I. L. Nikolaeva

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,) (1a,b,c) with a number of P(III) derivatives i.e. triamido- and diamidophosphites, triphenylphosphite, monoand polyhalogenides of P(III) 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-diethylamido)menthylphosphite, phosphorus trichloride and triphenylphosphite. Phosphorylation of calix[4]resorcinarene (1c) with chloroanhydrides of chloromethylphosphonic and bis(chloromethyl) 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 q...

Effect of Substituents on the Supramolecular Structure and Stability of Crystals of Dialkylaminomethylated Calix(4)resorcinolarenes

The crystal and molecular structure of previously unknown dimethyl- and diethylaminomethylated calix[4]resorcinolarenes was determined by X-ray diffraction. The calixarene molecules occur in the crystal in the coneform, stabilized by the system of hydrogen bonds at the upper rim of the macrocycle. The crystal structure of the dimethylaminomethylated derivative includes 4.5 benzene molecules and an ethanol molecule per calixarene molecule. No solvent molecules are located inside the macrocycle cavity. In the structure of the diethylaminomethylated derivative there is one benzene molecule per calixarene molecule. The benzene molecule is located in the macrocycle cavity. The supramolecular structure of crystals is analyzed.

Crystal and Molecular Structure of Calix[4]arene Originating from Pyrogallol

First example of X-ray diffraction analysis of the crystal structure of calix[4]pyrogallolarene is reported. The compound was prepared by acid-catalyzed condensation of pyrogallol with propionaldehyde in a water-alcohol medium, and it gave rise to a system of “host-guest” type. Calixarene molecules in a cone conformation are packed in molecular layers; therewith each “host” molecule contains an ethanol molecule in the cavity. Hydroxy groups, ethanol and water molecules form a hydrophilic layer between two layers; as a result arises an endless bilayer structure.

Functionalization of Calix[4]resorcinolarenes with Trimethylsilyl Isocyanate

Calix[4]resorcinolarenes and their dialkylaminomethylated derivatives react with trimethylsilyl isocyanate to form addition products containing four silylcarbamate groups. These compounds are unstable and, depending on the nature of alkyl groups at the lower rim of the macrocycle, undergo two types of transformations. Intramolecular silylation yields calixarenes containing four carbamate and four trimethylsilyloxy groups at the upper rim. In the case of dialkylaminomethylated calixarenes, the initially formed addition products can undergo intramolecular cyclization to form a cavitand with four six-membered fragments at the upper rim.

Phosphorylation of Dialkylaminomethyl-substituted Calix[4]resorcinolarenes with Hexaalkylphosphorous Triamides and Phosphorus(V) Dichlorides

A series of aminophosphino cavitands were synthesized by reactions of dialkylaminomethyl-substituted calix[4]resorcinolarenes with hexaalkylphosphorous triamides, and their properties were studied. New aminoalkylated (thio)phosphato(phosphonato) cavitands were prepared by phosphorylation of dialkylaminomethyl-substituted calix[4]resorcinolarenes with phosphorus(V) dichlorides in the presence of a base. Their reactions with electrophilic alkylating agents (methyl trifluoromethanesulfonate, methyl iodide, and triethyloxonium tetrafluoroborate) were examined.

Synthesis and Properties of Phosphorylated and Silylated α-Mercaptocarbonyl Compounds

Abstract Phosphorylation and silylation of α -mercaptooarbonyl compounds have been investigated. A novel type of 1.4 S-O migration trimethylsilyl and P(III) groups has been discovered. The thiophosphite-thiophosphonate rearrangement when exposed to oxygen as well as heterocyclization with the formation of 1,3,2-oxathiaphospholenes and 1,3,2-oxathiasilalenes were also found. Some regularities of these processes and the properties of heterocycles synthesized have also been brought out.