10<Emphasis Type="Italic">α</Emphasis>-Hydroxy-<Emphasis Type="Italic">β</Emphasis>-isomorphine,a by-product of the synthesis of 10<Emphasis Type="Italic">α</Emphasis>-hydroxymorphine

Abstract  A new compound was isolated from the reaction mixture after O-demethylation of 6-O-acetyl-10α-acetoxycodeine with boron tribromide. The structure of this compound, 10α-hydroxy-β-isomorphine, was elucidated by spectral data, and its spatial arrangement was deduced from an NOE experiment. Capillary zone electrophoresis was used for separation of morphine and its 10-hydroxy analogues. Graphical abstract        

Synthesis of <Emphasis Type="Italic">α</Emphasis>-chloropyridine derivatives of <Emphasis Type="Italic">γ</Emphasis>-aminobutyric acid

The sodium salt of N-(6-chloronicotinoyl)-γ-aminobutyric acid, a structural analog of the known nootropic and vasidilating drug picamilon, was synthesized via Schotten–Baumann acylation of γ-aminobutyric acid with 6-chloronicotinoyl chloride and subsequent neutralization of the N-(6-chloronicotinoyl)-γ-aminobutyric acid that was obtained in >60% yield.     

Synthesis of 20<Emphasis Type="Italic">S</Emphasis>-protopanaxadiol <Emphasis Type="Italic">β</Emphasis>-D-galactopyranosides

20S-Protopanaxadiol (3β,12β,20S-trihydroxydammar-24-ene) 3-, 12-, and 20-O-β-D-galactopyranosides were synthesized for the first time. Condensation of 12β-acetoxy-3β,20S-dihydroxydammar-24-ene (1) and 2,3,4,6-tetra-O-acetyl-α-D-galactopyranosylbromide (α-acetobromogalactose) (2) under Koenigs–Knorr conditions with subsequent removal of the protecting groups resulted in regio- and stereoselective formation of 20S-protopanaxadiol 3-O-β-D-galactopyranoside, an analog of the natural ginsenoside Rh₂. Glycosylation of 12β,20S-dihydroxydammar-24-en-3-one (5) by 2 with subsequent treatment of the reaction products with NaBH₄ in isopropanol and deacetylation with NaOMe gave 20S-protopanaxadiol 12- and 20-O-β-Dgalactopyranosides.     

<Emphasis Type="Italic">β</Emphasis>-Chloro-<Emphasis Type="Italic">α</Emphasis>,<Emphasis Type="Italic">β</Emphasis>-unsaturated carbonyls as convenient precursors of highly substituted benzenes

The Diels–Alder reactions of three β-chloro-α,β-unsaturated carbonyl compounds 1–3 with different dienes were carried out to afford highly functionalized cyclohexenes 4–9, bearing quaternary centers, in good yields. These cycloadducts (CAs) undergo dehydrochlorination with subsequent aromatization in the presence of 1,8-diazabicyclo[5.4.0]undec-7-ene DBU to produce new substituted benzenes 11–14. Compound 10 is the product of lactonization and removal of an HCl molecule from compound 7. All products were characterized by NMR, IR, elementary analysis and some of them by MS. Structure assignments of isomers were carried out on the basis of NMR chemical shifts and coupling constants using 1D, 2D and heteronOe NMR techniques.     

Spectroscopic and electrical characterization of <Emphasis Type="Italic">α</Emphasis>,<Emphasis Type="Italic">γ</Emphasis>-bisdiphenylene-<Emphasis Type="Italic">β</Emphasis>-phenylallyl radical as an organic semiconductor

The semiconductor properties of the earliest known stable radical, α,γ-bisdiphenylene-β-phenylallyl radical (Koelsch radical, 1^?) were assessed using spectroscopic and electrical techniques. This radical undergoes reversible redox processes, and it has low redox potentials. In addition, 1^? possesses long wavelength absorption bands, owing to the existence of a singly-occupied molecular orbital whose energy level lies between those of the HOMO and LUMO. A spin-coated thin-film of 1^? displays photocurrent and an electron mobility of 6.3 × 10^?7 cm² V^?1 s^?1 on a trially-fabricated organic field effect transistor.     

<Emphasis Type="Italic">N</Emphasis>′-tetrazolylmethoxyl derivatives of <Emphasis Type="Italic">N</Emphasis>-methyldiazene <Emphasis Type="Italic">N</Emphasis>-oxides

A preparation method was developed for previously unknown tetrazole derivatives containing in the 1, 2, and/or 5 positions of the tetrazole ring N-methyldiazene-N-oxide-N′-oxymethyl groups.     

