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.     

Application of Sulfonic Acid Functionalized SBA‐15 as a New Nanoporous Acid Catalyst in the Green One‐Pot Synthesis of Spirooxindole‐4H‐pyrans

Sulfonic acid functionalized SBA‐15 (SBA‐Pr‐SO₃H) as a new nanoporous solid acid catalyst was applied in the green one‐pot synthesis of spirooxindole‐4H‐pyrans via condensation of isatins, malononitrile or methyl cyanoacetate or ethyl cyanoacetate, and 4‐hydroxycoumarin in water solvent. SBA‐Pr‐SO₃H was proved to be an efficient heterogeneous nanoporous solid acid catalyst with a pore size of 6 nm that could be easily handled and removed from the reaction mixture by simple filtration and can be recovered and reused for several times without any loss of activity. The significant merits of present methodology are its simplicity, short reaction time, good yields, and environmentally benign mild reaction condition as water was used as a green solvent.     

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).

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.]     

Density functional studies of influences of Ni triad metals and solvents on oxidative addition of MeI to [M(CH3)2(NH3)2] complexes and C-C reductive elimination from [M(CH3)3(NH3)2I] complexes

Three metal square planar complexes of the type [M(CH₃)₂(NH₃)₂] (M = Ni, Pd, Pt), with a systematic variation in the metals, are chosen to investigating their S_N2-type oxidative addition reactions with methyl iodide by using the B3LYP levels of theory. The oxidative addition was found to take place via a transition state with a nearly linear arrangement of the I-CH₃-M moiety. Solvation effects in these oxidative addition reactions were also investigated. Considering the nature of the metal centre and solvation effects, the following conclusions emerge: (i) addition of MeI is exothermic for all three metals, and Pt is predicted to react with a much lower barrier than either Pd or Ni. The results describe that the MeI addition would be expected to be more favourable with the complex bearing the third-row metal (platinum) as compared to the other triad metals, nickel or palladium, in which case a more strongly bound MeI adduct is formed with a lower activation barriers and the reaction being more exothermic; (ii) the reaction is very difficult to occur in low polar solvents, such as benzene, due to the high barrier which is induced by dissociation of iodide anion from methyl group, but the reaction easily occurs in polar solvents, such as acetonitrile; this is attributed to the ability of polar solvents to solvate and therefore stabilize the related polar intermediate ion pair. Ethane reductive elimination from the M(VI) complexes fac-[M(CH₃)₃(NH₃)₂I] were also studied, indicating that the Ni(IV) and Pd(IV) complexes are very prone to undergo the reductive elimination while the Pt(IV) analogous is less reactive towards the reductive elimination. The results indicate that in contrast to the Me-Me reductive elimination, the S_N2 oxidative addition reaction of MeI to M(II) is much less sensitive to the nature of the metal centre, suggesting that the nucleophilicity of M(II) in [M(CH₃)₂(NH₃)₂] does not change significantly as one moves from M = Ni to Pt.     

Highly efficient synthesis of triazolo[1,2-a]indazole-triones and novel spiro triazolo[1,2-a]indazole-tetraones under solvent-free conditions

A new, convenient, and high yielding procedure for the synthesis of triazolo[1,2-a]indazole-triones by the condensation reaction between dimedone, aryl aldehydes, and ueazoles in the presence of a catalytic amount of sulfonated polyethylene glycol (PEG-SO₃H) as a highly stable and reusable eco-friendly degradable polymeric catalyst is described under solvent-free conditions. This procedure has also been applied successfully for the synthesis of novel spiro triazolo[1,2-a]indazole-tetraones.     

纳米孔碳负载Fe3O4催化剂上苯直接羟基化制苯酚

Fe3O4/CMK-3 was prepared by impregnation and used as a catalyst for the direct hydroxylation of benzene to phenol with hydro-gen peroxide. The iron species in the prepared catalyst was Fe3O4 because of the partial reduction of iron(III) to iron(II) on the surface of CMK-3. The high catalytic activity of the catalyst arises from the formation of Fe3O4 on the surface of CMK-3 and the high selectivity for phenol is attributed to the consumption of excess hydroxyl radicals by CMK-3. The effect of temperature,re...     

