Efficient Solvent‐Free Synthesis of Benzothiazine‐Fused Pyrrolo[3,4‐c]coumarins: Cycloaddition Reactions between Coumarin‐Based Dihydrobenzothiazoles and Isocyanides

A new and unusual synthesis of benzothiazine‐fused pyrrolo[3,4‐c]coumarins, involving the ring‐opening of coumarin‐based dihydrobenzothiazoles and subsequent [4+1] cycloaddition reaction with isocyanides, was described. Thus, simple heating of various 3‐(2,3‐dihydro‐2‐methylbenzo[d]thiazol‐2‐yl)coumarins with isocyanides produced the title compounds in good yields under solvent‐free conditions.     

Reinvestigation of the Synthesis of Ketanserin (5) and its Hydrochloride Salt (5.HCl) via 3‐(2‐Chloroethyl)‐2,4‐(1H,3H)‐quinazolinedione (2) or Dihydro‐5H‐oxazole(2,3‐b)quinazolin‐5‐one (1)

The synthesis of ketanserin ( 5 ) and its hydrochloride salt ( 5.HCl ) using respectively equimolar amounts of 3‐(2‐chloroethyl)‐2,4‐(1H,3H)‐quinazolinedione ( 2 ) with 4‐(parafluorobenzoyl)piperidine ( 3 ) and dihydro‐5H‐oxazole(2,3‐b)quinazolin‐5‐one ( 1 ) with hydrochloride salt of 4‐(parafluorobenzoyl)piperidine ( 3.HCl ) is reinvestigated. The one‐pot reaction of ethyl‐2‐aminobenzoate with ethyl chloroformate and ethanol amine has afforded 3‐(2‐chloroethyl)‐2,4‐(1H,3H)‐quinazolinedione ( 2 ) (86%) that was then refluxed with 4‐(parafluorobenzoyl)piperidine ( 3 ) in ethyl methyl ketone in the presence of sodium carbonate to obtain free base of ketanserin (87%). In another attempt, a very pure hydrochloride salt of ketanserin ( 5.HCl ) was synthesized using equimolar amounts of dihydro‐5H‐oxazole(2,3‐b)quinazolin‐5‐one ( 1 ) and hydrochloride salt of 4‐(parafluorobenzoyl)piperidine ( 3.HCl ) by a solvent‐less fusion method. Thus, under optimized conditions, 180°C and a reaction time of 30 min, the powder mixture was transformed into glassy crystals that were initially readily soluble in chloroform but were transformed afterwards over time (2 h) to white precipitates ( 5.HCl ) suspended in chloroform with a yield of 72%.     

Synthesis and application of a thermosensitive tri-block copolymer as an efficient sample treatment technique for preconcentration and ultra-trace detection of lead ions

We have designed and synthesized a thermosensitive tri-block copolymer for selective trace extraction of Pb(II) ions from biological and food samples. The polymer was characterized by Fourier transform IR and NMR spectroscopy, and by gel permeation chromatography. The critical aggregation concentration and lower critical solution temperature were determined via fluorescence and UV spectrophotometry, respectively. The effects of solution pH value, amount of copolymer, of the temperature on extraction and on phase separation, and of the matrix on the extraction of Pb(II) were optimized. Pb(II) ions were then quantified by FAAS. The use of this copolymer resulted in excellent figures of merit including a calibration plot extending from 0.5 to 160 μg L^?1 (with an R² of >0.99), a limit of detection (LOD) as low as 90 pg L^?1, an extraction efficiency of >98 %, and relative standard deviations of <4 % for eight separate extraction experiments.

Screen-printed electrodes for biosensing: a review (2008–2013)

Screen-printing is one of the most promising approaches towards simple, rapid and inexpensive production of biosensors. Disposable biosensors based on screen printed electrodes (SPEs) including microelectrodes and modified electrodes have led to new possibilities in the detection and quantitation of biomolecules, pesticides, antigens, DNA, microorganisms and enzymes. SPE-based sensors are in tune with the growing need for performing rapid and accurate in-situ analyses and for the development of portable devices. This review (with 226 refs.) first gives an introduction into the topic and then is subdivided into sections (a) on DNA sensors (including methods for the detection of hybridization and damage), (b) on aptasensors (for thrombin, OTA, immunoglobulins and cancer biomarkers), (c) on immunosensors (for microorganisms, immunoglobulins, toxins, hormones, lactoferrin and biomarkers), (d) on enzymatic biosensors (for glucose, hydrogen peroxide, various pharmaceuticals, neurotransmitters, amino acids, NADH, enzyme based sensors).