Theoretical and experimental NMR studies of the Swern oxidation of methyl 6<Emphasis Type="Italic">α</Emphasis>,7<Emphasis Type="Italic">β</Emphasis>-dihydroxyvouacapan-17<Emphasis Type="Italic">β</Emphasis>-oate

This work describes the synthesis of new derivatives of 6α,7β-dihydroxyvouacapan-17β-oic acid (1) employing the Swern method for the oxidation of C-6 and C-7 of methyl 6α,7β-di-hydroxyvouacapan-17β-oate (2) and the formation of methyl 6,7-dioxovouacapan-17β-oate (3). NMR structural studies associated with theoretical calculations of reaction intermediates and products are also reported. The mixture of methyl 7β-hydroxy-6-oxovouacapan-17β-oate (4; 21%) and methyl 6α-hydroxy-7-oxovouacapan-17β-oate (5; 79%) was the product from the first step of the oxidation of 2. The lower energy of 5, calculated by HF/6-31G* and DFT/BLYP/6-31G* methods, reinforces the thermodynamic control proposed for the reaction. After further Swern oxidation of the mixture of 4 and 5, the isomeric form methyl 6-hydroxy-7-oxovouacap-5-en-17β-oate (6) was obtained. Theoretical calculations indicate a lower energy for the mono-enol 6 than the 1,2-diketo 3 and the other mono-enol methyl 7-hydroxy-6-oxovouacap-7-en-17β-oate (7).     

Directed Aminomethylation of Pyrrole,Indole, and Carbazole with <Emphasis Type="Italic">N</Emphasis>,<Emphasis Type="Italic">N</Emphasis>,<Emphasis Type="Italic">N′</Emphasis>,<Emphasis Type="Italic">N′</Emphasis>-Tetramethylmethanediamine

Catalytic aminomethylation of pyrrole and indole with N,N,N′,N′-tetramethylmethanediamine in the presence of 5 mol % of ZrOCl₂·8H₂O proceeds selectively at the positions 2, 5 of pyrrole and 1, 3 of indole. Carbazole under the same conditions affords 3-formyl-9-aminomethyl derivative. The reaction in the presence of 5 mol % of K₂CO₃ occurs as monoaminomethylation: for pyrrole at the position 2, for indole at the position 3, and for carbazole at the nitrogen atom of the substrate. Water-soluble 1,1′-(1H-pyrrole-2,5-diyl)bis(N,N-dimethylmethanamine) exhibits a fungistatic activity with respect to phytopathogenic fungi Rhizoctonia solani.     

Allylic oxidation of 19<Emphasis Type="Italic">β</Emphasis>,28-epoxy-a-neo-5<Emphasis Type="Italic">β</Emphasis>-methyl-25-nor-18<Emphasis Type="Italic">α</Emphasis>-olean-9-ene

Allylic oxidation of 19β,28-epoxy-A-neo-5β-methyl-25-nor-18α-olean-9-ene by ozone produced 19β,28-epoxy-A-neo-5β-methyl-25-nor-18α-olean-9-en-1-one.     

Computer models of eutectic-type <Emphasis Type="Italic">T</Emphasis>–<Emphasis Type="Italic">x</Emphasis>–<Emphasis Type="Italic">y</Emphasis> diagrams with allotropy

Using the eutectic-type T–x–y diagram as an example, it can be represented the analysis of its geometrical construction dependence on the temperature of a component two polymorphous modifications which participate in mono- and invariant metatectic and invariant eutectic (eutectoid) transformations above or below (and within) binary eutectics temperature intervals and below a ternary eutectic temperature. Computer models for considered phase diagrams have been designed. Such models help to solve applied tasks like visualization, isopleths and isothermal sections decoding, mass balances calculation and evaluation of phase and conglomerate concentration in microstructure.     

Thermophysical properties of <Emphasis Type="Italic">N</Emphasis>,<Emphasis Type="Italic">N</Emphasis>-dimеthylacetamide mixtures with <Emphasis Type="Italic">n</Emphasis>-butanol

The refraction, dielectric, viscosity, density, data of the binary mixtures of N,N-dimethylacetamide (DMA) with n-butanol at 308.15 and 313.15 K. The measured parameters used to obtain derived properties like Bruggeman factor, molar refraction and excess static dielectric constant, excess inverse relaxation time, excess molar volume and excess viscosity, excess molar refraction. The variation in magnitude with composition and temperature of these quantities has been used to discuss the type, strength and nature of binary interactions. Results confirm that there are strong hydrogen-bond interactions between unlike molecules of DMA+ n-butanol mixtures and that 1: 1 complexes are formed and strength of intermolecular interaction increases with temperature.     

Synthesis of <Emphasis Type="Italic">α</Emphasis>-chloropyridine-containing oximes of 3<Emphasis Type="Italic">β</Emphasis>,5-dihydroxy-6-ketosteroids

New derivatives of steroidal 6-ketoximes containing α-chloropyridine neonicotinoid groups characteristic of bioactive compounds were synthesized by formation of oximes of cholestane and stigmastane 3β,5-dihydroxy-6-ketosteroids with O-(2-chloropyridin-5-ylmethyl)hydroxylamine in the presence of zinc or tin(IV) chloride.     

