Synthesis of New Phosphoruscontaining Three-Dimensional Structures on the Basis of Calix[4] Resorcinarenes

Abstract

Phosphorylation of calix[4]resorcinarenes with long chain aliphatic radicals (R=C6, C,. C,) (la,b,c) with a number of P(1II) derivatives i.e. triamido-and diamidophosphites, triphenylphosphite, monoand polyhalogenides of P(II1) is described. A series of phosphoamide cavitands (2),(3) were obtained. A new three-dimensional "container"-like structures, in which tetraresorcinol fragments are connected by means of phosphite bridges (13,14) were formed in the reaction of (Ib) with (-) bis(N,N-diethy1amido)menthylphosphite , phosphorus trichloride and triphenylphosphite. Phosphorylation of calix[4]resorcinarene (lc) with chloroanhydrides of chloromethylphosphonic and bis(ch1o-romethy1)phosphinic acids results in completely or partially posphorylated products depending on the reaction conditions. The synthesis of dimeric "head to head" macrocyclic derivative of chlormethylphosphonic acid (19) is described. Structures and properties of synthesized compounds were discussed on the basis of physical and quantum chemical methods.

Amides of Trivalent Phosphorus Acids as Phosphorylating Reagents for Proton-Donating Nucleophiles

“…The data on cyclophosphorylation of octaols with phosphorus diamides, whose molecules contain residues of biological molecules (steroids, carbohydrates, and menthol), appear especially promising. In this case, the corresponding conjugates can be formed. − In addition, coupling of two calixarene residues by a phosphorus diamide to give a complex three-dimensional structure has been reported. , …”

“…[279][280][281] In addition, coupling of two calixarene residues by a phosphorus diamide to give a complex three-dimensional structure has been reported. 282,283…”

Phosphorus-containing macrocyclic compounds: synthesis and properties

“…Generally, it was performed by the attachment of sulfur to trivalent phosphorus atoms of calix [4]resorcinols or cavitands pre-phosphorylated at the upper rim. 82,140,145,151,152,161 …”

Phosphorus-containing calixarenes

“…The macrocyclic phosphites 32 were detected only in the reactions of 31d,e with heptyl and octyl phosphorous diamides. 39 Phosphorylation of the calixarene 31e with (7)-menthyl tetraethylphosphorous diamide under mild conditions with different ratios of the reactants affords completely and partially phosphorylated optically active derivatives containing both cyclic phosphite groups and acyclic menthyl phosphorous amide fragments (for example, compound 35). When the ratio of the reactants is 1 : 2 and the reaction conditions are more drastic the `ball' structure 36 is formed.…”

“…40 The reaction of the calixarene 31d with 2-chloro-1,3,2-benzodioxaphospholene at any ratio of the reactants gives phosphite 37, occurring in an equilibrium with a slight amount of spirophosphorane 38. 41 Cavitands containing acyclic phosphinite (39) and cyclic phosphonite (40) fragments have been prepared by the reaction of the calixarene 31h with chloro(diphenyl)phosphine and dichloro(phenyl)phosphine, respectively, in the presence of pyridine. 42 The high complexation capacity of these calixarenes was confirmed by introducing them into reactions with Pt(II) and Au(I) salts.…”