Iron (III) Perchlorate Adsorbed on Silica Gel: A Reagent for Organic Functional Group Transformations

Adsorption of Fe(ClO₄)₃(H₂O)₆ onto chromatographic‐grade silica gel in the presence of organic solvents (S=water, acetonitrile, or lower fatty acids) produces a supported reagent, Fe(ClO₄)₃(S)₆/SiO₂. This reagent has been found to be effective for the rapid organic functional group transformations such as dimerization of alkynes, aromatic hydrocarbons, selective oxidation of thiols to disulfides, and transannular reactions in 1,5‐cyclooctadienes on grinding using pestle and mortar in the solid state.     

Cp*RhIII-Catalyzed Sterically Controlled C(sp3)−H Selective Mono- and Diarylation of 8-Methylquinolines with Organoborons**

Herein, the Rh^III-catalyzed selective monoarylation and diarylation (symmetrical and unsymmetrical) of 8-methylquinolines with organoboron reagents are disclosed. The selective monoarylation of primary C(sp³)−H bonds is achieved by using 7-substituted 8-methylquinolines or by changing the quantity of the aryl boronic acids. The method is also applicable for the arylation of 2-ethylpyridines, and the heteroarylation with thiophene-2-ylboronic acids. Symmetrical and unsymmetrical diarylation of 8-methylquinolines have been carried out in one-pot and sequential manner, respectively. Late-stage monoarylation of oxime derivatives and gram-scale synthesis of monoarylated products has also been carried out. A mechanistic study revealed that the current reaction is first order with respect to both reactants and a five-membered rhodacycle intermediate may be involved in the catalytic cycle.     

Coumarinolignans from the Root of Formosan Antidesma pentandrum var. barbatum

Four new coumarinolignans, antidesmanin A (=7‐(1,1‐dimethylallyl)‐2,3‐dihydro‐3‐(4‐hydroxy‐3,5‐dimethoxyphenyl)‐10‐methoxy‐2‐methyl‐6H‐1,4,5‐trioxaphenanthren‐6‐one; 1 ), antidesmanin B (=3,7‐bis(1,1‐dimethylallyl)‐2,3‐dihydro‐2‐(4‐hydroxy‐3‐methoxyphenyl)‐10‐methoxy‐6H‐1,4,5‐trioxaphenanthren‐6‐one; 2 ), antidesmanin C (=2,7‐bis‐(1,1‐dimethylallyl)‐2,3‐dihydro‐3‐(4‐hydroxy‐3‐methoxyphenyl)‐10‐methoxy‐6H‐1,4,5‐trioxaphenanthren‐6‐one; 3 ) and antidesmanin D (=2‐(3,4‐dihydroxyphenyl)‐3,7‐bis(1,1‐dimethylallyl)‐2,3‐dihydroxy‐10‐methoxy‐6H‐1,4,5‐trioxaphenanthren‐6‐one or 3‐(3,4‐dihydroxyphenyl)‐2,7‐bis(1,1‐dimethylallyl)‐2,3‐dihydro‐10‐methoxy‐6H‐1,4,5‐trioxaphenanthren‐6‐one; 4 ) have been isolated from the root of the Formosan Antidesma pentandrum var. barbatum. The structures of these new compounds were elucidated by spectroscopic data. Compounds 1 – 3 exhibited marginal cytotoxicity against MCF‐7 (breast) and SF‐268 (CNS) cancer cell lines in vitro.     

Crystal Nucleation Rates for Particles Experiencing Short-Range Attractions: Applications to Proteins

A kinetic model for the nucleation of a crystalline phase consisting of particles experiencing short-range attractions is developed. Of particular significance is the proximity of the metastable fluid/fluid phase boundary. The model incorporates self-consistent thermodynamics, changes in gradient diffusivity, and density fluctuations in the vicinity of the critical point. Density fluctuations associated with the spinodal of this metastable phase transition greatly enhance nucleation rates, suggesting that experimental conditions may be found where rapid nucleation and slow crystal growth can be achieved by moving the metastable critical point relative to the solubility boundary. Copyright 2000 Academic Press.     

