Biologically active compounds through catalysis: efficient synthesis of N-(heteroarylcarbonyl)-N'-(arylalkyl)piperazines

A practical route for the synthesis of new biologically active 5-HT(2 A) receptor antagonists has been developed. In only three catalytic steps, this class of central nervous system (CNS) active compounds can be synthesized efficiently with high diversity. As the initial step, an anti-Markovnikov addition of amines to styrenes provides an easy route to N-(arylalkyl)piperazines, which constitute the core structure of the active molecules. Here, base-catalyzed hydroamination reactions of styrenes with benzylated piperazine proceeded in high yield even at room temperature. After catalytic debenzylation, the free amines were successfully carbonylated with different aromatic and heteroaromatic halides and carbon monoxide to yield the desired compounds in good to excellent yields. The two key reactions, base-catalyzed hydroamination of styrenes and palladium-catalyzed aminocarbonylation of haloarenes/heterocycles, showed tolerance towards various functional groups, thereby demonstrating the potential to synthesize a wide variety of new derivatives of this promising class of pharmaceuticals.     

Encapsulating Au‐Fe3O4 Nanodots into AIE‐active Supramolecular Assemblies: Ambient Visible‐light Harvesting “Dip‐Strip” Photocatalyst for C−C/C−N Bond Formation Reactions

The present study demonstrates the development of a supramolecular porous ensemble consisting of hetero‐oligophenylene derivative 6 and Au‐Fe₃O₄ nanodots. Supramolecular assemblies of AIE‐active hetero‐oligophenylene derivative 6 served as reactors for the generation of Au‐Fe₃O₄ nanodots. The as prepared supramolecular ensemble functioned as an efficient recyclable photocatalytic system for C(sp²)?H bond activation of anilines for the construction of quinoline carboxylates. Interestingly, the “dip catalyst” prepared by depositing PTh‐co‐PANI‐6: Au‐Fe₃O₄ nanodots on a filter paper served as a recyclable strip (up to 10 cycles) for C?C/C?N bond formation reaction.     

Multiferroics by rational design: implementing ferroelectricity in molecule-based magnets

Multiferroic materials: A novel class of multiferroics based on organic-inorganic hybrid materials is synthesized. The ferromagnetic properties originate from the coordination network, whereas the ferroelectricity results from the polar organic ions (see picture, M=magnetization and P=polarization).     

Role of reactive species in processing materials at laboratory temperature by spray plasma devices

Processing the aerosol of metal salts in non-equilibrium plasma represents a promising technique that combines the advantages of spray pyrolysis with the high reactivity of plasmas at nearlaboratory temperature in order to produce mixed-oxides and perovskite materials. The aim of this paper is to describe the principles of this new technique and to present the various applications and latest developments. This technique’s capacity to deposit various mixed metal oxides with precise stoichiometry is demonstrated. It is shown that oxidant plasma species play a key role in the chemical transformation of starting materials into oxides at laboratory temperature, while the configuration of the reactor determines the morphology and texture of the deposited layers. Two different reactor configurations are presented. The porous layers of La _x Sr_1−x MnO₃ as the cathode for fuel cells were synthesised in a wave shock reactor configuration, while nanostructured ZnO-Al layers to form a transparent conductive cathode for photovoltaic cells were deposited in the spray plasma reactor of the latest generation for this technique. The experimental results emphasise the role of plasma species in the rate of chemical reactions and in the chemical composition of the deposited layers.     

Electron Ionization Mass Spectra of Organophosphorus Compounds. Part III: Mass Spectrometric Fragmentation of Diethyl Spiro[Pyrimidino[5,3′][1,2]Oxazole] Phosphonate,Diethyl (Oxazolo[5,4-D]Pyrimidine-4,6-Dione)Phosphonate,and Diethyl (Pyrimidino[4,5-B][1,4]Oxazine)Phosphonate Derivatives

Abstract

Fragmentation pathways of 14 organophosphorus compounds derived from diethyl spiro[pyrimidino[5,3][1,2]oxazole] phosphonates, diethyl (oxazolo[5,4-d]pyrimidine-4,6-dione)phosphonates, and diethyl (pyrimidino[4,5-b][1,4] oxazine)phosphonates were investigated by electron impact mass spectrometry (EI-MS). The intensity of the recorded molecular ion peaks showed various values depending on the nature of the compounds. Characteristic fragment ions were formed by successive loss of simple functional groups followed by decomposition of heterocycles connected to pyrimidine rings.     

Development and validation of HPLC method for simultaneous estimation of piperine and guggulsterones in compound Unani formulation (tablets) and a nanoreservoir system

An attempt has been made to develop and validate a simultaneous HPLC method for novel approach of drug release via oil‐in‐water (o/w) nanoemulsion formulation and Habb‐e‐Khardal Unani tablet containing piperine and guggul sterones E and Z as main ingredients. Nanoemulsion was prepared by titration method using sefsol‐218 as an oily phase, cremophor‐EL as a surfactant, transcutol as a co‐surfactant and distilled water as an aqueous phase. The formulation was optimized on the basis of thermodynamic stability and dispersibilty test. The nanoformulation was evaluated for particle size, surface morphology, electrical conductivity and viscosity determination. The in vitro dissolution was carried out by dialysis bag method. Drugs were quantified using an HPLC method developed in‐house with a C₁₈ column as stationary phase and acetonitrile and water as mobile phase at λ_max of 240 nm. The optimized formulation showed higher drug release, lower droplet size and less viscosity as compared with the conventional Habb‐e‐Khardal Unani tablet. The present study illustrated the potential of nanoemulsion dosage form in improving biopharmaceutic performance of piperine and guggul sterone. The HPLC method was also found to be quite sufficient for the routine quality control of formulations containing piperine and guggul sterone E and Z as ingredients and also for in vitro drug release studies. Copyright © 2011 John Wiley & Sons, Ltd.     

Multiple dot-in-rod PbS/CdS heterostructures with high photoluminescence quantum yield in the near-infrared

Pb cations in PbS quantum rods made from CdS quantum rods by successive complete cationic exchange reactions are partially re-exchanged for Cd cations. Using STEM-HAADF, we show that this leads to the formation of unique multiple dot-in-rod PbS/CdS heteronanostructures, with a photoluminescence quantum yield of 45-55%. We argue that the formation of multiple dot-in-rods is related to the initial polycrystallinity of the PbS quantum rods, where each PbS crystallite transforms in a separate PbS/CdS dot-in-dot. Effective mass modeling indicates that electronic coupling between the different PbS conduction band states is feasible for the multiple dot-in-rod geometries obtained, while the hole states remain largely uncoupled.     

A Facile Route to the Synthesis of New 2,3-Disubstituted Benzocoumarins

Triphenylphosphine catalyzes the reaction between 2-hydroxy-1-naphthaldehyde and π-deficient acetylenes to give the newly prepared benzo[f]chromenes. The mechanism for the formation of products is discussed.     

Reactive intermediates in the reaction of hydrazinecarbothioamides with 2-(bis(methylthio)methylene)malononitrile and ethyl 2-cyano-3,3-bis(methylthio)acrylate

Research on Chemical Intermediates - The reaction of N-substituted hydrazinecarbothioamides with both 2-(bis(methylthio)methylene)malononitrile and ethyl 2-cyano-3,3-bis(methylthio)acrylate...