MgO Nanoparticles as a Recyclable Heterogeneous Catalyst for the Synthesis of Polyhydroquinoline Derivatives under Solvent Free Conditions

Magnesium oxide nanopartticels in average size between 35–120 nm were prepared by sonochemistry method. Synthesis of polyhydroquinoline derivatives using MgO nanoparticles from the reaction of dimedone, benzaldehyde, ethyl acetoacetate and ammonium acetate under solvent‐free conditions is reported. Easy handling, reusability, thermal stability and non‐toxicity of the catalyst make the present protocol as an eco‐friendly and economically acceptable method for synthesis of these heterocycles.     

Multiobjective optimization scheme for industrial synthesis gas sweetening plant in GTL process

In industrial amine plants the optimized operating conditions are obtained from the conclusion of occurred events and challenges that are normal in the working units. For the sake of reducing the costs, time consuming, and preventing unsuitable accidents, the optimization could be performed by a computer program. In this paper, simulation and parameter analysis of amine plant is performed at first. The optimization of this unit is studied using Non-Dominated Sorting Genetic Algorithm-II in order to produce sweet gas with CO 2 mole percentage less than 2.0% and H 2 S concentration less than 10 ppm for application in Fischer-Tropsch synthesis. The simulation of the plant in HYSYS v.3.1 software has been linked with MATLAB code for real-parameter NSGA-II to simulate and optimize the amine process. Three scenarios are selected to cover the effect of (DEA/MDEA) mass composition percent ratio at amine solution on objective functions. Results show that sour gas temperature and pressure of 33.98 ? C and 14.96 bar, DEA/CO 2 molar flow ratio of 12.58, regeneration gas temperature and pressure of 94.92 ? C and 3.0 bar, regenerator pressure of 1.53 bar, and ratio of DEA/MDEA = 20%/10% are the best values for minimizing plant energy consumption, amine circulation rate, and carbon dioxide recovery.     

Ambidentate coordination of dimethyl sulfoxide in rhodium(III) complexes

The two dimethyl sulfoxide solvated rhodium(III) compounds, [Rh(dmso-κO)(5)(dmso-κS)](CF(3)SO(3))(3) (1 & 1* at 298 K and 100 K, respectively) and [Rh(dmso-κO)(3)(dmso-κS)(2)Cl](CF(3)SO(3))(2) (2), crystallize with orthorhombic unit cells in the space group Pna2(1) (No. 33), Z = 4. In the [Rh(dmso)(6)](3+) complex with slightly distorted octahedral coordination geometry, the Rh-O bond distance is significantly longer with O trans to S, 2.143(6) ? (1) and 2.100(6) ? (1*), than the mean Rh-O bond distance with O trans to O, 2.019 ? (1) and 2.043 ? (1*). In the [RhCl(dmso)(5)](3+) complex, the mean Rh-O bond distance with O trans to S, 2.083 ?, is slightly longer than that for O trans to Cl, 2.067(4) ?, which is consistent with the trans influence DMSO-κS > Cl > DMSO-κO of the opposite ligands. Raman and IR absorption spectra were recorded and analyzed and a complete assignment of the vibrational bands was achieved with support by force field calculations. An increase in the Rh-O stretching vibrational frequency corresponded to a decreasing trans-influence from the opposite ligand. The Rh-O force constants obtained were correlated with the Rh-O bond lengths, also including previously obtained values for other M(dmso)(6)(3+) complexes with trivalent metal ions. An almost linear correlation was obtained for the MO stretching force constants vs. the reciprocal square of the MO bond lengths. The results show that the metal ion-oxygen bonding of dimethyl sulfoxide ligands is electrostatically dominated in those complexes and that the stretching force constants provide a useful measure of the relative trans-influence of the opposite ligands in hexa-coordinated Rh(III)-complexes.