Regioselective Synthesis of Diltiazem Analogue Pyrazolo[4,3-c][1,5]benzothiazepines and Antifungal Activity

A dry media procedure has been developed for the synthesis of a series of new class of pyrazolo [4,3-c][1,5]benzothiazepines 6 under microwave irradiation using montmorillonite K10 as solid support. The catalyst can be recovered and reused. Thus, the procedure provides a simple and green synthetic methodology under environmentally friendly conditions. Antifungal screening of synthesized compounds has shown promising activity.

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

Synthesis,Spectral, and Structural Characterization of Bisthiocarbohydrazone Derivatives

Abstract

Bisthiocarbohydrazone derivatives of three heterocyclic ketone ligands, having a flexible coordination ability; 1, 5-bis (2-acetylthiophene) thiocarbohydrazone; 1, 5-bis (2-acetylfuran) thiocarbohydrazone; and 1, 5-bis (2-acetylpyrrole) thiocarbohydrazone were synthesized and characterized by elemental analysis, UV-visible, FT-IR, cyclic voltammetry, and ¹H and ¹³C-NMR spectral studies. All bisthiocarbohydrazone exhibited the thioketone—thioenol tautomeric forms, as evidenced by IR spectral data and single crystal X-ray diffraction studies of 1, 5-bis (2-acetylfuran) thiocarbohydrazone and 1, 5–bis (2-acetylpyrrole) thiocarbohydrazone.

Supplementary materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfer, and Silicon and the Related Elements for the following free supplemental files: Additional figures and tables.     

Functionalized Organotellurium Halides: Synthesis,Characterization, and Observation of Intra- and Intermolecular Secondary Bonding

Abstract

Activated tellurium, but not selenium, reacts with para-substituted benzoylmethyl bromides as well as with iodoacetamide at their melting points in absence of a solvent to give bis(p-substituted benzoylmethyl)tellurium dibromides, (p-YC₆H₄COCH₂)₂TeBr₂, (Y = H, Me, and MeO) and bis(acetamido)tellurium diiodide, (H₂NCOCH₂)₂TeI₂, respectively. Quick reduction of (p-YC₆H₄COCH₂)₂TeBr₂, with sodium metabisulphite in a two-phase system yields crystalline (p-YC₆H₄COCH₂)₂Te. These tellurides undergo smooth oxidative addition of halogens, interhalogen ICl or a pseudohalogen (SCN)₂. Intramolecular coordination of the carbonyl group in these functionalized diorganotellurium dihalides is evident from IR spectra and shorter Te···O (carbonyl) distances in comparison to the sum of van der Waals radii and completes six coordination around Te atom. Not unexpectedly, therefore, intermolecular secondary bonding effects of the type Te…O, Te···X and X···X are missing in (PhCOCH₂)₂TeBr₂, (p-MeOC₆H₄COCH₂)TeBr₂ and (PhCOCH₂)₂TeI₂. Instead, these compounds provide rare examples, among organotellurium compounds, of supramolecular architecture, where C–H···Br and C–H···O hydrogen bonds and π-π (phenyl ring) interactions appear to be the noncovalent intermolecular associative forces that dominate the crystal packing.     

RP-HPLC method for simultaneous estimation of lamivudine, tenofovir disoproxil fumarate and efavirenz in tablet formulation

A simple, rapid, and precise reversed-phase high-performance liquid chromatographic method for the simultaneous determination of lamivudine, tenofovir disoproxil fumarate and efavirenz in bulk and tablet dosage form has been developed and validated. Chromatography was performed on a 150 mm × 4.6 mm i.d., 5-μm particle, Phenomenex Luna C₁₈ column with 30: 45: 25 (v/v/v) acetonitrile: methanol: water as mobile phase at a flow rate of 0.5 mL/min. UV detection was done at 258 nm; lamivudine, tenofovir disoproxil fumarate and efavirenz were eluted with retention times of 3.27, 4.58 and 10.90 min, respectively. The method was validated in accordance with ICH guidelines. Validation revealed the method is specific, rapid, accurate, precise, reliable and reproducible. Calibration plots were linear over the concentration ranges 1–6 μg/mL for lamivudine and tenofovir disoproxil fumarate and 2–12 μg/mL for efavirenz. Limits of detection were 0.05, 0.09 and 0.11 μg/mL and limits of quantification were 0.15, 0.28 and 0.34 μg/mL for lamivudine, tenofovir disoproxil fumarate and efavirenz, respectively. The high recovery and low coefficients of variation confirm the suitability of the method for the simultaneous determination of these three drugs in bulk and tablets.     

