Synthesis, structure, and transformations of N-(bicyclo[2.2.1]hept-5-en-endo-2-ylmethyl)-N-[(oxiran-2-yl) methyl]-arenesulfonamides

Reaction of N-(bicyclo[2.2.1]hept-5-en-endo-2-ylmethyl)arenesulfonamides with epichlorohydrin in the presence of tetramethylammonium iodide afforded a group of framework N-[(oxiran-2-yl)methyl]sulfonamides and also a series of new dioxiranes, N-(oxiran-2-yl)methyl-N-(exo-5,6-epoxybicyclo[2.2.1]heptan-endo-2-ylmethyl)arenesulfonamides. The aminolysis of N-(oxiran-2-yl)methyl]arenesulfonamides with benzylamine and benzylpiperazine led to the chemo- and regioselective opening of the epoxy ring according to Krasusky rule. The structure of compounds was established by spectral methods and the XRD analysis.     

Natural and synthetic manganese minerals

The mineral and microelement composition and structures have been studied and a comparative analysis has been carried out for manganese minerals with the general formula [Mn(O,OH)₂]⁺[R_0.5–1(OH)_21.5] · nH₂O (R = Mn, Na, K, Ni, Co, Ca, and others) that built iron-manganese concretions raised from different areas of the Sea of Okhotsk and the Bering Sea, and their synthetic analogues. The structures of synthetic manganese species were found to better withstand temperature impacts than those of the native minerals studied under the same conditions.     

Synthesis of (±)-2-Methoxy-9a-Carbamorphinan and (±)-2-Methoxy-9a-Carba-14α-Morphinan: Acid Catalyzed Cyclizations of 1-m-Methoxybenzyl-4, 4a,5,6,7,8-Hexahydronaphthalen-2(3H)-ONE and 1 -m-Methox Ybenzyloctalins

The bridged-ethers, (±)-2-methoxy-9a-carbamorphinan (1b) and (±)-2-methoxy-9a-carba-14α-morphinan(2b) have been synthesized. The acid-catalyzed cyclizations of 1-m-methoxy benzyloctalone 3b and 1-m-methoxybenzyloctalins 4b proceed with high regio-and stereoselectivities leading mostly to the bridged-ketone 14 and ether 1b respectively, along with o-methoxy-tetracyclic ketone 15 and the ether 17, in addition to other minor products.     

Regioselective Synthesis of Thiopyrano[3,2‐c][1]benzothiopyran‐5(2H)‐one and Thieno[3,2‐c][1]benzothiopyran‐4(2H)‐one

4‐Mercaptothiocoumarin was alkylated with different propargylic and allylic halides under phase‐transfer‐catalyzed conditions in the presence of tetrabutylammonium bromide (TBAB) or benzyl triethylammonium chloride (BTEAC) catalyst in dichloromethane–aqueous NaOH solution (1%) at room temperature. These 4‐thiopropynyl and thioallyl thiocoumarins were then refluxed in chlorobenzene and quinoline to give thiopyrano[3,2‐c][1]benzothiopyran‐5(2H)‐one and thiopyrano[3,2‐c][1]benzothiopyran‐4‐one respectively.     

The unambiguous synthesis and NMR assignment of 4-alkoxy and 3-alkylquinazolines

Contrary to a number of reports, alkylations of the privileged 3,4-dihydroquinazoline scaffold provide N3-alkylated products, and not 4-alkoxyquinazolines. To correctly assign the structure, ¹³C NMR shifts of the –Z–CH_n– (Z=O, N) fragment are necessary; resonances in the 45–55 ppm range are indicative of N3-alkylation. Treatment of 3,4-dihydroquinazoline-4-one with p-TsCl afforded the N3-tosylated compound, whose reaction with an amine yielded the corresponding N3-alkyl derivative. A mechanism corroborated by ¹⁵N-labeling involving pyrimidine ring opening and recyclisation is proposed. Finally, the unambiguous preparation of 4-alkoxyquinazolines is described via treatment of 3,4-dihydroquinazoline-4-ones with PCl₅ followed by an alkoxide.     

Volumetric and Acoustic Studies of Binary Liquid Mixtures of Dipropylene Glycol Dimethyl Ether with Methyl Acetate, Ethyl Acetate and n-Butyl Acetate in the Temperature Range T = (288.15, 293.15, 298.15, 303.15, and 308.15) K

Densities and ultrasonic speeds have been measured over the whole composition range for binary liquid mixtures of dipropylene glycol dimethyl ether, CH₃(OC₃H₆)₂OCH₃, with methyl acetate, ethyl acetate, and n-butyl acetate using an Anton Paar DSA 5000 M density and speed sound analyzer at T = (288.15, 293.15, 298.15, 303.15, and 308.15) K and atmospheric pressure in order to evaluate the behavior of these binaries. From these data excess the molar volume, $ V_{m}^{\text{E}} $ , and deviation in isentropic compressibility, ?κ _S , have been calculated. These excess properties have been fitted with the Redlich–Kister type polynomial equation to get their coefficients and standard deviations which provide a base for discussing the forces operating in solutions.     

