Microwave-assisted syntheses of N-heterocycles using alkenone-, alkynone- and aryl-carbonyl O-phenyl oximes: formal synthesis of neocryptolepine

This research aimed to provide a new and "clean" synthetic method that would enable both known and novel N-heterocycles to be prepared efficiently. O-Phenyl oximes were found to be excellent precursors for iminyl radicals with a variety of acceptor side chains. Dihyropyrroles were made in good yields from O-phenyl oximes containing pent-4-ene acceptors. The analogous process with a hex-5-enyl acceptor did not yield a dihydropyridine, probably because the 6-exo-trig ring closure of the iminyl radical was too slow to compete with H-atom abstraction. The iminyl radical from a precursor with a pent-4-yne type side chain underwent ring closure followed by rearrangement to afford a pyrrole derivative. Suitably substituted iminyl radicals ring closed readily onto aromatic acceptors, thus enabling several polycyclic systems to be accessed. Quinolines were made from 3-phenylpropanones via their O-phenyl oximes. Syntheses of phenanthridines starting from 2-formylbiphenyls were particularly efficient, and this approach enabled the natural product trisphaeridine to be made. Starting from 2-phenylnicotinaldehyde derivatives, ring closures of the derived iminyl radicals onto the phenyl rings yielded benzo[h][1,6]naphthyridines. Similarly, ring closure onto a phenyl ring from a benzothiophene-based iminyl yielded a benzo[b]thieno[2,3-c]quinoline. By way of contrast, iminyl radical ring closure onto pyridine rings was not observed. However, iminyl radicals did cyclize onto indoles, enabling indolopyridines to be prepared. The latter route was exploited in a short formal synthesis of neocryptolepine starting from 2-((1H-indol-3-yl)methyl)cyclohexanone.     

Combined experimental and computational study of W(II), Ru(II), Pt(IV) and Cu(I) amine and amido complexes using 15N NMR spectroscopy

Using 2D proton-coupled gHSQC pulse sequences in addition to 1D ¹⁵N NMR experiments of ¹⁵N labeled systems, ¹⁵N NMR chemical shifts of a range of transition metal amido and amine complexes were determined. Tungsten(II), ruthenium(II), platinum(IV) and copper(I) complexes with aniline and their anilido variants were studied and compared to free aniline, lithium anilido and anilinium tetrafluoroborate. Upon coordination of aniline to transition metals, upfield chemical shifts of 20–60 ppm were observed. Deprotonation of the amine complexes to form amido complexes resulted in downfield chemical shifts of 40–60 ppm for all of the complexes except for the tungsten d⁴ system. For the tungsten(II) complexes, the cationic aniline complex displayed a downfield shift of approximately 56 ppm relative to the neutral anilido complex. The change in chemical shift for amine to amido conversion is proposed to depend on the ability of the amido ligand to π-bond with the metal center, which influences the magnitude of the paramagnetic screening term.     

High-Performance Thin-Layer Chromatographic Method for Analysis of Racecadotril in the Bulk Drug

JPC – Journal of Planar Chromatography – Modern TLC - A new simple, rapid, reproducible, and stability-indicatiiig highperformance thin-layer chromatographic method for analysis of...     

An experimental and theoretical study of the reactions OIO+NO and OIO+OH

The kinetics of the reaction OIO+NO were studied by pulsed laser photolysis/time-resolved cavity ring-down spectroscopy, yielding k(235-320 K)=7.6(+4.0)(-3.1) x 10(-13) exp[(607+/-128)/T] cm3 molecule-1 s-1. Quantum calculations on the OIO+NO potential-energy surface show that the reactants form a weakly bound OIONO intermediate, which then dissociates to the products IO+NO2. Rice-Ramsberger-Kassel-Markus (RRKM) calculations on this surface are in good accord with the experimental result. The most stable potential product, IONO2, cannot form because of the significant rearrangement of OIONO that would be required. The reaction OIO+OH was then investigated by quantum calculations of the relevant stationary points on its potential-energy surface. The very stable HOIO2 molecule can form by direct recombination, but the bimolecular reaction channels to HO2+IO and HOI+O2 are closed because of significant energy barriers. RRKM calculations of the HOIO2 recombination rate coefficient yield krec,0=1.5x10(-27) (T/300 K)(-3.93) cm6 molecule-2 s-1, krec,infinity=5.5x10(-10) exp(46/T) cm3 molecule-1 s-1, and Fc=0.30. The rate coefficients of both reactions are fast enough around 290 K and 1 atm pressure for these reactions to play a potentially important role in the gas phase and aerosol chemistry in the marine boundary layer of the atmosphere.     

Selective Electrochemical Epinephrine Sensor Using Self‐Assembled Monomolecular Film of 1,8,15,22‐Tetraaminophthalocyanatonickel(II) on Gold Electrode

This article describes the highly sensitive and selective determination of epinephrine (EP) using self‐assembled monomolecular film (SAMF) of 1,8,15,22‐tetraamino‐phthalocyanatonickel(II) (4α‐Ni^IITAPc) on Au electrode. The 4α‐Ni^IITAPc SAMF modified electrode was prepared by spontaneous adsorption of 4α‐Ni^IITAPc from dimethylformamide solution. The modified electrode oxidizes EP at less over potential with enhanced current response in contrast to the bare Au electrode. The standard heterogeneous rate constant (k°) for the oxidation of EP at 4α‐Ni^IITAPc SAMF modified electrode was found to be 1.94×10^?2 cm s^?1 which was much higher than that at the bare Au electrode. Further, it was found that 4α‐Ni^IITAPc SAMF modified electrode separates the voltammetric signals of ascorbic acid (AA) and EP with a peak separation of 250 mV. Using amperometric method the lowest detection limit of 50 nM of EP was achieved at SAMF modified electrode. Simultaneous amperometric determination of AA and EP was also achieved at the SAMF modified electrode. Common physiological interferents such as uric acid, glucose, urea and NaCl do not interfere within the potential window of EP oxidation. The present 4α‐Ni^IITAPc SAMF modified electrode was also successfully applied to determine the concentration of EP in commercially available injection.     

Development of an automated in situ fracture stage for a ToF‐SIMS system

The design philosophy and implementation of an ultra high vacuum (UHV), PC controlled, automated in situ fracture stage for a surface analysis system is described. ToF‐SIMS spectra are shown to illustrate the improvement in spectral quality obtained from micro‐compact tension (CT) tests of polymer matrix fracture surfaces produced using the fracture stage in UHV compared to those obtained from a sample tested at air. This system is flexible in that by changing the capacity of the load cell it is possible to reduce or increase maximum loads as the specimen type and material demands. The stage has been designed with instrumental flexibility in mind, utilising commercial SEM‐stub type sample mounts, and can thus be used for AES/SAM and XPS investigations, as well as ToF‐SIMS analysis, in the authors' laboratory. Copyright © 2008 John Wiley & Sons, Ltd.