Diethyl acetylphosphonate

The expected product from the reaction of diethyl acetylphosphonate with sodium bisulfite and sodium cyanide is diethyl l-cyano-l-hydroxyethylphosphonate. However, a rearrangement takes place during the preparation under alkaline conditions (pH > 8) that leads to diethyl 1-cyanoethyl phosphate (Scheme By a similar procedure, long-chain diethyl a-cyanohy-... 

Diazoalkanes are well known as reagents for carbon insertion reactions through the intermediacy of carbenes. Here, diethyl acetylphosphonate has been shown to react with diazomethane to give a mixture of 2-(diethoxyphosphinoyl)-2-methyloxirane (the major product) together with traces of diethyl (2-oxopropyl)phosphonate the reaction between dimethyl acetylphosphonate and diazoethane and that between diethyl ben-zoylphosphonate and diazomethane both afford only the (2-oxoalkyl)phosphonic... 

The facility with which the phosphorus-carbon bond in acylphosphonic derivatives is cleaved by the action of the more basic nucleophiles has already been commented upon. Those nucleophiles include alkoxides and amines, but it may be noted that thiols undergo normal addition to the carbonyl group. With regard to the latter, diethyl acetylphosphonate yields the monothioacetals 256 the derivatives may not be stable thermally but their decomposition occurs with cleavage of the phosphorus-carbon bond Reactions between the same substrate and simple carboxamides in the presence of an acid catalyst under dry conditions furnish the acylated enamides 257 ". ... 

M/V-Diettiylacetamide Diethyl 2-acelarnidornalonate /V./V-Diettiylacetoacetamide Diethyl acetylphosphonate... 

In the presence of piperidine in benzene, benzaldehyde reacts with diethyl (nitromethyl)-phosphonate to afford at 67% yield of diethyl (2-hydroxy-l-nitro-2-phenylethyl)phos-phonate, presumably as a mixture of diastereoisomers. However, a similar reaction with 4-nitrobenzaldehyde leads to phosphorus-carbon bond cleavage and the formation of 1-nitro-2-(4-nitrophenyl)ethane. The converse procedure, i.e. a reaction which involves a nitroalkane and an (oxoalkyl)phosphonic diester, is also subject to certain restrictions. The base-catalysed nucleophilic additions of nitromethane to dialkyl acetylphosphonates (Scheme 7 R = Me) to give dialkyl [(1-hydroxy-l-nitromethyl)alkyl]phosphonates have... 

The reaction of ketene with diethyl hydrogen phosphonate leads to diethyl ace-toxyvinylphosphonate (equation 46) This reaction was assumed to involve the initial formation of acetylphosphonate, which underwent enolization and reaction with a second molecule of ketene to the final product. Infrared spectral examination of the product mixture revealed the formation of an additonal product, presumably a jS-lactone (v = 1830 cm ) which could be formed through 2 + 2 cycloaddition of a ketene molecule to the C=0 group of the acetylphosphonate. 

The synthesis of l-bis(trimethylsilyl)phosphinyl-l-trimethylsilyloxyvinylphosphonate (30) was studied thoroughly, because this compound is a starting material to a diphosphorus analog of phosphoenol pyruvate (equation 88)". It was found that bis(trimethylsi-lyl) acetylphosphonate can be silylated by using either chlorotrimethylsilane with triethylamine or A, iV-diethyl-iV-(trimethylsilyl)amine. 

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