Study of<Emphasis Type="Italic"> β</Emphasis>–<Emphasis Type="Italic">α</Emphasis> recrystallization of the polypropylene

The crystalline modifications and of polypropylene (PP) were studied by using polarized light microscopy (PLM), wide-angle X-ray diffraction (WAXD), and differential scanning calorimetry (DSC). Typically crystals surrounded by spherulites were observed at low temperature. With increasing temperature the crystals melted and a new crystal appeared. More interestingly, the melting temperature of the new crystal was about 5 ° higher than that of spherulites originally present in the sample formed isothermally. It was assumed that this new crystal was the recrystalline crystal. This assumption was supported by the DSC results. Furthermore, the crystallization kinetics of the PP used was studied on the basis of the traditional Avrami analysis. As a result, the Avrami exponents of crystallization temperature from 120 to 130 °C ranged between 4.21 and 3.60, indicating that the crystallization mechanism of PP order melt was spherulitic growth and random nucleation.     

1,3-Diamino-2-Hydroxypropane-<Emphasis Type="Italic">N</Emphasis>,<Emphasis Type="Italic">N</Emphasis>,<Emphasis Type="Italic">N</Emphasis>′,<Emphasis Type="Italic">N</Emphasis>′-Tetraacetic Acid: Crystal and Molecular Structures

The synthesis, IR spectroscopic study, and X-ray diffraction analysis (CIF file CCDC no. 1574078) are carried out for 1,3-diamino-2-hydroxypropane-N,N,N′,N′-tetraacetic acid (I). The structural units of a crystal of compound I are (H_4.5HPdta)^0.5– anions, (H_5.5HPdta)^0.5+ cations, and molecules of water of crystallization joined by a branched network of hydrogen bonds: strong intermolecular O–H…O and intramolecular N–H…O bonds.     

Characterization of ethyl chloroformate derivative of <Emphasis Type="Italic">β</Emphasis>-methylamino-<Emphasis Type="SmallCaps">l</Emphasis>-alanine

Beta-methylamino-L-alanine (BMAA) is a neurotoxic amino acid that can be produced by cyanobacteria in aqueous environments. To analyze this compound by gas chromatography/mass spectrometry (GC/MS), BMAA must be derivatized to a nonpolar, volatile compound. This can be accomplished by reacting BMAA with ethyl chloroformate. While carrying out electron ionization (EI) mass spectrometric analysis on the (13)C-labeled derivative, it was discovered that the formation of an ion with a peak at m/z 245.12 is the result of [CH(3)CH(2)O.] loss from the amino groups resulting from alpha-cleavage. This differs from previous reports that attributed this peak to alpha-cleavage of the carboxylic ester portion of the BMAA derivative. This finding is important for understanding BMAA derivative mass spectrometric fragmentation patterns and ultimately to properly identifying and quantifying BMAA. Fragmentation pathways for the formation of other major peaks observed in the EI mass spectra are also proposed.     

Complex formation of magnesium and calcium ions with trimethylenediamine-<Emphasis Type="Italic">N</Emphasis>,<Emphasis Type="Italic">N</Emphasis>,<Emphasis Type="Italic">N</Emphasis>’,<Emphasis Type="Italic">N</Emphasis>’-tetraacetic acid

Stability constants and heat effects of the formation reactions of magnesium and calcium trimethylenediaminetetraacetates at 298.15 K and ionic strength of 0.1, 0.5, and 1.0 (mol/L KNO₃) have been determined by means of potentiometry and calorimetry. Standard thermodynamic parameters (log K⁰, Δ_rG⁰, Δ_rH⁰, and Δ_rS⁰) of the studied equilibriums have been determined.     

Synthesis of lupane and 19<Emphasis Type="Italic">β</Emphasis>,28-epoxy-18<Emphasis Type="Italic">α</Emphasis>-oleanane 2,3-<Emphasis Type="Italic">seco</Emphasis>-derivatives based on betulin

The α-hydroxyoximes of methyl betulonate and allobetulone were synthesized. Beckmann fragmentation of them produced the lupane and 19β,28-epoxy-18α-oleanane 2,3-seco-derivatives. Translated from Khimiya Prirodnykh Soedinenii, No. 5, pp. 491–494, September-October, 2008. Original article submitted July 4, 2008.     

Expression of a Glucose-tolerant β-glucosidase from <Emphasis Type="Italic">Humicola grisea</Emphasis> var. <Emphasis Type="Italic">thermoidea</Emphasis> in <Emphasis Type="Italic">Saccharomyces cerevisiae</Emphasis>

A β-glucosidase gene (bgl4) from Humicola grisea var thermoidea was successfully expressed in Saccharomyces cerevisiae. The recombinant protein (BGL4 ^Sc ) was initially detected associated with yeast cells and later in the culture medium. BGL4 ^Sc showed optimal pH and temperature of 6.0 and 40 °C, respectively, and an apparent molecular mass of 57 kDa. The enzyme showed activity against cellobiose and synthetic substrates, and was inhibited more than 80% by Fe²⁺, Cu²⁺, Zn²⁺, and Al³⁺. Using p-nitrophenyl-β-d-glucopyranoside (pNPG) as substrate, BGL4 ^Sc presented a V _max of 6.72 μmol min⁻¹ mg total protein⁻¹ and a K _m of 0.16 mM under optimal conditions. Most important, BGL4 ^Sc is resistant to inhibition by glucose and the calculated K _i value for this sugar is 70 mM. This feature prompts BLG4 ^Sc as an ideal enzyme to be used in the saccharification process of lignocellulosic materials for ethanol production.