Michaelis-Becker-Nylen reaction

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-... 

In contrast to the Michaelis-Arbuzov reaction, which is carried out by heating the reactants together at 120-160° for several hours, the Mi-chaelis-Becker-Nylen reaction often takes place at room temperature, particularly when tetrahydrofuran is employed as the solvent (128). The temperature advantage is frequently offset by the greater tendency of the ionic phosphorus reagents to participate in side reactions. The mechanism of the Michaelis-Becker-Nylen reaction, often assumed to be SN2, is not established with certainty (283). 

Nylen successfully used the Michaelis-Becker reaction for the preparation of phosphonoacetic esters. 56 Thus, diethyl l-(ethoxycarbonyl)methylphosphonate can be obtained in satisfactory yield (50%) by the reaction of sodium diethyl phosphite with ethyl chloroacetate in refluxing Et20 (Scheme The choice of the reaction solvent is crucial to the success of the reaction.For... 

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