Solvent-controlled dehydration and diastereoselective formation of indenone-fused thiazolo[3,2-a]pyridines via a one-pot four-component reaction

A solvent-controlled four-component reaction has been described for the preparation of either hydroxy-tetrahydro-thiaza-cyclopenta[c]fluoren-6-one or dihydro-thiaza-cyclopenta[c]fluoren-6-one from nitroketene dithioacetals, cysteamine hydrochloride, 1,3-indandione and aromatic aldehydes starting materials by changing solvent systems. These reactions proceed under catalyst-free conditions affording a range of two types of skeletally distinct thiazolo[3,2-a]pyridines-based heterocycles. Hydroxy-tetrahydro-thiaza-cyclopenta[c]fluoren-6-one was obtained in H₂O/EtOH (3:1, v/v) in high yield and diastereoselectivity but in contrast dihydro-thiaza-cyclopenta[c]fluoren-6-one was synthesised in EtOH in moderate to good yields and in the longer reaction time. The structural diversities have been confirmed spectroscopically, by IR ¹H and ¹³C NMR, and EI-MS spectra, which agree with the proposed structures.     

Sorptive thin film microextraction followed by direct solid state spectrofluorimetry: A simple,rapid and sensitive method for determination of carvedilol in human plasma

A poly acrylate-ethylene glycol (PA-EG) thin film is introduced for the first time as a novel polar sorbent for sorptive extraction method coupled directly to solid-state spectrofluorimetry without the necessity of a desorption step. The structure, polarity, fluorescence property and extraction performance of the developed thin film were investigated systematically. Carvedilol was used as the model analyte to evaluate the proposed method. The entire procedure involved one-step extraction of carvedilol from plasma using PA-EG thin film sorptive phase without protein precipitation. Extraction variables were studied in order to establish the best experimental conditions. Optimum extraction conditions were the followings: stirring speed of 1000 rpm, pH of 6.8, extraction temperature of 60 °C, and extraction time of 60 min. Under optimal conditions, extraction of carvedilol was carried out in spiked human plasma; and the linear range of calibration curve was 15–300 ng mL⁻¹ with regression coefficient of 0.998. Limit of detection (LOD) for the method was 4.5 ng mL⁻¹. The intra- and inter-day accuracy and precision of the proposed method were evaluated in plasma sample spiked with three concentration levels of carvedilol; yielding a recovery of 91–112% and relative standard deviation of less than 8%, respectively. The established procedure was successfully applied for quantification of carvedilol in plasma sample of a volunteer patient. The developed PA-EG thin film sorptive phase followed by solid-state spectrofluorimetric method provides a simple, rapid and sensitive approach for the analysis of carvedilol in human plasma.     

Synthesis of novel 1,4-, 3,4-, and 4,5-dihydropyrimidines: First successful POCl3 chlorination and regioselective alkoxycarbonylation

Chlorination of 5,6-dihydropyrimidine-4-(3H)-one derivatives (1) with POCl₃ gave 1,4(3,4)-dihydropyrimidines (3), whose alkoxycarbonylation (ClCOOREt₃N or NaH) afforded regioselectively novel compounds (4). A new Pummerer rearrangement of compound (1, X= ---S(O)CH₃) with ₃, gave compound (5h).     

Characterization of atmospheric tritiated water concentration in the vicinity of the fukushima daiichi nuclear power plant

Journal of Radioanalytical and Nuclear Chemistry - This paper discusses the spatiotemporal variation in atmospheric tritiated water (HTO) concentration near the Fukushima Daiichi Nuclear Power...     

Applications of Dainshefsky's Dienes in the Asymmetric synthesis of Aza‐Diels‐Alder Reaction

Asymmetric hetero‐Diels‐Alder (AHDA) reactions provide a multitude of opportunities for the highly efficient, regio‐ and stereoselective construction of various heterocycles in enantiomerically pure form. The asymmetric aza‐Diels‐Alder (A‐aza‐DA) reaction using diversely hetero‐dienophiles and hetero‐dienes have been increasingly developed as a valuable method for the synthesis of functionalized nitrogen ring systems. The purpose of this review is to give a detailed discussion of the A‐aza‐DA reaction particularly, the stereoselective reactions of imines as dienophiles with Dainshefsky dienes to obtain optically pure aza‐Diels‐Alder products. The development of stereoselective variants of the reaction make use of imines as the dienophile and Dainshefsky dienes is at the forefront of these studies. This review updates the A‐aza‐DA reactions covering the literature from 1972 till date     

Pyrrole studies part 41. Reactivity of 3,4-diformyl-2,5-dimethylpyrrole with diaminoalkanes. An unusual formation of 2-azafulvenes

3,4-Diformyl-2,5-dimethylpyrrole (1) reacts with ,ω-diamino-alkanes, NH₂(CH₂)_nNH₂t' to form either the potentially tautomeric 2:2 macrocyclic adduct (7a) (8), when N = 2, or the potentially tautomeric 1:1 bicyclic adduct (18) (19), when N = 4, 5, 6, and 12. ¹H and ¹³C N.m.r. spectral data indicate that the 2-azafulvene structures predominate for both types of cycloadducts. Only polymeric material was obtained when N = 3.     

One-pot synthesis of 4,5-disubstituted 1,2,3-(NH)-triazoles by silica supported-zinc bromide in the aerobic condition

An efficient one-pot cross-coupling/1,3-dipolar cycloaddition sequence was developed for a convenient synthesis of 4,5-disubstituted-1,2,3-(NH)-triazoles, starting from various acid chlorides, terminal alkynes and sodium azide in the presence of silica supported-zinc bromide under aerobic conditions.