Mixed valence copper(I)–copper(II) complexes of N,S donor ligands and their 7,7′,8,8′-tetracyanoquinodimethane derivatives

The reaction of the CuCl2·2H2O with the N,S donor ligands bis(o-aminobenzenethio)ethane, bis(o-aminoben-zenethio)propane and bis(o-aminobenzenethio)butane (abbreviated as eN2S2, pN2S2 and bN2S2, respectively) yielded mononuclear CuII complexes of stoichiometry Cu(L)Cl2 (L=eN2S2, pN2S2 or bN2S2). When the reactions were performed in the presence of 2,6–diacetylpyridine and NaClO4, binuclear mixed valence CuI–CuII complexes of stoichiometry [Cu2(L)][ClO4]3 (L=eN6S4, pN6S4 or bN6S4) were formed. Metatheses between the binuclear complexes and the lithium salt of 7,7,8,8-tetracyanoquinodimethane (TCNQ) yielded complexes of stoichiometry Cu2(L)(TCNQ)2 (L=eN6S4, pN6S4 or bN6S4). All of the complexes were characterised by analytical and spectroscopic techniques.     

Sampling of Atmospheric Carbonyls with Small DNPH-Coated C18 Cartridges and Liquid Chromatography Analysis with Diode Array Detection

Abstract

Carbonyls in air are sampled using small DNPH-coated C18 cartridges and analyzed by liquid chromatography with diode array detection. Carbonyl structure confirmation is obtained by comparing diode array spectral scans of samples to the uv-visible spectra (190–600 nm) of some 20 carbonyl hydrazones recorded in the CH₃CN—H₂O eluent used for LC analysis. Analytical detection limits are 0.09–3.4 nanograms carbonyl and correspond to 0.14–1.24ppb in 60 L air samples. Accuracy was ±5% as measured for independently prepared hydrazone standards. The precision was 1–5% for multiple injections of hydrazone standards and 2–10% for replicate analysis of indoor and outdoor air samples. Excellent agreement was obtained in an interlaboratory comparison that included hydrazone standards as well as indoor air samples.

Cartridge collection efficiency has been tested over a range of conditions (sampling flow rate, volume of air sampled, presence of co-pollutants including photochemical oxidants) and is >0.95 for monofunctional carbonyls, unsaturated carbonyls, and alpha dicarbonyls. Carbonyl recovery by cartridge elution is >0.99 for all carbonyls tested. Examples of applications are given in the fields of atmospheric chemistry, indoor air pollution in museums, and outdoor air quality.     

Inositol derived crown ethers: effect of auxiliary protecting groups and the relative orientation of crown ether oxygen atoms on their metal ion binding ability

The binding constants of crown ethers prepared from tetra-O-substituted myo- and scyllo-inositol derivatives and 2-O-substituted myo- and scyllo-inositol-1,3,5-orthoformates, with metal picrates show that the O-substituents and the relative orientation of the crown ether oxygen atoms contribute significantly to the binding of crown ethers with metal ions. In particular, the binding efficiency of myo-inositol derived crown ethers to silver and potassium ions could be enhanced by introducing benzyl ethers in the inositol ring. Hence binding efficacy and selectivity of metal ions to inositol derived crown ethers can be tuned by varying substituents on the myo-inositol ring and/or the relative orientation of crown ether oxygen atoms.     

Spectrophotometric determination of ciprofloxacin by ion pair formation

Various aspects of application of derivative spectrophotometry to chemical analysis and investigations of equilibria and kinetics of reactions are scrutinised. In this work the viability of a spectrophotometric technique for the determination of ciprofloxacin has been deliberated. The method is based on the formation of ion-association complexes of ciprofloxacin with nickel(II) tetra thiocyanate, which are extracted into organic solvent (40% n-butanol in methylene chloride) having absorption maxima at 623 nm. The precision and accuracy of the method was checked by UV reference methods. The validation study indicated the parameters, which are in good agreement with the data obtained from standard methods. The proposed method was fruitfully applied to determine ciprofloxacin in their tablet formulations.