A facile synthesis of 4-acylamino-tetrahydroindazoles via the Ritter reaction

A new route toward 4-acylamino- and 4-amino-substituted tetrahydroindazoles is disclosed. The title compounds are obtained in good to excellent yields in the Ritter reaction between 4-hydroxy-tetrahydroindazoles and various nitriles. The reactivity of the tetrahydroindazole-derived carbenium ion is both sufficiently high to react with trichloroacetonitrile and sufficiently selective to resist the azide functionality within its structure. The present approach adds a method to the toolbox of tetrahydroindazole chemistry and facilitates the structural modifications of the scaffold, which has found important applications in medicinal chemistry.     

Separation and identification of selenotrisulfides in epithelial cell homogenates by LC–ICP–MS and LC–ESI-MS after incubation with selenite

To elucidate how selenite is metabolised in the intestine after oral intake, it was incubated with homogenized epithelial cells from pigs. When the metabolites were analysed by LC–ICP–MS, two major selenium metabolites were separated in the supernatant from the homogenate. These metabolites were formed instantly but disappeared within 15 min. No other selenium-containing compounds appeared during this time. Hence, the secondary reaction products were either volatilised or precipitated. To verify the identity of the compounds, a larger amount of selenite was incubated with epithelial cells. The presence of Cys-Se-SG and GS-Se-SG was verified by LC–ESI-MS. Selenotrisulfides were synthesized by reaction of L-cysteine and L-glutathione with sodium selenite. The reaction mixture contained three main products: selenodicysteine (Cys-Se-Cys), selenocysteine glutathione (Cys-Se-SG), and selenodiglutathione (GS-Se-SG). The two transient selenium compounds in the epithelial cell incubation mixture co-eluted with the synthesized Cys-Se-SG and GS-Se-SG, respectively. The identities of these compounds were verified by LC–ESI-MS. Hence, these selenium metabolites have now been identified by ESI-MS after isolation from epithelial cells.     

Hadronization of quark systems

Hadronization in simple models of quark systems is discussed with emphasis on the combinatorial aspects. The numberN of quarks and the numberN _c of colours are the relevant variables. In onedimension and in the meson and baryon sector the problem is completely soluble. When multiquark hadrons are included an iterative procedure still allows a complete solution. Higher dimensions are difficult to treat but global hadronization, without dimensionality constraints, is again soluble. As a general result the baryon/meson ratio is, for large quark densities, rather large, ?1/3 and may grow without limit asN→∞.     

Synthesis of novel 3-deoxy-3-C-triazolylmethyl-allose derivatives and evaluation of their biological activity

Recently, monosaccharide-triazole conjugates have proved to possess a large variety of useful biological activities. This paper describes synthesis of a new series of 3-deoxy-3-C-triazolylmethyl-allose derivatives. These new compounds are obtained from acetonide-protected 3-deoxy-3-azidomethyl allose and commercial alkynes via Cu(I) catalyzed 1,3-dipolar cycloaddition. The obtained molecular scaffolds differ from those described earlier by the presence of a methylene linker (-CH₂-) between the C(3) of allose and the triazole moiety. It was demonstrated that acetonide-protected monosaccharide, 3-deoxy-3-C-(4-phenyl-1H-1,2,3-triazol-1-yl)methyl-1,2:5,6-di-O-isopropylidene-α-d-allofuranose, inhibited α-L-fucosidase for 26% at 0.1 mM concentration, but a deprotected analog, 3-deoxy-3-C-(4-(4-tert-butylphenyl)-1H-1,2,3-triazol-1-yl)methyl-β-d-allofuranose, showed 15% inhibition of β-glucosidase at 1 mM concentration.      

Spin-disorder resistivity in the Cu2Mn(Al1−xSnx) heusler alloys

Electrical resistivity measurements have been performed on the Cu₂Mn(Al_1?xSn_x) Heusler alloys, where x = 0; 0.05; 0.10; 0.15, in the temperature range of 4–800 K. The experimental curves clearly show the importance of the ferromagnetic character on the resistivities of the alloys. The results obtained are in agreement with an interpretation in terms of a spin-disorder model.     

Expeditious asymmetric synthesis of a stereoheptad corresponding to the C(19)-C(27)-ansa chain of rifamycins: formal total synthesis of Rifamycin S

In the presence of sulfur dioxide and an acid promoter, (-)-(1E,3Z)-2-methyl-1-((1S)-1-phenylethoxy)penta-1,3-dien-3-yl isobutyrate reacts with (Z)-3-(trimethylsilyloxy)pent-2-ene giving a silyl sulfinate intermediate that undergoes, in the presence of palladium catalyst, a desilylation and retro-ene elimination of SO(2) with formation of (-)-(1Z,2S,3R,4S)-1-ethylidene-2,4-dimethyl-5-oxo-3-((1S)-1-phenylethoxy)-heptyl isobutyrate as major product. This ethyl ketone undergoes cross-aldol reaction with (2S)-2-methyl-3-[(tert-butyldimethylsilyl)oxy]propanal giving an aldol that is reduced into a stereoheptad corresponding to the C(19)-C(27)-segment of Rifamycins with high diastereoselectivity and enantiomeric excess.     

Estuarine increase of chromium surface sediments: Distribution, transport and time evolution

Chromium is an estuarine contaminant due to its industrial applications like leather tanning, dyeing or chromium plating. The most common explanation about the presence of this metal is the frequent estuarine spill, particularly in ecosystems like rivers, estuaries and coasts near anthropogenic activities.The purpose of this study is the investigation of the distribution and evolution of chromium in sediments of the surface layer of an estuary, determining directly the total content by electrothermal atomic absorption spectroscopy (ETAAS) using slurries. Results were correlated with the environmental conditions and the chemistry of the metal to have a partial overview of the potential risk of chromium presence in the water column and the biota of the estuary. The pH values, oxidation–reduction potential (ORP), elemental analysis (carbon, nitrogen and hydrogen content), and changes of total chromium with time were analysed. This information was used to establish the environmental conditions where chromium appeared, was transported and was accumulated in the marine sediments collected following a time evolution of two years.     

Synthesis of long-chain polyketide fragments by reaction of 1,3-dioxy-1,3-dienes with allylsilanes: umpolung with sulfur dioxide

[reaction: see text] In the presence of a Lewis or protic acid and at low temperature, 1,3-dioxy-1,3-dienes add to sulfur dioxide generating zwitterionic intermediates that can react with carbon nucleophiles such as allylsilanes. After a retro-ene elimination of SO(2), valuable polyketide precursors are obtained.     

Analytical uses of some n-nitroso-n-alkyl (or -n-cyclo-alkyl)hydroxylamines : Part I. N-Nitroso-n-cyclohexylhydroxylamine

The analytical properties of N-nitroso-N-cyclohexylhydroxylamine (“hexahydrocupferron”) are described. This reagent is much more stable in acidic media than its analogue cupferron, but offers very similar reactions and sensitivities. The solubility, R_F and pK values, u.v. and i.r. spectra for the reagent are given. Very sensitive qualitative tests for iron, vanadium and titanium are reported. A turbidimetric determination of aluminium(III), suitable for 0.6–10 μg Al ml^-1, is evaluated.