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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.

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