Synthesis of 3,4‐Fused γ‐Lactone‐γ‐Lactam Bicyclic Moieties as Multifunctional Synthons for Bioactive Molecules

A short approach for the synthesis of 3,4‐fused γ‐lactone‐γ‐lactam bicyclic systems ( 1 ) in diastereomeric mixtures from chiral D ‐alanine methyl ester hydrochloride is described. The key step towards lactonisation is the reduction of the carbonyl ketone of the 5R‐configured 3,5‐dimethylpyrrolidine‐2,4‐dione diastereomers ( 8 ) via sodium borohydride in the presence of hydrochloric acid. With the presence of ethyl acetyl functionality at C3‐position, ester hydrolysis of 8 occurred concomitantly with keto reduction leading to lactonisation and eventually affording the anticipated (3S,4S,5R), (3R,4R,5R), (3R,4S,5R) and (3S,4R,5R) bicyclic moieties. The formation of the fused systems was confirmed by mass spectroscopy (MS) and nuclear magnetic resonance (NMR) analyses.     

Effect of Sn additions on the microstructure,mechanical properties,corrosion and bioactivity behaviour of biomedical Ti–Ta shape memory alloys

Ti–Ta and Ti–Ta–xSn shape memory alloys (SMAs) were produced successfully by microwave sintering. Tin element was added to Ti–Ta SMA with three different atomic percentages (0.37, 0.745 and 2.26 at.%). The influences of Sn addition on microstructure, transformation temperatures, mechanical properties, shape memory behaviours, corrosion resistance and bioactivity were investigated. It was found that the morphologies of the modified and unmodified Ti–Ta alloys contain a plate-like and needle-like structure, where the former structure is related to the β phase and the latter related to the α phase. The transformation temperatures of M _s to M _f with and without Sn additions were observed to be in the range of 389.65 to 355 K, while the transformation temperatures of A _s to A _f were found to be in the range of 250.42 to 365.8 K. By increasing the proportion of Sn, the compressive fracture strength and shape memory behaviour were enhanced; however, the corrosion resistance tended to be decreased. Based on the bioactivity results, antibacterial activity was improved with the addition of Sn. In conclusion, the existent results indicate that Ti–30 at.% Ta SMAs may be a convenient alternative to Ni–Ti for certain biomedical applications.

     

A new convenient procedure for the thionation of carbonyl compounds utilizing tetrachlorosilane-sodium sulfide

A combination of tetrachlorosilane (TCS) and sodium sulfide in acetonitrile is found to be an efficient thionating reagent for aromatic aldehydes in the absence of catalysis to give the corresponding thioaldehydes as trimers in good yields. Under cobalt(II) chloride catalysis, α,β-unsaturated ketones react with TCS-Na₂S to give the respective disulfides in good yields via the intermediacy of β-mercaptoketones at ambient temperature.     

Thermodynamics of Amino Acid Methyl Ester Hydrochlorides—Crown Ether Complexes in Methanol at 25°C

Stability constants, free energies, and enthalpies and entropies of the complexation of L-alanine methyl ester hydrochloride (L-Ala-HCl), L-phenylalanine methyl ester hydrochloride (L-Phe-HCl), and valine methyl ester hydrochloride (L-Val-HCl) with 15-crown-5 (15C5), benzo-15-crown-5 (B15C5), 18-crown-6 (18C6), benzo-18-crown-6 (B18C6), dicyclohexano-18-crown-6 (DC18C6), and dicyclohexano-24-crown-8 (DC24C8) in methanol are reported for 20°C. No significant variation in the stability constants and free energies of complexation is observed, indicating that the various crown ethers are poorly selective in binding the amino acids. However, the nature of the crown ether and the amino acid and their pattern of substitution cause a remarkable variation in the enthalpies and entropies of complexation. This indicates a strong enthalpy–entropy compensation effect. The enthalpy–entropy compensation effect for the crown ether complexes of the amino acid methyl ester hydrochlorides reported herein is compared with that of the crown ethers complexes of the amino alcohols and the free amino acid. It is found that the enthalpy–entropy compensation effect holds equally for the three classes of complexes.     

An Efficient Synthesis of Thioesters Via TFA-Catalyzed Reaction of Carboxylic Acid and Thiols: Remarkably Facile C–S Bond Formation

Abstract

A general, facile, and efficient new synthetic path to thioesters was established by employing defined TFA-catalyzed reaction of carboxylic acid and thiol under mild conditions. The structure of the newly synthesized compounds was determined by infrared spectroscopy, nuclear magnetic resonance, and a single crystal X-ray crystallographic analysis.

Supplemental materials are available for this paper. Go to the publisher's online edition of Phosphorus, Sulfur, and Silicon and the Related Elements to view the free supplemental file.     

Determination of Canrenone in Spironolactone Using Second Derivative Spectrophotometry

Second derivative spectrophotometry has been used to determine canrenone (I), the main degredation product in spironolactone (II). Second derivative at 300 nm was found linearly related to concentration in the range of 0.2–1 mg% I has been determined in II down to concentration level of 0.2 mg%. The results were found reproducible with a relative standard deviation of 1.7%.     

Novel Method for Determination of Anthracene by Coupling Dispersive Liquid-Liquid Extraction to First-Derivative Synchronous Spectrofluorimetry

A novel method could be adopted successfully for determination of anthracene in environmental samples, utilizing dispersive liquid-liquid extraction followed by first-derivative synchronous fluorimetry at a constant wavelength difference Δλ?=?165 nm, where a linear calibration curve was obtained in a concentration range of 0.5–100 ng mL^?1 at 244 nm. The detection limit was 0.1 ng mL^?1. The method can be easily adopted for determination of anthracene in aqueous media including tap water and river water. The recoveries obtained were 85.40–108.02 %. The proposed method was validated according to International Conference of Harmonization (ICH) guide lines and successfully applied to determine anthracene in pure form and in water samples including real life water samples from different sources. All the results obtained were compared with those of published method, where no a significant difference was observed.     

Chromatographic Application on Calixarene Bonded Stationary Phases: A Stability Indicating Method for Simultaneous Determination of Paracetamol, Caffeine and Acetylsalicylic Acid in Excedrin Tablets

A simple, rapid and accurate, routine-LC method is described for simultaneous determination of paracetamol, caffeine and acetylsalicylic acid in a tablet formulation. This study represents a new application for the calixarene stationary phases. The chromatographic separation of the three pharmaceuticals was achieved on a Caltrex BIIE column (250 × 4 mm, 5 μm) using a binary mobile phase of 14% ACN and 86% 50 mM NaH₂PO₄ pH 3.0 at 1 mL min^?1 flow rate. Detection was at 214 nm. Separation was achieved in less than 15 min. The method was validated for system efficiency, linearity, accuracy, precision, limit of detection and quantification, specificity, stability and robustness. The limits of detection were 4.88, 9.77 and 78.13 ng per 10 μL of their injected volumes, respectively. The recovery values of this method were between 94.63 and 101.85 and the reproducibility was within 3.88. The method could also be used for separation and determination of salicylic acid which is considered the most important degradation product of acetylsalicylic acid.