Infrared spectra of N2O-(ortho-D2)N and N2O-(HD)N clusters trapped in bulk solid parahydrogen

High-resolution infrared spectra of the clusters N2O-(ortho-D2)N and N2O-(HD)N, N=1-4, isolated in bulk solid parahydrogen at liquid helium temperatures are studied in the 2225 cm-1 region of the nu3 antisymmetric stretch of N2O. The clusters form during vapor deposition of separate gas streams of a precooled hydrogen mixture (ortho-D2para-H2 or HDpara-H2) and N2O onto a BaF2 optical substrate held at approximately 2.5 K in a sample-in-vacuum liquid helium cryostat. The cluster spectra reveal the N2O nu3 vibrational frequency shifts to higher energy as a function of N, and the shifts are larger for ortho-D2 compared to HD. These vibrational shifts result from the reduced translational zero-point energy for N2O solvated by the heavier hydrogen isotopomers. These spectra allow the N=0 peak at 2221.634 cm-1, corresponding to the nu3 vibrational frequency of N2O isolated in pure solid parahydrogen, to be assigned. The intensity of the N=0 absorption feature displays a strong temperature dependence, suggesting that significant structural changes occur in the parahydrogen solvation environment of N2O in the 1.8-4.9 K temperature range studied.     

Plasma-assisted synthesis and properties of Na(3)N

Dark-blue sodium nitride, Na(3)N, was prepared by the reaction of metallic sodium or liquid Na-K alloy with plasma-activated nitrogen at low pressure. The compound crystallizes in the cubic anti-ReO(3)-type structure (space group Pm3m with a = 4.73301(6) Angstrom and Z = 1) according to powder and single-crystal X-ray diffraction data. Na(3)N decomposes above 104 degrees C into the elements, with DeltaH(f) estimated at +64(2) kJ/mol.     

Heteronuclear (Co-Ca, Co-Ba) 2,3-pyridinedicarboxylate complexes: synthesis, structure and physico-chemical properties

Three pyridine 2,3-dicarboxylate complexes have been synthesized and characterized by IR spectroscopy, thermal analysis and single crystal X-ray diffractometry. Their magnetic properties have also been studied by EPR and magnetisation measurements. The decomposition of such complexes in air leads to the generation of mixed metal oxides, as confirmed by powder X-ray diffraction.     

Crystal and molecular structure of the 4-O-[bis(N,N-diethylamido)thionephosphate]-2,3; 5,6-bis-O,O-(N,N-diethylamidothionephosphate)-N,N-dimethylamide of D-gluconic acid

Conclusions The crystal and molecular structure of the SS P-diastereomer of the 4-O-[bis(N,N-diethylamido)thionephosphate]-2,3; 5,6-bis-O,O-(N,N-diethylamidothionephosphate)-N,N-dimethyl-amide of D-gluconic acid were determined.Translated from Izvestiya Akademii Nauk SSSR, Serlya Khimicheskaya, No. 6, pp. 1274–1279, June, 1986.     

Efficient access to isomeric 2,3-dihydroxy lupanes: first synthesis of alphitolic acid

Alphitolic acid (3) is a naturally occurring lupane type of pentacyclic triterpene, which possesses various pharmacological properties. Efficient synthesis of 3 has been accomplished in 10 steps with an overall yield of 19% starting from the readily available diketone 11. An alternative approach to the key intermediate 17 has also been developed, and based on this approach, 3 could be obtained in 10 steps with an overall yield of 26% starting from 11. Moreover, seven other isomeric 2,3-dihydroxy lupanes 4-10 have been synthesized. The synthesized triterpenes 3-10 were evaluated for their inhibitory activity against rabbit muscle GPa (RMGPa), and some of them exhibited moderate inhibitory activity against RMGPa.     

Antiproliferative activity of chelating N,O- and N,N-ruthenium(II) arene functionalised poly(propyleneimine) dendrimer scaffolds

Chelating neutral (N,O) and cationic (N,N) first- and second-generation ruthenium(II) arene metallodendrimers based on poly(propyleneimine) dendrimer scaffolds were obtained from dinuclear arene ruthenium precursors by reactions with salicylaldimine and iminopyridyl dendritic ligands, respectively. The N,N cationic complexes were isolated as hexafluorophosphate salts and were characterised by NMR and IR spectroscopy, and MALDI-TOF mass spectrometry. Related mononuclear complexes were obtained in a similar manner and their molecular structures have been determined by X-ray diffraction analysis. The cytotoxicities of the mono- and multinuclear complexes were established using A2780 and A2780cisR human ovarian carcinoma cancer cell lines.     

