Systems Tl2MoO4-E(MoO4)2, where E = Zr or Hf, and the crystal structure of Tl8Hf(MoO4)6

Systems Tl₂MoO₄-E(MoO₄)₂ (E = Zr, Hf) are studied using X-ray powder diffraction, DTA, and IR spectroscopy. Compounds Tl₈E(MoO₄)₆ and Tl₂E(MoO₄)₂ are found in these systems. T-x diagrams for the Tl₂MoO₄-Zr(MoO₄)₂ system are designed. Single crystals are grown and structure is solved for Tl₈Hf(MoO₄)₆. The compound crystallizes in a monoclinic structure with the unit cell parameters a = 9.9688(6) Å, b = 18.830(1) Å, c = 7.8488(5) Å, β = 108.538(1)°, Z = 2, space group C2/m. The main structural fragment is a [HfMo₆O₂₄]^8? isle group. Three crystallographically independent types of Tl polyhedra uniformly fill spaces between [HfMo₆O₂₄]^8? fragments to form a three-dimensional framework.     

Synthesis and valence isomerization of dienicβ-keto esters

Conclusions A number of dienic– keto esters was synthesized and it was shown that a labile equilibrium exists in them between the cis-dienones and -pyrans, and also between the cis- and trans-isomers at the , double bond.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 10, pp. 2356–2359, October, 1973.     

Lipophilic pigments and fatty acids from the aerial parts of certain plant species of the genus Limonium. VII

Pigments and lipids from the aerial parts of six plant species from the genus Limonium (Plumbaginaceae, Limoniacea) were studied. Xanthophylls dominated among the carotinoids; chlorophyll, the chlorophylls, according to spectrophotometry. Unsaturated fatty acids, the content of which reached 80%, dominated in all samples according to GC. The principal fatty acids were 18:1 and 18:2. __________ Translated from Khimiya Prirodnykh Soedinenii, No. 5, pp. 412–414, September–October, 2006.     

Triterpene glycosides of Pulsatilla dahurica structures of glycosides A,B, C,and D

The isolation of four triterpene glycosides from the roots of the dahurian anemonePulsatilla dahurica (Fisch. ex DC) Spreng, is described together with their identification, on the basis of chemical transformations, spectral characteristics, and literature analogies, as hederagenin 3-O--L-arabinoside, hederagenin 3-O-[O--D-glucopyranosyl-(12)--L-arabinopyranoside], hederagenin 3-O--L-arabinopyranoside 28-O-[O--L-rhamnopyranosyl-(14)--D-glucopyranosyl-(16)--D-glucopyranoside], and hederagenin 3-O-[O--D-glucopyranosyl-(14)--L-arabinopyranoside] 28-O-[O--L-rhamnopyranosyl-(14)--D-glucopyranosyl-(16)--D-glucopyranoside].Pacific Ocean Institute of Bioorganic Chemistry, Far Eastern Branch, Russian Academy of Sciences, Vladivostok. Translated from Khimiya Prirodnykh Soedinenii, Nos. 3,4, pp. 349–356, May–August, 1992.     

Reactions of Phosphonioalkyl Derivatives of Phenylhydrazine and Hydroxylamine

Triphenyl- and tributyl[2-(2-phenylhydrazino)ethyl]phosphonium salts undergo dehydrogenation on heating to form the corresponding phenylhydrazones in high yields. The phenylhydrazone formed from the triphenylphosphonium salt can also be prepared from triphenyl(1-alkoxy-2-bromoethyl)phosphonium bromides. The latter reaction is proposed to involve reduction of the COC group with phenylhydrazine. N,N-Diphosphonioethylation and N,N-diphosphoniopropylation of hydroxylamine are performed. Alkaline hydrolysis of the resulting diphosphonium salts gave N, N-bis[2-(diphenylphosphoryl)ethyl(propyl)]hydroxylamines in high yields.__________Translated from Zhurnal Obshchei Khimii, Vol. 75, No. 7, 2005, pp. 1132–1136.Original Russian Text Copyright © 2005 by Ovakimyan, Barsegyan, Kikoyan, Indzhikyan.     

Thermodynamic parameters of sublimation of calix[4]arenes

The temperature dependences of the vapor pressure of calix[4]arenes were determined by the Knudsen effusion method. Some calix[4]arenes can form congruently subliming intramolecular compounds with a solvent. The thermodynamic parameters of the sublimation of the compounds were calculated. Molecules of organic solvents incorporated in the cavity of calix[4]arenes stabilize the crystal lattice, increasing the enthalpy of sublimation. The electrostatic interactions presumably make a significant contribution to stabilization of the crystal lattice of stoichiometric complexes of calix[4]arenes with solvents.     

Complex formation of mono-and binuclear dimeric cyclophane zinc diphenylporphyrinates with pyridine

The formation of host-guest complexes between zinc diphenylporphyrinates of dimeric diphenylporphyrins and pyridine in toluene has been studied by the spectrophotometric titration method and ¹H NMR spectroscopy. The zinc porphyrinates with pyridine form “internal” or “external” 1: 1 or 1: 2 complexes, depending on the length of binding ether O(CH₂)_nO bridges (n = 2, 3) of the cyclophane dimers and the reactant concentration. The stability constants of the porphyrinate-ligand complexes and concentration ranges of their formation have been determined.     

Five-component reciprocal systems Na,K∥Cl,CO<Subscript>3</Subscript>,MoO<Subscript>4</Subscript>,WO<Subscript>4</Subscript> and Na,K∥F,CO<Subscript>3</Subscript>,MoO<Subscript>4</Subscript>,WO<Subscript>4</Subscript>

Five-component reciprocal systems Na,K∥Cl,CO₃,MoO₄,WO₄ and Na,K∥F,CO₃,MO₄,WO₄ have been studied by differential thermal analysis (DTA) and X-ray powder diffraction (XPD). The systems have been triangulated to phase simplexes. The main reciprocal and complex-formation reactions have been revealed. The stability of [Na,K]₂CO₃, Na₂[Mo,W]O₄, and K₂[Mo,W]O₄ binary solid solutions and the nonexistence of quintuple invariant points in the title systems have been verified.     

Syntheses in the 4,5-dihydro-1,2,4-triazin-6-one-series

A study was carried out of alkylation, acylation and aminomethylation reactions were studied in the 5-alkyl-4,5-dihydro-1,2,4-triazin-4-one series. Alkylation by alkyl halides proceeds in the presence of sodium methylate at the N ₍₁₎ and N ₍₄₎ atoms with the formation of a mixture of alkylated compounds of three types: derivatives of 4,5-dihydrotriazine, unsaturated triazine, and their dimers. Acylation with isocyanates leads to the formation of heterocyclic ureas — derivatives at the N ₍₄₎ atom. Mono- and bisaminals were obtained by the reaction of triazines with ethoxymethyldiethylamine.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 963–970, July, 1991.