Michaelis-Arbuzov reaction related reactions

R. G. Harvey and E. R. De Sombre, The Michaelis-Arbuzov and related reactions, in Topics in Phosphorus Chemistry, Vol. 1 (M. Grayson and E. J. Griffith, eds.), Wiley-Interscience, New York, 1964. 

For a review of the related area of Michaelis-Arbuzov reactions of alkyl phosphite ligands, see Brill, T. B. Landon, S. J. Chem. Rev. 1984, 84, 577. 

Apart from their behaviour as ligands in metal catalyst systems, studies of the reactivity of phosphites towards a wide variety of other substrates have attracted attention. New aspects and applications of the classical Michaelis-Arbuzov reaction and its variants continue to appear. Evidence of the thermal disproportionation of methyltriaryloxyphosphonium halides formed in the reactions of triarylphosphites with alkyl halides, together with the formation of P-O-P intermediates, has been reported. The Michaelis-Arbuzov reaction has been used in the synthesis of phosphonate-based styrene-divinylbenzene resins and polyphosphonated chelation therapy ligands.Treatment of electron-rich benzylic alcohols dissolved in triethylphosphite with one equivalent of iodine affords a low-temperature one-pot route to the related benzylic phosphonates, compounds which are otherwise difficult to prepare. Upper-rim chloromethylated thiacalix[4]arenes have also been shown to undergo phosphonation on treatment with a phosphite ester in chloroform at room temperature. The nickel(II)-catalysed reaction of aryl halides with phosphite esters in high boiling solvents, e.g., diphenyl ether, (the Tavs reaction), has also... 

Winum, J.-Y., Kamal, M., Agnaniet, H., Leydet, A., Montero, J.-L. Study of the Michaelis-Arbuzov reaction during ultrasonic activation. Phosphorus, Sulfur Silicon Relat. Bern. 1997, 129, 83-88. 

Alkyl, Cycloalkyl. Aralkyl and Related Acids. - Reports on Michaelis-Arbuzov reactions continue to be widely distributed throughout the literature. Phosphite-phosphonate isomerization occurs in the presence of copper(I)... 

The Michaelis-Arbuzov reaction is supplemented by a closely related reaction, variously referred to as the Michaelis reaction (86), the Michaelis-Becker reaction (185), or the Michaelis-Becker-Nylen reaction (115), which involves the use of the salts of dialkyl hydrogen phos-phonates. For example, diethyl 2-diethylaminoethylphosphonate was obtained by this method despite failure of the Michaelis-Arbuzov reac-... 

It is evident that the interaction of a phosphorus(III) triester and the alkylating species RX can be pictured as an S 2 process (reaction 2) or, for those alkylating reagents capable of forming a carbocation, as an S l process (reaction 3). Several reactions testify to the importance of carbocationic carbon for the Michaelis-Arbuzov reaction in pursuance of its normal course they include the ease of reaction of cyclopropene dihalides, already encountered, and the ready formation of complexes with species having particularly weakly nucleophilic counter ions. Phosphonic acid formation also takes place with cyclic azonium salts and related ions. 9-Chloroacridine reacts with triethyl phosphite to afford a product thought to be the bisphosphonic acid ester 49 The related phosphonic esters 51 are obtainable when the onium salts 50 (X = NH, NR, O or S) are treated with trimethyl... 

The use of an electron-rich trivalent phosphorus center for addition to or substitution at an electrophilic site is a long-established approach to the formation of carbon-phosphorus bonds. The classical studies of the Michaelis-Arbuzov, Michaelis-Becker, Abramov, Pudovik, and related reactions and their mechanisms and synthetic utilities have been thoroughly reviewed. In this chapter, we present only a brief introduction to these reactions and provide several examples of their more facile uses from the older literature. More attention is given to relatively recent developments regarding such reactions that are seen as improvements in their general utility. 

Virtually simultaneously with the development of the Michae-lis-Arbuzov reaction, another closely related approach toward C-P bond formation was introduced. This involved the reaction of the salts of trivalent phosphorus-centered oxyacids with the same haloal-kanes as used in the Michaelis-Arbuzov reaction. First reported by Michaelis and Becker,142 this approach is commonly known as the "Becker reaction" or the "Michaelis-Becker reaction." Fundamental aspects of this reaction system have been reviewed previously.1 2 143... 

Classical Michaelis-Arbuzov or Michaelis-Becker approaches toward formation of C-P bonds involving aromatic carbon sites are (understandably) not generally feasible. Nucleophilic substitution reactions on aromatic carbon proceed only under particular circumstances relating to the nature of attendant additional substituents, and then often with mechanisms quite different from those observed in... 

A related reaction that yields the same types of products as does the Michaelis-Arbuzov reaction begins with either a phosphinous acid or a monoester of a phosphonous acid. (The corresponding reaction may also be performed with a diester of phosphorous acid.) By treatment with an appropriate base, the conjugate base of the phosphorus-containing acid is generated that serves as the nucleophihc reagent for direct formation of the phosphonate or phosphine oxide product (or phosphonate product from a phosphorous acid diester). This procedure is commonly referred to as the Michaehs Becker reaction. ... 

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