Development of new methods for the synthesis of 2,3-bis(nitroxymethyl)-2,3-dinitrobutane-1,4-diol dinitrate and its intermediates

Known methods for the synthesis of 2,3-bis(nitroxymethyl)-2,3-dinitrobutane-1,4-diol dinitrate and its intermediates were investigated. New procedures were developed for the preparation of these compounds. 2,3-Bis(nitroxymethyl)-2,3-dinitrobutane-1,4-diol dinitrate was studied by X-ray diffraction.

     

Thio Analogs of Pyrimidine Bases: Synthesis And Spectroscopic Study of New Potentially Biologically Active Disulfides of N,O-(N,N- or O,O-)-Di- and N,N,O-Tri-(o-, m-, and p-)bromobenzyl-2-thiouracils

Nine new disulfides of N,O-(N,N- or O,O-)-di- and N,N,O-tri-(o-, m- and p-)bromobenzyl-2-thiouracils have been prepared. The structures of these compounds were confirmed by spectroscopic (FT-IR, UV-Vis, ¹H NMR) and elemental analyses. Estimation of pharmacotherapeutic potential has been made for synthesized compounds on the basis of Prediction of Activity Spectra for Substances (PASS).     

Novel methods for the synthesis of N-trichloroacetyl- and N-formyl-S,S-diarylsulfilimines

N-Trichloroacetyl-S,S-diarylsulfilimines are prepared in quantitative yields from sulfilimines and trichloroacetamide; whereas N-formyl-S,S-diarylsulfilimines are obtained quantitatively by alkaline cleavage of N(l-hydroxy-2,2,2-trichloroethyl)-S,S-diarylsulfilimines.     

季铵化N,O-(2-羧乙基)壳聚糖的制备及其抑菌性能

以缩水甘油基三甲基氯化铵(GTMA)、缩水甘油基三乙基氯化铵(GTEA)、缩水甘油基三丙基氯化铵(GTPA)、缩水甘油基三丁基氯化铵(GTBA)和缩水甘油基二甲基苄基氯化铵(GDMBA)等活性季铵盐为季铵化试剂,对N,O-2-羧乙基壳聚糖(N,O-2-CEC)进行了化学改性,得到了系列季铵化N,O-2-CEC(QCEC...     

Investigations on the synthesis, structures, and properties of new copper(I) 2,3-dimethylpyrazine coordination compounds

Five new coordination compounds were prepared, structurally characterized, and investigated for their thermal properties. In the structure of the ligand-rich 4:9 compound, tetra(mu2-chloro)bis(mu2-2,3-dimethylpyrazine-N,N')tetrakis(2,3-dimethylpyrazine-N)tetracopper(I) tris(2,3-dimethylpyrazine)solvate (I), discrete complexes are formed by build up of two [(CuCl-(2,3-dimethylpyrazine)2]2 dimers, which are connected by two 2,3-dimethylpyrazine ligands via mu-N,N' coordination. In the 1:1 compound poly[mu2-chloro-mu2-2,3-dimethylpyrazine-N,N'-copper(I)] (II), (CuCl)2 dimers are found, which are connected by the 2,3-dimethylpyrazine ligands into layers. For this composition, a second polymorphic modification was found (III), which exhibits a different topology of the coordination network and a different packing of the layers. In the most stable 3:2 compound catena[tri(mu2-chloro)bis(mu2-2,3-dimethylpyrazine-N,N')tricopper(I)] (IV), six-membered rings of (CuCl)3 are found, which are connected by the 2,3-dimethylpyrazine ligands into chains. In the ligand-deficient 2:1 compound, poly[di(mu3-chloro)(mu2-2,3-dimethylpyrazine-N,N')dicopper(I)] (V), CuCl double chains are found, which are connected by the 2,3-dimethylpyrazine ligands into layers. On heating, compound I transforms quantitatively into the 3:2 compound IV without the formation of II or III as intermediates. Compound IV is also obtained by heating either the 1:1 compound II or III. On further heating, the 3:2 compound IV loses additional ligands, forming the ligand-deficient 2:1 compound V, which then decomposes into CuCl. The stability, thermal reactivity, and the transition behavior of all compounds were investigated using different thermoanalytical methods. These results are compared with those previously reported for the structurally similar CuCl(2-ethylpyrazine) coordination compounds. The formation and the stability of the different compounds in solution were also investigated.     

