Handling, Storage, and Precautions: oxygen- and moisture-sensitive; preparation and reaction should be conducted under rigorously oxygen-free and anhydrous conditions.

Aryl Ether Synthesis.

Alkyl phenyl ethers (eq 1) and diphenyl ether (eq 2) are prepared in good yield using CuI phenoxide.1 Phenyl ether synthesis proceeds under milder reaction conditions than the Williamson ether synthesis. CuI phenoxide has been proposed to be an intermediate of the Ullmann ether synthesis.

Sulfur Substitution.

CuI phenoxide reacts with carbon disulfide at room temperature to afford phenyl orthocarbonate (eq 3).2 Substituted CuI phenoxides can also be used. This reaction has been called the thiophilic reaction of CuI and provides a synthetic method for phenyl orthocarbonate without using phosgene. Nucleophilic addition and substitution in a tetrameric CuI phenoxide cluster has been proposed. The reaction in the presence of a tri-n-butylphosphine ligand produces thiocarbonate (PhO)2C=S in excellent yield. At the elevated reaction temperature of 65 °C, the reaction of CuI phenoxide with thiocarbonates takes place to give mixed orthocarbonates (ArO)2(PhO)2C. Substitution of the sulfur atom of sodium xanthates ROCSSNa, dithioesters RCSSR, and trithiocarbonates (RS)2CS by the phenoxide anion occurs to afford mixed thiocarbonates (PhO)(RO)C=S, phenyl thioesters R(PhO)C=S, and phenyl thiocarbonate (PhO)2C=S, respectively.

Chlorine Substitution of CCl4.

CuI phenoxide reacts with CCl4 via a radical mechanism to afford phenyl orthocarbonate (eq 4),3 while nucleophilic reaction of sodium phenoxide with CCl4 does not give phenyl orthocarbonate. The reaction depends upon the substitution pattern at the ortho positions of the phenyl group. Two examples are shown in eqs 5 and 6.

Oxygenolysis.

Cleavage of the carbon-carbon bond of CuI phenoxide takes place upon exposure to oxygen to afford cis,cis-muconic acid monophenyl ester (eq 7).4 CuI phenoxide has been proposed to be an active reaction intermediate in the copper-promoted oxygenolysis of phenol.


1. Whitesides, G. M.; Sadowski, J. S.; Lilburn, J. JACS 1974, 96, 2829.
2. Narasimhamurthy, N.; Samuelson, A. G. PIA(A) 1989, 55, 383.
3. Harrod, J. F.; van Gheluwe, P. CJC 1979, 57, 890.
4. Demmin, T. R.; Swerdloff, M. D.; Rogić, M. M. JACS 1981, 103, 5795.
5. Kawaki, T.; Hashimoto, H. BCJ 1972, 45, 1499.
6. Eller, P. G.; Kubas, G. J. JACS 1977, 99, 4346.

Tetsuo Tsuda

Kyoto University, Japan



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