A quantum-chemical investigation of deoxypeganine and its salts II. The photochemical oxidation of deoxypeganine hydrochloride

The stability of deoxypeganine hydrochloride under the action of light has been established. The kinetics of the oxidation of deoxypeganine hydrochloride in aqueous solution in the presence of deoxyvasicinone hydrochloride have been studied. The structures and electronic conformations of hypothetical models of the salt DOP HCl in the ground and excited states have been considered by the MO LCAO method in the AM1 approximation. The difference in the resistance of the molecules of the base deoxypeganine and its hydrochloride to photochemical oxidation is discussed on the basis of the results of experiments and calculations.Abbreviations HPLC high-performance liquid chromatography - MO LCAO molecular orbitals as linear combinations of atomic orbitals - AM1 Austin Model 1 - DOP HCl deoxypeganine hydrochloride - DOV HCl deoxyvasicinone hydrochloride Institute of the Chemistry of Plant Substances, Academy of Sciences of the Republic of Uzbekistan, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 5, pp. 729–733, September–October, 1993.     

Synthesis and structure of tricyclic quinazoline alkaloid oxalates

Oxalates of the alkaloids deoxyvasicinone, 2,3-tetra-, and their seven-membered analog 2,3-pentamethylen-3,4-dihydroquinazol-4-one and the complex of 2,3-pentamethylen-3,4-dihydroquinazol-4-one hydrochloride with oxalic acid were synthesized. It was found that 2:1, 2:1, and 1:1 alkaloid:oxalic acid complexes, respectively, were formed. The last complex had 2,3-pentamethylen-3,4-dihydroquinazol-4-one, oxalic acid, and HCl in a 2:1:2 ratio, respectively. X-ray crystal structures of single crystals were performed. The oxalate of 2,3-pentamethylen-3,4-dihydroquinazol-4-one and its hydrochloride formed salts with a protonated N1 atom and involvement of only one hydroxyl. The other alkaloids formed a complex with oxalic acid through N1…H-O H-bonds involving both acid hydroxyls. __________ Translated from Khimiya Prirodnykh Soedinenii, No. 2, pp. 152–156, March–April, 2007.     

Ab Initio Study of the (DMF) m · (HCl) n (m,n = 0–2) Complexes

Based on the results of ab initio calculations (B3LYP, 6-31++G(d,p)), the structures and stability of the complexes DMFA · HCl, (DMF)₂ · HCl, DFF · (HCl)₂, and (DMF · HCl)₂ are compared. In the complex with a 1 : 1 composition, DMF and HCl form a hydrogen bond of the molecular type. In the heterotrimers with compositions 1 : 2 and 2 : 1, the hydrogen bond noticeably strengthens. In the tetramer (DMF · HCl)₂, the most pronounced proton transfer takes place and two quasi-symmetric hydrogen bridges O···H···Cl are formed and stabilize this complex. The results of calculations are compared with data on the structure of complexes between HCl and DMF obtained by crystal-structure XRD and vibrational spectroscopy in solutions.     

A quantum-chemical investigation of deoxypeganine and its salts II. The photochemical oxidation of deoxypeganine hydrochloride

The stability of deoxypeganine hydrochloride under the action of light has been established. The kinetics of the oxidation of deoxypeganine hydrochloride in aqueous solution in the presence of deoxyvasicinone hydrochloride have been studied. The structures and electronic conformations of hypothetical models of the salt DOP HCl in the ground and excited states have been considered by the MO LCAO method in the AM1 approximation. The difference in the resistance of the molecules of the base deoxypeganine and its hydrochloride to photochemical oxidation is discussed on the basis of the results of experiments and calculations.     

Study of the Stable Nanocrystalline TiO<Subscript>2</Subscript> Hydrosol and its Fractions

Nanodisperse TiO₂ hydrosol and two of its fractions stabilized by HCl are studied. The anatase nanocrystalline fractions are obtained by the stepped coagulation of the stable sol using dependence of coagulation thresholds on size of nanocrystallites. X-Ray investigation in small and wide angles of scattering has revealed that the anatase nanocrystallites have a shape of 2.5–3 nm thick elongated plates with 8–18 nm lateral sizes. The concentrated hydrosols with the reduced HCl content prepared from the anatase fractions are shown to form an ordered structure. Narrow fractions of TiO₂ nanocrystallites obtained from the stable hydrosols seem to be promising for the preparation of highly ordered structures with a nanometer periodicity.     