Effect of grain size on the sorption and desorption of SeO4 2− and SeO3 2− in columns of crushed granite and fracture infill from granitic water under dynamic conditions

The sorption of 2 × 10^?5 mol/dm³ Na₂SeO₄ and Na₂SeO₃ dissolved in synthetic granitic water (SGW) were investigated in columns of crushed granite and fracture infill (clay minerals) of various grain sizes. Desorption was studied using pure SGW. The goal of study was the quantification of the effect of grain size on the retardation and distribution coefficients of SeO₄ ^2? and SeO₃ ^2?, as well as on the other transport parameters (Peclet number and hydrodynamic dispersion coefficient). A model based on the erfc-function, assuming a non-linear reversible equilibrium sorption/desorption isotherm, was used for evaluation of sorption/desorption and transport parameters. The determination of selenium was performed using an ICP-MS technique. The experimental breakthrough curves were fitted using non-linear regression procedure, in the course of which the parameters mentioned were sought. Summing up, no sorption was recorded in the case of SeO₄ ^2? under these conditions. The values of retardation coefficients were practically one for all studied grain sizes. On the other hand, significant sorption was found for SeO₃ ^2?: depending on the grain size, the retardation coefficients varied between 1.6–8.7 in pure granite and 1.8–37.2 in infill materials. These values correspond to distribution coefficients of 0.2–2.5 and 0.2–12.7 cm³/g, respectively. The both parameters have similar values in a case of desorption which reflects the reversible character of sorption process. It was found that retardation and distribution coefficients and sorption capacity for SeO₃ ^2? also increase with decreasing grain size.     

Sorption of 125I−, 137Cs+, 85Sr2+ and 152,154Eu3+ during their transport in undisturbed vertical and horizontal soil cores under dynamic flow conditions

Transport and sorption of ¹²⁵I^?, ¹³⁷Cs⁺, ⁸⁵Sr²⁺ and ^152,154Eu³⁺ in undisturbed soil cores have been studied under dynamic conditions. Radionuclides were dissolved in synthetic groundwater (SGW) of 0.015 mol/dm³ ionic strength, pH 8.4 and redox potential E_h = 145 mV. The soil samples were taken vertically and horizontally from the river bed at 5–100 cm depths, about 120 m southward of the Dukovany Low and Medium Level Radioactive Waste Repository. The respective water-soluble carriers in the 10^?6 mol/dm³ concentration were added into the SGW prior to the experiments. The soil cores of 9 cm height and 3.8 cm in diameter were placed into columns made of 150 cm³ PE injection syringes of suitable dimensions. The SGW was introduced into columns from the Mariotte’s bottle through a glass manifolds to supply the soil columns by gravity flow at a constant flow-rate about 1.2 cm³/h. Into the water stream, radioactive nuclides were added individually in a form of a short pulse in 0.1 cm³ of demineralized water. In the case of ¹²⁵I^? transport, retardation and hydrodynamic dispersion coefficients were determined, using an integral form of a simple advection-dispersion equation. For each radionuclides, sorption and desorption data have been obtained, evaluated and the results were compared mutually. Residual distributions of the sorbed cationic radionuclides along the soil columns were also presented.     

An efficient and facile synthesis of Zn(II) complexes with 2-substituted benzothiazoles and glycine- and alanine-based ligands having antifungal and antibacterial activities

We carried out an efficient and facile synthesis of Zn(II) complexes with heterocyclic ligands based on 2-substituted benzothiazole moieties, 2-(2′-hydroxynaphthyl)benzothiazole, 2-(2′-hydroxyphenyl)benzothiazole, and 2-(2′-merceptophenyl)benzothiazole, and amino acids, glycine and alanine, are reported and also examined for antifungal and antibacterial activities. Ligands and complexes were characterized by FTIR, ¹H NMR, and elemental analysis.     

Synthesis of Derivatives of 2,6-Dideoxy-2,2-Difluoro-3-O-Methyl-l-Arabinopyranose (2,2-Difluorooleandrose)

Abstract

L-Oleandrose is the carbohydrate constituent of the potent anthelmintic agents the avermectins. Diethylaminosulfur tri-fluoride treatment of appropriate uloses did not give gem-difluoro sugars. Trifluorofluoroxymethane or xenon difluoride addition to the double bond of 4-O-benzoyl-6-deoxy-2-fluoro-3-O-methyl-L-glucal produced protected 2,2-difluorooleandrose derivatives activated at their anomeric center and ready for glycosidation.