In situ characterisation of the aqueous gold colloid interface using CO as a surface probe: IR spectroscopic studies

Fourier transform infrared (FTIR) spectra are presented of CO gas-treated protected gold colloids prepared from hydrazinium hydrate reduction of an Au(III) precursor which reproducibly feature a weak, shortlived peak at ca. 2169 cm(-1). When the gold colloid was treated with 99% isotopically enriched (13)CO gas, the IR peak shifted to a frequency of 2114 cm(-1) which indicated that it represented a simple gold monocarbonyl species. The value of 2169 cm(-1) for the CO stretching frequency suggests the peak represents CO physisorbed on oxidised gold atoms on the colloid surface. The peak is not observed when the concentration of the colloidally dispersed gold is reduced either by use of lower starting salt concentrations or by aggregation. It is also not observed when solutions of the protecting agent or reducing agent or the dispersion medium (water) or even the starting Au(III) salts are CO-treated individually. This confirms that the spectral feature is uniquely associated with colloidally dispersed gold. In general, the work has shown that the surfaces of Au colloids in situ have partially oxidised Au character which is of interest in systems where supported nanoparticulate gold derived from colloid preparations are considered for low temperature oxidation catalysts for CO.     

A new three-component domino synthesis of 1,4-dihydropyridines

Cerium ammonium nitrate (CAN) catalyzed the three-component domino reaction between aromatic amines, α,β-unsaturated aldehydes, and ethyl acetoacetate, providing an efficient new entry into 1,4-dihydropyridines. This new reaction requires very mild reaction conditions, has water as the only side product and is complementary to the classical Hantzsch synthesis in that it is well suited to the preparation of N-aryl-5,6-unsubstituted dihydropyridines. Experiments in the presence of a radical trap suggest that a one-electron oxidative mechanism can be excluded and that CAN acts as a Lewis acid.     

Chemo,stereo, and regioselective addition of α‐(2‐methoxyaryl)‐N‐aryl nitrones to diarylidineacetone: Synthesis of novel isoxazolidines

A new set of 2,3,4,5‐tetrasubstituted isoxazolidines with an α,β‐unsaturated carbonyl function at position 4 has been synthesized. The multicomponent approach and microwave irradiation protocol have also been investigated for the above synthesis.     

Microwave assisted synthesis of thiazolo[3,2‐b][1,2,4]‐triazoles containing 1,8‐naphthyridine moiety

A simple and efficient protocol for the synthesis of 5‐aryl‐2‐(2‐substituted‐1,8‐naphthyridin‐3‐yl)‐thiazolo[3,2‐b][1,2,4]triazoles ( 4 ) is achieved by cyclocondensation of 3‐(2‐substituted‐1,8‐naphthyridin‐3‐yl)‐1,2,4‐triazoles ( 3 ) with α‐halogenoketones in anhyd. methanol under microwave irradiation. The products are obtained in good yields and in a state of high purity.     

Facile immobilization of potassium-copper hexacyanoferrate nanoparticles using a room-temperature ionic liquid as an ionic binder and its application towards BHA determination

In this paper, a facile immobilization of copper hexacyanoferrate nanoparticles (CuHCFNP) on a paraffin wax-impregnated graphite electrode (PIGE) was carried out using the room-temperature ionic liquid (RTIL) 1-ethyl-3-methylimidazolium tetrafluoroborate (EMIMBF₄) as an ionic binder. The characteristics of the CuHCFNP/EMIMBF₄ gel-modified electrode were investigated by cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) techniques, and the modified electrode morphology was also characterized using field emission scanning electron microscopy (FESEM). The electrocatalytic behavior of butylated hydroxyl anisole (BHA) at the modified electrode has been investigated in 0.1 M KNO₃ in static and dynamic conditions. Under the optimum conditions, the oxidation peak current was proportional to the BHA concentration in the range from 1.5 to 1000 μM with a detection limit of 0.5 μM (S/N = 3). The proposed method was applied to determine BHA content in real samples with satisfactory results.

