Reaction of tert-Butyl Tetraethylphosphorodiamidite with Bromomalonic Ester

Russian Journal of General Chemistry -     

Reactions of Phosphorodiamidous Acid Esters with α-Halocarbonyl Compounds

Reactions of ethyl and tert-butyl phosphorodiamidites with chloroacetone, bromoacetone, and -chloroethyl acetate were studied. The reaction pathway is determined by the structure of the intermediate quasiphosphonium compound responsible for the formation of the Arbuzov product as well as for the occurrence of the amonalous reaction yielding vinyl phosphate.     

tert-Butyl Tetraethylphosphorodiamidite in Reactions with α,β-Unsaturated Dicarbonyl Compounds

Reactions of tert-butyl tetraethylphosphorodiamidite with benzylideneacetylacetone, benzylideneacetoacetic ester, and benzylidenemalonic ester are studied. It is shown that the reaction pathway significantly depends on the solvent and temperature. The reaction with benzylidenacetylacetone in ether gives rise to a stable diketophosphonate, while the same reaction in boiling benzene involves elimination of diethylamine and yields a phospholene. The reaction with benzylideneacetoacetic ester proceeds analogously, while with benzylidenemalonic ester the corresponding phospholene is formed exclusively.     

Aminophosphonates in the Synthesis of New Radioprotecting Agents

Reactions of bis(trimethylsilyl) hydrogen phosphite with Schiff bases derived from indole-3-carbaldehyde and aniline or ethyl p-aminobenzoate, as well as of diisopropyl hydrogen phosphite with N-benzylideneaniline, gave water-soluble sodium salts of -aminophosphonic acids which are potential radioprotecting agents.     

Unexpected Reaction Pathway of tert-Butyl Tetraethylphosphorodiamidite with Benzyl Chloride

Russian Journal of General Chemistry -     

Reactions of tert-Butyl Tetraethylphosphorodiamidite with Acetic and Trifluoroacetic Acids

Reactions of tert-butyl tetraethylphosphorodiamidite with acetic and trifluoroacetic acids involve substitution of the amido group. This process was described by a scheme beginning with protonation of phosphorus and proved by modeling separate reaction stages. A probable scheme of the proposed reactions is described.     

Mechanism of Reactions of P(III) Amidoesters with Carboxylic Acid Chlorides

Russian Journal of General Chemistry -     

Reactions of tert-Butyl Phosphoramidites with Carbon Tetrachloride and Chloroform

The reactions of 2-tert-butoxy-3-phenyl-1,3,2-oxazaphospholane and di-tert-butyl diethylphosphoramidite with carbon tetrachloride and chloroform were studied. These reactions proceed via formation of an intermediate quasiphosphonium compound. In the process, carbon tetrachloride acts as a source of positively charged halogen, and chloroform, as a C-H acid.