Larisa K. Vasyanina

Nature of acid-catalyzed alcoholysis of amides of trivalent-phosphorus acids

Abstract To study the chemical nature of the acid catalysis of amides oftrivalent-phosphorus acids (ATPA) alcoholysis the most important procedural problems have been solved. Simple and efficacious techniques for the purification of original ATPA from amine hydrohalides have been worked out. A precise and reliable way has been chosen to control the residual amount of amine hydrohalides in ATPA having been subjected to the various purification procedures. The nature of the dependence of alcoholysis rate constants for ATPA of different structures on the aminehydrohalide concentration has been established. The general acid catalysis was established using the Bronsted equation, so that the process includes the formation of a catalytic H-complex incorporating substrate and catalyst on the whole. Amides P(III) of different types treated with anhydrous hydroborofluoric acid readily form the corresponding P-protonated salts. The conversions of corresponding products of complete protonation have been investigated. The structure of P-protonated salt 23 has been studied by means of X-ray analysis.

Complexes of P(III)-phosphocavitands with Groups VI and VII transition metal carbonyls

Abstract A study has been made of the interaction between the new type of cavitands, P(III)-phosphocavitands, and the Cr, Mo, W, and Mn carbonyl complexes. The possibility has been shown for the directed coordination of all or some phosphorus atoms of the cavitand molecules with metals. The effect of the substituents at the phosphorus atoms in the macrocycles on the process selectivity has been revealed. The first metallocomplexes of phosphocavitands containing trivalent phosphorus atoms have been obtained.

AMIDOPHOSPHITES IN THE CHEMISTRY OF CALYX[4]RESORCINOLARENE

Abstract The possibility of using phosphorous amides for the phosphorylation of calyx[4]resorcinolarenes is found. This reaction can be directed to the synthesis of their octaphosphorylated derivatives or phosphocavitands. It is shown that the obtained compounds demonstrate substantially different properties depending on the character of their molecular matrix.

TETRAPROPYLPHOSPHOCAVITANDS: SYNTHESIS, STRUCTURE, AND PROPERTIES

Abstract Cyclophosphorylation of tetrapropylcalyxresorcin[4]arene by phosphorous amides gave P(III)-phosphocavitands, modification of which resulted in a series of P(V)-phosphocavitands with different substituents at phosphorus atoms. The first alkylation of amidophosphocavitands has been performed.

Dismutation of diamidoarylphosphites

Some examples of spontaneous dismutation of diamidoarylphosphites in different solvents were studied, and features of the process were revealed.

First heterobimetallic complexes of phosphocavitands

Abstract The synthesis and characterisation were described for tetranuclear phosphocavitand complexes 4 , where each phosphorus atom is coordinated to the silver atom, and tetranuclear heterobimetallic phosphocavitand complexes 6 , in which only three phosphorus atoms are coordinated to silver and the fourth phosphorus atom is coordinated to molybdenum. Compounds 4 were obtained by the reaction of AgBr with amidophosphitocavitands 1 . Compounds 6 were synthesised by the reaction of AgBr with mononuclear molybdenum complexes of amidophosphocavitands 3 . It was found that, in the presence of diethylammonium cation, 4a forms anionic complex [(C 2 H 5 ) 2 NH 2 ][cavitand·Ag 4 (μ-Br) 4 (μ 4 -Br)] ( 5 ), whose structure was supported by X-ray diffraction analysis.

THE SYNTHESIS AND STRUCTURE OF P(III)-PHOSPHORYLATED 2-AMINOPYRIDINES AND THEIR DERIVATIVES

Abstract A number of the derivatives of 2-aminopyridine and diisopropyl-phosphinous, neopentylene- and pyr-ocatecholphosphorus acids 1−3 and also the diphosphorylated derivative 4 have been obtained. Phosphinite 1 was alkylated by triethyloxoniumtetrafluoroborate with the formation of quasi-phosphonium salt 5 and was protonated by hydrogen chloride at the endocyclic nitrogen atom to form pyridinium salt 6. The structure of all obtained compounds was studied by 1H, 13C, 15N and 31P NMR spectroscopy and it was shown that they exist predominantly in the phosphoaminopyridine form A.

Dismutation of Bisphosphorylated Aromatic Diols

Abstract The first study of the dismutation of aromatic diol bisdiamidophosphites has been performed. Derivatives of condensed aromatic systems dismutate more rapidly than their mononuclear analogues. Amide derivatives with aliphatic substituents at the nitrogen atom undergo dismutation more readily than their heterocyclic analogues. In methylene chloride, the process proceeded most rapidly regardless of the aromatic component and the substituent at the phosphorus atom. Apolar solvents (benzene and diethyl ether) did not favor the dismutation. Temperature had no effect on the time of dismutation, and a catalyst decreased it by a factor of 1.5–2.

COMPLEXES OF PHOSPHOCAVITANDS WITH GROUP VI METALS

Abstract The first complexes of amidophosphito- and phosphitocavitands with the group VI transition metal hexacarbonyls have been obtained. It was shown that the liganding ability of P(III)-phosphocavitands depended on the nature of exocyclic substituents at the phosphorus atoms.

The Synthesis and Some Chemical Properties of New 1,2:5,6-DI-O-Isopropylidene-α -D-Glucofuranose Hydrophosphoryl Derivatives

Methods for the synthesis of major monosaccharide hydrophosphoryl derivatives have been developed with the phosphorylation of 1,2:5,6-di-O-isopropylidene-α -D-glucofuranose (diacetoneglucose) as an example. The study of their chemical transformations has been launched.