Michaelis—Arbuzov—Kaehne reaction

The Michaelis-Arbuzov reaction is also known as the Michaelis-Arbuzov-Kaehne reaction or the Michaelis-Arbuzov rearrangement and is sometimes named after Arbuzov only. For reviews of the reaction see Refs 6, 12,17, and 18. 

The Michaelis-Arbuzov-Kaehne reaction is probably the most widely used reaction in organophosphorus chemistry for the preparation not only of phosphonic and phosphinic acids (as their esters), but also of tertiary phosphine oxides. The reaction, discovered by Michaelis and Kaehne in 1898, and extensively developed by A. Arbuzov in the early years of this century, consists essentially in the interaction of phosphorus(III) acid ester with a reactive carbon-based species, generally an alkyl halide, and can be represented in very general terms as in equation 1 the reaction has been extensively reviewed... 

This reaction, discovered by Alichaelis and Kaehne (222) and explored later by Arbuzov (15), has been widely employed for the synthesis of phosphonate and phosphinate esters and phosphine oxides. The extensive literature on the Michaelis-Arbuzov reaction has been summarized through 1949 in two reviews by Kosolapoff (177,178). 

From a synthetic viewpoint, the significant feature of the classical Michaelis-Arbuzov reaction of an alkyl halide with a P(III) ester is the formation of a carbon-phosphorus bond. Since its discovery by Michaelis and Kaehne (222) in 1898, it has been the principle synthetic route to the phosphonic acids, which, with their esters and amides, probably outnumber all other compounds containing the carbon-phosphorus bond (105). 

Michaelis and Kaehne isolated a product with saltlike properties from the reaction of triphenyl phosphite and methyl iodide. This observation has been confirmed by Arbuzov and Sazonova (30) and by Landauer and Rydon (206,284), who used this salt as a reagent for the preparation, in excellent yields, of alkyl halides, including neopentyl iodide, from the corresponding alcohols. The course of this reaction... 

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