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Asymmetric synthesis of (–)-leiocarpin A via (–)-(S)-goniothalamin employing Julia–Kocienski olefination

A concise and enantioselective syntheses of antileukemic natural products such as (–)-(S)-goniothalamin and (–)-leiocarpin A has been accomplished in excellent yields. By employing reported conditions on suitable substrates via Julia–Kocienski olefination, intramolecular lactonization, and subsequently dehydroxylative olefination, (–)-(S)-goniothalamin was synthesized. Then Sharpless asymmetric dihydroxylation–intramolecular Michael addition on (–)-(S)-goniothalamin provided (–)-leiocarpin A.     

Copper(I) iodide–catalyzed amidation of phenylboronic acids/aryl bromides using 4-dimethylaminopyridine as ligand

An efficient one-pot synthesis of N-arylbenzamide is described via reaction of phenylboronic acid/aryl bromide with benzamide in the presence of CuI (5 mol%) as catalyst, 4-dimethylaminopyridine (20 mol%) as the ligand, and Cs₂CO₃ (2 mmol) as the base. This protocol was applied to synthesize a small library of N-arylbenzamide in high yields.     

Synthesis and characterization of arsacycloalkanes and their palladium and platinum complexes,and X‐ray structure of [PdCl2(PhAsCH2CH2CH2CH2CH2)2]

Reactions of PhAsCl₂ with BrMg(CH₂)_nMgBr (n = 4 or 5) in THF gave phenylarsacycloalkanes as colourless oily liquids which could be distilled under vacuum. Treatment of PhAs(CH₂)_n­with MCl₂(RCN)₂ (M = Pd or Pt; R = Ph­or Me) afforded mononuclear complexes, [MCl₂{PhAs(CH₂)_n}₂]. Reactions with [Pt₂Cl₂(μ‐Cl)₂(PEt₃)₂] gave mixed‐ligand complexes, [PtCl₂(PEt₃){PhAs(CH₂)_n]. The palladium complexes adopt a trans geometry whereas the platinum complexes exist in a cis configuration. The crystal and molecular structure of [PdCl₂(PhAsCH₂CH₂CH₂CH₂CH₂)₂] was determined by X‐ray diffraction methods. The molecule consists of a square‐planar palladium atom with trans chlorides and trans arsa ligands. The six‐membered ‘AsC₅′ ring adopts a chair conformation. Copyright © 1999 John Wiley & Sons, Ltd.     

A regioselective 1,3‐dipolar cycloaddition of 2‐arylidene‐1‐tetralones with DPNI

Synthesis of a series of novel 1,3‐diphe nyl‐4‐arylspiropyrazolines[5.2¹]‐1¹‐tetralones has been accomplished in good yield by regioselective 1,3‐dipolar cycloaddition of diphenylnitrilimine with (E)‐2‐arylidene‐1‐tetralones. X‐ray crystal structure analysis of one of the products 4b confirms the structure and the regiochemistry of cycloaddition. © 1999 John Wiley & Sons, Inc. Heteroatom Chem 10: 331–336, 1999     

Stereoselective multicomponent synthesis of [3‐(5‐substituted 2‐methoxyphenyl)‐5‐aryl‐2‐phenyltetrahydro‐4‐isoxazolyl](2‐thienyl)methanones via 1,3‐dipolar cycloaddition

Three‐component stereoselective synthesis of a set of new tetra substituted isoxazolidines from 5‐substi‐tuted 2‐methoxybenzaldehydes, N‐phenylhydroxylamine and 1‐(2‐thienyl)‐3‐arylprop‐2‐en‐1‐ones has been achieved. The effect of microwave irradiation on the reaction under solvent‐free conditions has also been investigated. The stereochemistry of the final products has been confirmed by NMR and single crystal X‐ray analysis.