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.     

Soluble polyelectrolytes based on some heterocyclic compounds

With the purpose of synthesizing the new types of soluble polyelectrolytes for special purposes radical polymerization and copolymerization of a number of heterocyclic compounds in solvents of different types with wide interval of pH medium was investigated. Interrelationships between reaction ability of the studied monomers and dielectric polarization of the media was established. An essential influence of water and pH medium on the polymerization rate and molecular weight of the synthesized polymers is found. The obtained effects are described on the basis of ionized monomers. The possibility to synthesize stereoisomeric polymers based on individual 3-buten-1-ynylpiperidinol isomers was shown. Some perspective ways of their practical application are given.     

Amphoteric ion-exchangers based on pyridine carboxylic acids

Conclusions Amphoteric ion-exchangers have been prepared by the reaction of styrene and divinylbenzene copolymers of conventional and macroporous structure with pyridine carboxylic acids.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya. No. lO, pp. 2366–2367,October, 1970.