Synthesis,Characterization and Photocatalytic Activity of Mg‐Impregnated ZnO–SnO2 Coupled Nanoparticles

ZnO–SnO₂ nanoparticles were prepared by coprecipitation method; then Mg, with different molar ratios and calcination temperatures, was loaded on the coupled nanoparticles by impregnation method. The synthesized nanoparticles were characterized by X‐ray diffraction (XRD), field emission scanning electron microscopy (FESEM), energy dispersive X‐ray spectroscopy (EDX), transmission electron microscopy (TEM), diffuse reflectance spectroscopy (DRS), and Brunauer–Emmett–Teller (BET) techniques. Based on XRD results, the ZnO–SnO₂ and Mg/ZnO–SnO₂ nanoparticles were made of ZnO and SnO₂ nanocrystallites. According to DRS spectra, the band gap energy value of 3.13 and 3.18 eV were obtained for ZnO–SnO₂ and Mg/ZnO–SnO₂ nanoparticles, respectively. BET analysis revealed a Type III isotherm with a microporous structure and surface area of 32.051 and 49.065 m² g^?1 for ZnO–SnO₂ and Mg/ZnO–SnO₂, respectively. Also, the spherical shape of nanocrystallites was deduced from TEM and FESEM images. The photocatalytic performance of pure ZnO–SnO₂ and Mg/ZnO–SnO₂ was analyzed in the photocatalytic removal of methyl orange (MO). The results indicated that Mg/ZnO–SnO₂ exhibited superior photocatalytic activity to bare ZnO–SnO₂ photocatalyst due to high surface area, increased MO adsorption and larger band gap energy. Maximum photocatalytic activity of Mg/ZnO–SnO₂ nanoparticles was obtained with 0.8 mol% Mg and calcination temperature of 350°C.     

Spectroscopic studies and molecular orbital analysis on platinanaphthalenes and ring-fused B-N platinanaphthalenes

The electronic structure and properties of the platinanaphthalenes, and ring-fused B-N platinanaphthalenes isomers have been explored using the hybrid density functional mpw1pw91 theory. The energetic aspect shows that stability of Ptb and Pta isomers are isoenergetic in platinanaphthalenes. On the other hand, BNa1 isomer is the most stable isomer of ring-fused B-N platinanaphthalenes. This is compatible with principles of minimum energy and minimum polarizability in ring-fused B-N platinanaphthalenes. Molecular orbital analysis shows increasing of hardness in ring-fused B-N platinanaphthalenes isomers. Also, electronic spectra analysis indicates that, in all the molecules HOMO-1 → LUMO transition makes the major contribution in most intense electronic transition.     

Novel Four-Step Synthesis of Thioxo-quinazolino[3,4-a]quinazolinone Derivatives

A novel synthesis of thioxo-quinazolino[3,4-a]quinazolinone framework was developed through a four-step reaction starting from isatoic anhydride. The resulting 2-aminobenzamides from the reaction of isatoic anhydride and different amines underwent coupling–cyclization reaction with 2-nitrobenzaldehydes, reduction of nitro group, and then cyclization reaction with carbon disulfide (CS₂). All steps were carried out under easy and user-friendly conditions in a short time without using expensive catalysts or reagents.

[Supplementary materials are available for this article. Go to the publisher's online edition of Synthetic Communications® for the following free supplemental resource(s): Full experimental and spectral details.]     

Efficient Synthesis of Pyrrolo[1,2-f]phenanthridine Derivatives via Dipolar Cycloaddition of Phenanthridine,Activated Acetylenes,and Ethyl Bromopyruvate

The three-component reactions of phenanthridine, activated acetylenes, and ethyl bromopyruvate through both of simultaneous and stepwise process are surveyed. The reactions afforded the corresponding pyrrolo[1,2-f]phenanthridine derivatives in good yields without using any catalyst and activation.

[Supplementary materials are available for this article. Go to the publisher's online edition of Synthetic Communications® for the following free supplemental resource(s): Full experimental and spectral details.]     

Vilsmeier Reagent: An Efficient Reagent for the Transformation of 2-Aminobenzamides into Quinazolin-4(3H)-one Derivatives

Clean and easy preparation of quinazolin-4(3H)-one derivatives using 2-aminobenzamides and Vilsmeier reagent is described. 2-Aminobenzamides were converted into the corresponding quinazolinones under mild and efficient conditions, in good yields without undesirable by-products.

[Supplementary materials are available for this article. Go to the publisher's online edition of Synthetic Communications® for the following free supplemental resource(s): Full experimental and spectral details.]