Vasiliy V. Brusko

Crystal structure of t-Butylcalix[8]arene octamethyl ether

Abstract The title compound 1a crystallized with a molecule of chloroform in a triclinic lattice, space group P-1, with a=16.5215(19) A, b=17.4181(19) A, c=18.7403(18) A, α=78.328(8)°, β=64.210(8)°, γ=87.863(9)°, Z=2. The molecule assumes a not yet observed conformation with approximate (not crystallographic) C4V-symmetry with the inclusion of one molecule of chloroform in the molecular cavity. Layers of molecules are packed in alternating order in the crystal lattice.

New Cyclization of Some N -Thiophosphorylthioureas

We determined that the bis-thiourea 1 react with base bringing to elimination molecule of the isothiocyanate 3 and formation the N-thioposphorylbenzimidazolimide 2 (80% yield). Structure of compounds 1 and 2 was determined using single-crystal X-ray difraction. Process of cyclization greatly accelerated by oxidizer (I2). In contrast to 1 the bis-thiourea 4 is converted to potassium salt by treatment with a base. This salt reacts with iodine and forms iminoimidazolidine 5. One thiourea group kept safe in this compound. Nucleophilic activity of the endocyclic nitrogen atom of 5 more than nitrogen atom of strongly conjugated imidazolimide 2, therefore compound 5 don’t eliminate phosphorylisothiocyanate 3 (All R = OPr-i).

Immobilization of macrocyclic compounds with the purpose of development of ion-selective electrode for definition of rare-earths metals

The chemistry of macrocyclic compounds is one of the fastest developing areas of chemical researches. Objects of research served calix[4]resorcinarene (n = 4, R = CH2 N(CH3) CH3 (O)P(OC2H5)2; R1 = CH3) — one of representatives the class of macrocyclic receptors formed by para-substituted phenolic units linked ortho by methylene groups1 and N,N′-bis-(diisopropoxythiophosphoryl amidothiocarbonyl)-1,10-diaza-18-crown-6 — one of representatives of crown containing thiophosphorylated elementoorganic compounds.2 The methods of immobilization calix[4]resorcinarene on nitrocellulose film and N,N′-bis-(diisopropoxythiophosphoryl amidothiocarbonyl)1,10-diaza-18-crown-6 on acetylcellulose film was developed. Their methods were based on mechanical incorporation of organoelement compounds into nitroor acetylcellulose film with usage of organic solvents and covalently binding glutaraldehyde. The concentrations for immobilization were 1× 10−5 and 1× 10−4 M. The data of spectrophotometry at 250–300 nm at the presence of different buffer solutions with pH 4.1–9.7 were showed, that both of this compounds retained cellulose matrix strongly. These results can be used for development ion-selective electrode for definition of metal ions.

Coordination Chemistry of C(X)NHP(Y) Ligands: Progress and Prospects

Coordination chemistry of the N-(thio)phosphorylated (thio)ureas and (thio)amides R C(X) NH P(Y)R′2 (X, Y = O, S; R = Alk, Ar, NR2R3; R′ = OAlk) was born in 1967 (A. Schmidpeter, H. Groeger, Chem. Ber.) and revive now. These ligands can be prepared with a variation of substituents at phosphorus, carbon and exocyclic nitrogen atoms, which suppose to affect a steric environment around a metal atom in a complex. The ligands can form complexes with soft (Ag, Cd, Co, Cu, Hg, Pb, Pd, Pt, Ni, Zn) or hard metals depending on nature of atoms X and Y. K and Na form salts with the ligands having different combination of X and Y atoms. NH proton can be eliminated from the molecule or remain in the one during the complexation. It depends on nature of the ligands and methods of synthesis. At first case, the complexes formed have chelate structure. At second, one ligand behave as monodentate and uncharged particle.