Thermal studies of hypervalent iodine reagents

The use of unconventional synthesis methods in the formation of CaO·2Al₂O₃ (CA₂) is justified because it reduces the formation temperature of the compound. CA₂ is formed by classical method at temperatures above 1,400 °C. The polymeric precursor method allows a significant temperature decrease in CA₂ synthesis reaching temperatures of 1,000 °C. This paper deals with CA₂ synthesis by “citrate” method which is often presented as Pechini method, starting from a mixture of citric acid, ethylene glycol and calcium, and aluminum nitrates. A method based on the formation of a polymeric precursor was also used, starting from a mixture of acrylic acid and nitrates of calcium and aluminum. The results showed a net difference in favor of samples obtained from acrylic acid, which by annealing at 800 °C for 1 h, contain pure CA₂. The samples obtained from citric acid, after annealing at 800 °C are amorphous. After annealing at 900 °C in all samples CA₂ is single phase.     

Structural Transformation of Bovine Serum Albumin Induced by Dimethyl Sulfoxide and Probed by Fluorescence Correlation Spectroscopy and Additional Methods

Determining the structure of a protein and its transformation under different conditions is key to understanding its activity. The structural stability and activity of proteins in aqueous–organic solvent mixtures, which is an intriguing topic of research in biochemistry, is dependent on the nature of the protein and the properties of the medium. Herein, the effect of a commonly used cosolvent, dimethyl sulfoxide (DMSO), on the structure and conformational dynamics of bovine serum albumin (BSA) protein is studied by fluorescence correlation spectroscopy (FCS) measurements on fluorescein isothiocyanate (FITC)‐labeled BSA. The FCS study reveals a change of the hydrodynamic radius of BSA from 3.7 nm in the native state to 7.0 nm in the presence of 40 % DMSO, which suggests complete unfolding of the protein under these conditions. Fluorescence self‐quenching of FITC has been exploited to understand the conformational dynamics of BSA. The time constant of the conformational dynamics of BSA is found to change from 35 μs in its native state to 50 μs as the protein unfolds with increasing DMSO concentration. The FCS results are corroborated by the near‐UV circular dichroism spectra of the protein, which suggest a loss of its tertiary structure with increasing concentration of DMSO. The intrinsic fluorescence of BSA and the fluorescence response of 1‐anilinonaphthalene‐8‐sulfonic acid, used as a probe molecule, provide information that is consistent with the FCS measurements, except that aggregation of BSA is observed in the presence of 40 % DMSO in the ensemble measurements.     

An Efficient Procedure for the Preparation of 3′-Acetyl-2′,3′-dihydrobenzothiazoles by Ring Contraction of 2′,3′-Dihydro-1,5-Benzothiazepines Under Acetylating Conditions

Reaction of 2-benzoyl-6-hydroxy-3-methyl-5-(2′-substituted-2′,3′-dihydro-1,5-benzothiazein-4′-yl) benzofurans (4a-f) with a mixture of acetic anhydride and pyridine afforded 6-acetoxy-2-benzoyl-3-methyl-5-(3′-acetyl-2′-substitutedstyryl-2′,3′-dihydrobenzothiazole-2′-yl) benzofurans (5a-f) as sole products in good yields. A reaction mechanism for the ring contraction is proposed. All the compounds (5a-f) were screened for their antifeedant activity by the “Non-Choice test method” using 6 h prestarved fourth instar larvae of Spodoptera litura F. Compounds 5a, 5c and 5d exhibited highest antifeedant activity.