Uranyl ion complexes with long chain aminoalcoholbis(phenolate) [O,N,O,O′] donor ligands

The reaction between uranyl nitrate hexahydrate and phenolic ligand precursor [(N,N-bis(2-hydroxy-3,5-dimethylbenzyl)-4-amino-1-butanol) · HCl], H₃L1 · HCl, leads to a uranyl complex [UO₂(H₂L1)₂] (1a) and [UO₂(H₂L1)₂] · 2CH₃CN (1b). The ligand [(N,N-bis(2-hydroxy-5-tert-butyl-3-methylbenzyl)-4-amino-1-butanol)H₃L2 · HCl], H₃L2 · HCl, yields a uranyl complex with a formula [UO₂(H₂L2)₂] · CH₃CN (2). The ligand [(N,N-bis(2-hydroxy-3,5-dimethylbenzyl)-5-amino-1-pentanol) · HCl], H₃L3 · HCl, produces a uranyl complex with a formula [UO₂(H₂L3)₂] · 2CH₃CN (3) and the ligand [(N,N-bis(2-hydroxy-5-tert-butyl-3-methylbenzyl)-5-amino-1-pentanol) · HCl], H₃L4 · HCl, leads to a uranyl complex with a formula [UO₂(H₂L4)₂] · 2CH₃CN (4). The ligand [(N,N-bis(2-hydroxy-5-tert-butyl-3-methylbenzyl)-6-amino-1-hexanol) · HCl], H₃L5 · HCl, leads to a uranyl complex with a formula [UO₂(H₂L5)₂] · 4toluene (5). The complexes 1–5 are obtained using a molar ratio of 1:2 (U to L) in the presence of a base (triethylamine). The molecular structures of 1a, 1b, 3, 4 and 5 were verified by X-ray crystallography. All complexes are neutral zwitterions and have similar centrosymmetric, mononuclear, distorted octahedral uranyl structures with the four coordinating phenoxo ligands in an equatorial plane. In uranyl ion extraction studies from water to dichloromethane with ligands H₃L1 · HCl–H₃L5 · HCl, ligands H₃L1 · HCl, H₃L4 · HCl and H₃L5 · HCl are the most effective ones.     

Aminoalkylbis(phenolate) [O,N,O] donor ligands for uranyl(VI) ion coordination: Syntheses,structures, and extraction studies

The syntheses of five new aminoalkylbis(phenolate) ligands (as hydrochlorides) and their uranyl complexes are described. The reaction between uranyl nitrate hexahydrate and phenolic ligand [(N,N-bis(2-hydroxy-5-tert-butyl-3-methylbenzyl)-1-aminopropane) · HCl], H₂L1 · HCl, forms a uranyl complex [UO₂(HL1)₂] · 2CH₃CN (1). The ligand [(N,N-bis(2-hydroxy-5-tert-butyl-3-methylbenzyl)-1-aminobutane) · HCl], H₂L2 · HCl, forms a uranyl complex with a formula [UO₂(HL2)₂] · 2CH₃CN (2). The ligand [(N,N-bis(2-hydroxy-5-tert-butyl-3-methyl benzyl)-1-aminohexane) · HCl], H₂L3 · HCl, yields a uranyl complex with a formula [UO₂(HL3)₂] · 2CH₃CN (3) and the ligand [(N,N-bis(2-hydroxy-5-tert-butyl-3-methylbenzyl)-cyclohexylamine) · HCl], H₂L4 · HCl, yields a uranyl complex with a formula [UO₂(HL4)₂] (4). The ligand [(N,N-bis(2-hydroxy-5-tert-butyl-3-methylbenzyl)-benzylamine) · HCl], H₂L5 · HCl, forms a uranyl complex with a formula [UO₂(HL5)₂] · 2MeOH (5). The molecular structures of 1, 2′ (2 without methanol), 3, 4 and 5 were verified by X-ray crystallography. The complexes 1–5 are neutral zwitterions which form in a molar ratio of 1:2 (U to L) in the presence of a base (triethylamine) and bear similar mononuclear, distorted octahedral uranyl structures with the four coordinating phenoxo ligands forming an equatorial plane and resulting in a centrosymmetric structure for the uranyl ion. In uranyl ion extraction studies from water to dichloromethane with ligands H₂L1 · HCl–H₂L5 · HCl, the ligands H₂L2 · HCl and H₂L4 · HCl are the most effective ones.     

The lignin of the algaFucus vesiculosus

Summary 4-Thio analogs of deoxyvasicinone have been synthesized by the reaction of deoxyvasicinone and its derivatives and homologs with phosphorus pentasulfide. The reduction of these thio analogs has given deoxypeganine and its homologs.Institute of the Chemistry of Plant Substances, Academy of Sciences of the Uzbek SSR, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 5, pp. 668–670, September, October, 1977.     

