Diphenyl chlorophosphonate

Diphenyl chlorophosphonate (= Azirenes from amides. Kete lates. Further reaction with NaN, I... 

By warming ofthe diazo-compound with traces of rhodium acetate in toluene at 80°C, the carbenoid inserts smoothly into the neighbouring N-H bond. This reaction step is ofparticular importance, since it constitutes a new methodology for the construction ofthe carbapenem skeleton. Although investigations on comparable bicycUc -ketoesters showed that these exist almost entirely in their keto-form, reaction with diphenyl chlorophosphonate and Himig s Base leads to the enol phosphate. 

Polyphosphazenes are flexible inorganic phosphorus-containing polymers which have been phosphonated and studied as electrolyte membranes. For example, brominated poly(aiylo g hosphazene) has been phosphonated via lithiation and reaction with diphenyl chlorophosphonate (Scheme 13.1h). Membranes cast from N,Af-dimethylformamide (DMF) had proton conductivities between 10 and 100 mS cm after equilibration in water. " ... 

The methodology has been successfully apphed to the synthesis of diphenyl a-chloro-4-pyridylmethylphosphonate, which was obtained in 80% yield from diphenyl a-hydroxy-4-pyridyl-methylphosphonate with POCI3 and catalytic quantities of diethylaniline. The a-chlorophosphonate products react with various 4-substituted benzaldehydes in the presence of t-BuOK (2 eq) to produce, by the Homer-Wadsworth-Emmons reaction, 4-pyridylacetylenes showing interesting nonlinear optical properties (Scheme 3.16). °... 

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