Design, synthesis, structure, and gas (N2, Ar, CO2, CH4, and H2) sorption properties of porous metal-organic tetrahedral and heterocuboidal polyhedra

A strategy based on assembling metal ions and organic carboxylate links has been applied for the design and synthesis of a new class of porous, truncated tetrahedral and heterocuboidal polyhedra, whose pore size and functionality can be systematically varied. The synthesis of this series of metal-organic polyhedra (MOPs) employs sulfate-capped oxygen-centered iron-carboxylate trimers, Fe3O(CO2)3(-)(SO4)3, as rigid nodes separated by linear (phenyl, biphenyl, terphenyl, and tetrahydropyrene) or trigonal (benzenetriphenyl) links to yield five highly crystalline polyhedra of general formula [NH2(CH3)2]8[Fe12O4(-)(SO4)12(link)x(py)12].G (x = 6 for linear or 4 for trigonal, py = pyridine, G = guests). In this series, the size of each polyhedron has been varied from 20.0 to 28.5 A (on edge), and the corresponding pore diameter from 7.3 to 13.3 A. Gas sorption isotherms were measured for three members of this series to reveal significant uptake of gases (N2, Ar, CO2, H2, CH4) and benzene and exhibit Type I sorption behavior that is indicative of permanent porosity. The apparent surface areas for these compounds range from 387 to 480 m(2)/g.     

Sol-gel synthesis and sorption properties of calcium monoaluminate

Method for synthesis of calcium aluminate and sorbents based on this compound was developed on its basis of the sol-gel technology. The method makes it possible to obtain the target product with specific surface areas in the range from 7 to 120 m² g^–1. The compounds obtained were characterized by scanning electron microscopy, X-ray phase analysis, and X-ray fluorescence microanalysis. It was found that the main phase of the sorbents is rhombohedral calcium monoaluminate CaAl₂O₄. The method of Hammett indicator adsorption was used to determine the content of active centers on the surface of the sorbents and the distribution of these centers over ionization constants. It was shown that the surface characteristics of the sorbents depend on their synthesis method. The retention parameters, polarities, and thermodynamic characteristics were determined for organic compounds of various classes. The possibility of using calcium aluminate modified with sodium chloride for gas-chromatographic separation of aliphatic and aromatic hydrocarbons and carbonyl compounds was demonstrated.     

One-pot synthesis of bis-1,5,3-dithiazepanes and their sorption properties toward silver(I) and palladium(II)

The possibility of one-pot synthesis of bis-1,5,3-dithiazepanes by multicomponent condensation of amines (NH₄Cl, hydrazine, and 1,2-ethylenediamine) with formaldehyde and 1,2-ethanedithiol was described. Their sorption properties relative to Ag(I) and Pd(II) were studied by a static method. It was shown that at room temperature bis-1,5,3-dithiazepanes recovered with high efficiency silver(I) and palladium(II) from nitrate solutions and hydrochloric acid solutions, respectively.     

含O-, S-, N-和C-2,3-不饱和糖苷的合成

以3,4,6-三-O-乙酰基-D-葡萄烯糖为原料,(NH₄)₂S₂O₈为催化剂,利用Ferrier重排反应制得一系列含O-, S-,N-和C-2,3-不饱和糖苷,其结构经¹H NMR, IR和MS（ESI）确证。考察了催化剂及其用量,溶剂和温度对产率的影响。结果表明：在最优条件［反应温度80 ℃,乙腈为溶剂,(NH₄)₂S₂O₈为催化剂(1 eq.)］下,3a产率高达83%。     

Sol-gel synthesis of carbonate-containing zirconium(IV) hydroxide and its sorption properties toward alkaline-earth elements

Carbonate-containing zirconium hydroxide with a CO₂ content of up to 0.5 mol per mole of ZrO₂ was prepared by the sol-gel procedure. The sorption power of the carbonate-containing zirconium(IV) hydroxide toward Sr²⁺, Ca²⁺, and Mg²⁺ ions was studied. The effect of pH and electrolyte concentration on the sorption power was examined.     

Chiron approach to callipeltin A: first synthesis of fully protected (2R,3R,4S)-4,7-diamino-2,3-dihydroxy heptanoic acid

Stereoselective synthesis of protected (2R,3R,4S)-4,7-diamino-2,3-dihydroxy heptanoic acid, which is present as a side chain attached to the main macrocyclic depsidecapeptide backbone of callipeltin A (a potent, cytotoxic, anti-HIV and anti-fungal agent) starting from a carbohydrate, is described.