Alkaloids ofNitraria komarovii. XV. Vasicinone and deoxyvasicinone N-oxides

Two new alkaloids have been isolated from the epigeal part ofNitraria komarovii — the N-oxides of vasicinone and of deoxyvasicinone. Their structures have been established on the basis of spectral results and chemical transformations.Institute of the Chemistry of Plant Substances, Academy of Sciences of the Republic of Uzbekistan. Translated from Khimiya Prirodnykh Soedinenii, No. 4, pp. 580–582, July–August, 1993.     

Can Water Clusters Ionize HCl under the Conditions of Arctic Stratosphere? 1. Intermolecular Interactions

Pseudopotential model was constructed to simulate the H₃O⁺(H₂O) _n Cl^– clusters at room and stratosphere temperatures using the Monte Carlo method. Numerical values of interaction parameters were restored from the experimental data on the free energy and entropy of vapor nucleation on ions in the combination with the data of quantum chemical calculations of the optimal configurations of HCl(H₂O) _n clusters. The stability of various cluster structures and the probability of the rupture of intramolecular HCl bond in these clusters were analyzed.     

Thermal decomposition of new ruthenium(II) complexes containing <Emphasis Type="Italic">N</Emphasis>-alkylphenothiazines

Thermal decomposition of chlorpromazine hydrochloride (CP·HCl), trifluoperazine dihydrochloride (TF·2HCl) and thioridazine hydrochloride (TR·HCl), and the ruthenium complexes with dimethyl sulfoxide (dmso) of composition [RuCl₂(dmso)₄] and L[RuCl₃(dmso)₃]·xEtOH, L = CP·HCl, TF·2HCl or TR·HCl is described. The phenothiazines are stable to temperature range of 200–280 °C with an increasing stability order of TF·2HCl < CP·HCl < TR·HCl. The decomposition of all the compounds takes place in superposing steps. For detection of chlorides and sulfides, EGD analysis was performed. The decomposition pattern of the complexes, due to their similar structure, is similar. The thermal data unambiguously resolve the contradiction between the elemental analysis and X-ray structural data for (TF·2HCl)[RuCl₃(dmso)₃]Cl·EtOH. The compound crystallizes with one EtOH, evaporating in part at room temperature.     

Ion-molecular interactions and the equilibrium composition in the HCl-1-methyl-2-pyrrolidone-1,1,2,2-tetrachloroethane system according to IR spectroscopy data

Multiple Attenuated Total Reflectance (MATR) IR spectra of solutions of HCl in 1-methyl-2-pyrrolidone (N-MP) (0–43.4 % HCl) were studied in the 900–4000 cm^–1 range. Spectra were recorded for theN-MP-HCl-1,1,2,2-tetrachloroethane (TCE) ternary system at a TCE N-MP ratio of 1 1. Depending on the ratio between the components, complexes of the compositionN-MP · HCl (C-1),N-MP · 2HCl (C-2), and 2N-MP · HCl (C-3) are formed in the system. Complex C-1 has a quasiionic structure, (CH₂)₃N(Me)CO...H...Cl, formed by a strong quasisymmetrical H-bond between the carbonyl O atom and the Cl atom. The addition of anN-MP molecule to complex C-1 yields complex C-3, in which the quasiionic character of the bond betweenN-MP and HCl is retained. When excess HCl is present, the quasiionic structure is destroyed, theN-MP molecule is protonated, and the Cl^– anion interacts with HCl to give an ion with a strong symmetrical H bond (Cl...H...Cl)^–. Complex C-2 is an ion pair.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1757–1763, September, 1995.This work was carried out with financial support of the Russian Foundation for Basic Research (Project No. 93-03-18356).     

Ion-molecular interactions in the HCl—isopropanol system

Multiple Attenuated Total Reflectance (MATR) IR spectra of solutions of HCl in isopropanol, containing 0 to 43 mol. % HCl, were studied in the 900–4000 cm^–1 range. The addition of HCl to PrⁱOH yields proton disolvates with strong symmetrical H-bonds. At high concentrations of HCl (C _HCl ⁰ > 5.7 mol L^–1, /C⁰ _HCl < 2), when the number of alcohol molecules is not enough to form disolvates with all of the protons present in the solution, (Cl...H...Cl)^– ions are formed, in addition to (C₃H₇OH)₂H⁺. The spectra of these ions have been assigned.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1753–1756, September, 1995.This work was carried out with financial support of the Russian Foundation for Basic Research (Project No. 93-03-18356).     

