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        

<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.     

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).     

An efficient synthesis of <Emphasis Type="Italic">β</Emphasis>-methoxycarbonyl-<Emphasis Type="Italic">γ</Emphasis>-butyrolactones

β-Methoxycarbonyl-γ-butyrolactones bearing a γ-aromatic substituent were prepared via copper-catalyzed reductive aldol addition/lactonization domino reactions of ketones with α,β-unsaturated dicarboxylate esters and a silane under ambient temperature. The reaction has advantage of using readily available reagents, mild conditions and high efficiency.     

<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.     

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.     

Phase Diagrams of the <Emphasis Type="Italic">n</Emphasis>-Decane–<Emphasis Type="Italic">n</Emphasis>-Hexadecane–Cyclododecane, <Emphasis Type="Italic">n</Emphasis>-Decane–Cyclododecane,and <Emphasis Type="Italic">n</Emphasis>-Hexadecane–Cyclododecane Systems

The n-decane–n-hexadecane–cyclododecane, n-decane–cyclododecane, and n-hexadecane–cyclododecane systems are studied by means of low-temperature differential thermal analysis using a differential scanning heat flow calorimeter. It is noted that all studied systems belong to the eutectic type. It is concluded that in the n-decane–n-hexadecane–cyclododecane system, the eutectic composition contains 85.0 wt % n-С₁₀Н₂₂, 4.0 wt % n-С₁₆Н₃₄, and 11.0 wt % С₁₂Н₂₄. It has a melting point of ?35.0°C.     

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.     

New heteroscorpionate lanthanide complexes for ring-opening polymerisation of <Emphasis Type="Italic">ε</Emphasis>-caprolactone and <Emphasis Type="Italic">rac</Emphasis>-lactide

Yttrium and lanthanum amido-complexes with bis(pyrazol-1-yl)acetates in their coordination spheres were studied as the catalysts in ε-caprolactone and lactide ring-opening polymerisation. A high molecular mass poly(ε-caprolactone) (PCL) was obtained in almost quantitative yield under mild conditions. rac-Lactide polymerisations were less efficient and required quite harsh experimental conditions to obtain atactic PLA samples with moderate yields. The average chain-length of PCL was dependent upon the choice of the metal centre and the presence of substituents on the pyrazole rings of the ancillary ligand. The ground-state geometries of the complexes and the first stages of ε-caprolactone polymerisation were computationally modelled by means of DFT calculations.     

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.     

Novel <Emphasis Type="Italic">β</Emphasis>-<Emphasis Type="Italic">N</Emphasis>-acetylglucosaminidases from <Emphasis Type="Italic">Vibrio harveyi 650</Emphasis>: Cloning,expression, enzymatic properties,and subsite identification

Background  

Since chitin is a highly abundant natural biopolymer, many attempts have been made to convert this insoluble polysaccharide into commercially valuable products using chitinases and β-N-acetylglucosaminidases (GlcNAcases). We have previously reported the structure and function of chitinase A from Vibrio harveyi 650. This study t reports the identification of two GlcNAcases from the same organism and their detailed functional characterization.     

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.     

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.     

Synthesis and structure of the cobalt(II) coordination compounds with <Emphasis Type="Italic">N,N</Emphasis>-dimethyl-<Emphasis Type="Italic">N</Emphasis>′,<Emphasis Type="Italic">N</Emphasis>′-dimethylthiocarbamoylsulfenamide

The CoLX₂ complexes were obtained by the reaction of N,N-dimethyl-N′,N′-dimethylthio-carbamoylsulfenamide (L) with CoX₂ (X = Cl, Br, I, NCS). The complexes were investigated by elemental and X-ray analysis, IR, ¹H NMR, and electron spectroscopy, conductometry, magnetochemistry, thermogravimetry. It is found that these compounds are high-spin complexes of pseudotetraedral structure with bidentate coordination of L through the thione sulfur atom and sulfenamide nitrogen atom.     

Synthesis and characterization of some <Emphasis Type="Italic">o</Emphasis>,<Emphasis Type="Italic">o</Emphasis>′-dihydroxyazo dyes and their metal complexes

The synthesis and characterization of azo dyes containing o,o′-dihydroxy groups and their azo-metal(II) [Cu, Co, Ni, Zn] chelates by ¹H N.M.R., IR, AAS, UV–VIS, magnetic susceptibility and thin-layer chromatography techniques are reported. The stochiometry of the azo-metal chelates was determined by the spectroscopic titration method to be 1:2 (ML₂). The synthesized azo dyes and azo-metal chelate dyes were applied on wool fabric. Fastness to light and washing were measured.     

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.     

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.     

Synthesis, <Emphasis Type="Italic">β</Emphasis>-<Emphasis Type="Italic">Glucuronidase</Emphasis> Inhibition,and Molecular Docking Studies of 1,2,4-Triazole Hydrazones

A series of 1,2,4-triazole hydrazones 1–25 has been synthesized and characterized using different spectroscopic techniques including FT-IR, ¹H-NMR, and ESI MS spectrometry. The synthetic derivatives were evaluated for their β-glucuronidase enzyme inhibition properties. Among them, 17 compounds demonstrated potential inhibitory activity towards β-glucuronidase with IC₅₀ values ranging between 2.50 and 53.70 µM. Compounds 1 having IC₅₀?=?2.50?±?0.01 µM was found to be the most active compound of the series and showed remarkable activity and found to be far more potent than the standard d-saccharic acid 1,4-lactone (IC₅₀?=?48.4?±?1.25 µM). Furthermore, the possible binding interaction of active compounds was explored by in silico studies. These compounds can be used for anti-diabetic drug development process.