Determination of Hf, Sc and Y in geological samples together with the rare-earth elements

 A method is described for the determination of Hf, Sc and Y simultaneously with the REE in geological materials. An earlier method for REE separation from major elements was studied with the aim to apply it also to the determination of Hf, Sc and Y. Sample decomposition was carried out by melting with LiBO₂. The method involves separation and concentration stages, using the cation-exchange resin DOWEX AG 50W-X8. Matrix elements were eluted with 2 mol/l HCl, whereas 6 mol/l HNO₃ with oxalic acid and 8 mol/l HNO₃ were used to elute the elements to be determined. Some of the matrix elements could not be completely removed. This effect as well as the recovery rates of the determined elements were investigated. The measurements were performed by ICP-AES. Spectral interferences were also tested. Received: 8 November 1995/Revised: 12 March 1996/Accepted: 14 March 1996     

Synthesis of 2,2,6,6-tetramethyl-1-oxyl-4-piperidyloxy-tert-butylperoxyalkylsilanes

2,2,6,6-Tetramethyl-1-oxyl-4-piperidyloxy-tert-butylperoxyalkylsilanes were obtained by condensation of 2,2,6,6-tetramethyl-4-hydroxypiperidine-1-oxyl with organosilicon chloroperoxides ClR₂SiOOR' (R = Me, Et; R' = Bu^t) in ether at 0–5 °C in the presence of a tertiary amine as an HCl acceptor.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 984–985, May, 1995.     

Determination of plutonium in environmental samples by controlled valence in aniion exchange

The title method was successfully used for collecting^239,249Pu from 200 litres of seawater by coprecipitation with 16 g FeSO₄·7H₂O under redcing conditions witout filtering. The plutonium is leached by concentrate HNO₃+HCl from the coprecipitate and the solid particles. The precipitate is heated at 400°C and digested in aqua regia. Na₂SO₃ and NaNO₂ have been applied to obtain the Pu⁴⁺ valence state in 0.5–1N HNO₃ for different samples. Plutonium and thorium are coadsorbed on anionic resin from 8N HNO₃. The column is eluted with 8N HNO₃ containing fresh NaNO₂ to keep the Pu⁴⁺ state for uranium decontaination. The system of the column is changed from 8N HNO₃ to concentrated HCl with 50 ml concentrated HCl containing a few milligrams of NaNO₂. Furtheer decontaimination of torium was achieved by elution with concentrated HCl instead of 9N HCl. The plutonium is successfully stripped by H₂O, NaOH, 2N HNO₃ and 0.5N HNO₃ containign 0.01M NaNO₃. The chemica yield of plutonium for a 2001 seawate sample is 60–80%. The resolution of the electroplated thin source is very good.     

Alkaloids ofNitraria komarovii. XV. Vasicinone and deoxyvasicinone N-oxides

Two new alkaloids have been isolated from the epigeal part ofNitraria komarovii — the N-oxides of vasicinone and of deoxyvasicinone. Their structures have been established on the basis of spectral results and chemical transformations.     

Crystal and molecular structure of the complex salt of peganine with zinc chloride

The crystal structure of peganine in its complex with ZnCl₂·2H₂O has been established by the x-ray structural method (diffractometer, CuK radiation, 1796 reflections, direct method, R = 0.079). A similarity has been found in the solvation of the crystalline complexes with ZnCl₂·HCl of the alkaloids peganine and deoxypeganine. A tendency to the averaging of the N 1=C2 and N3-C2 bonds in quinazolines protonated at N1 is observed.Institute of the Chemistry of Plant Substances, Academy of Sciences of the Republic of Uzbekistan, Tashkent, fax (3712) 89 14 75. Translated from Khimiya Prirodnykh Soedinenii, No. 3, pp.426–430, May–June, 1995. Original article submitted June 20, 1994. submitted June 20, 1994.     

The extraction of HCl by TDPO in benzene

The results of the extraction of HCl by TDPO in benzene and the co-extraction of water are discussed. From the infrared spectra of normal (HCl-H₂O) and deuterated (DCl-D₂O) systems it may be concluded that TDPO·HCl·H₂O is formed in the organic phase on extraction from aqueous solutions with c_HCl≤5M, and TDPO·HCl with c_HCl>5M. Compounds such as TDPO·2HCl are found in the organic phase if there is an excess of HCl in the organic phase. From cryoscopic and viscosity measurements of the organic phase, conclusions can be made about the presence of polymeric compounds in this phase.     

Activity Coefficients for the System HCl +GaCl3 + H2O from 5 to 55°C

Activity coefficients for HCl in HCl + GaCl₃ + H₂O at eleven different temperatures from 5 to 55°C have been determined at total experimental ionic strengths from 0.01 to 3.0 mol-kg^–1 using a cell of the type: Pt; H₂(g, 1 atm)|HCl (m_A) + GaCl₃(m_B)|AgCl, Ag (A) The results for the 770 experimental emf data points have been used to determine the variation of the activity coefficients of HCl with the change in molality of GaCl₃ in the solution. It is found that the linear form of Harned's rule is not obeyed for this system.