Highly diastereoselective synthesis of new chromenylaminoanthraquinones through a one-pot, three-component hetero Diels–Alder reaction

A new, efficient, and diastereoselective one-pot synthesis of cis-fused pyrano and furano chromenylaminoanthraquinones through hetero Diels–Alder reaction of 1-aminoanthraquinone and salicylaldehydes with electron-rich alkenes such as 3,4-dihydro-2H-pyran, 2,3-dihydrofuran, and ethyl vinyl ether under mild conditions is reported.     

[1+1+3] Annulation of Diazoenals and Vinyl Azides: Direct Synthesis of Functionalized 1‐Pyrrolines through Olefination

A dirhodium carboxylate catalyzed [1+1+3] annulation reaction of diazoenals and vinyl azides that gives synthetically important enal‐functionalized 1‐pyrroline derivatives was developed. The reaction involves a novel rhodium‐catalyzed olefination of diazoenals with vinyl azides via electrophilic enal carbenoids, resulting in a new class of enal acrylates. The annulation reaction was used for the direct synthesis of valuable deuterated 1‐pyrrolines. Structural diversification of the enal‐functionalized 1‐pyrrolines resulted in the biologically important pyrrolidine‐fused oxaziridine, amino acid derivatives, and a 6‐azabicyclo[3.2.1]octane motif present in polycyclic alkaloids.     

Variable‐Temperature Powder X‐ray Diffraction of Aromatic Carboxylic Acid and Carboxamide Cocrystals

The effect of temperature on the cocrystallization of benzoic acid (BA), pentafluorobenzoic acid (FBA), benzamide (BAm), and pentafluorobenzamide (FBAm) is examined in the solid state. BA and FBA formed a 1:1 complex 1 at ambient temperature by grinding with a mortar and pestle. Grinding FBA and BAm together resulted in partial conversion into the 1:1 adduct 2 at 28 °C and complete transformation into the product cocrystal at 78 °C. Further heating (80–100 °C) and then cooling to room temperature gave a different powder pattern from that of 2 . BAm and FBAm hardly reacted at ambient temperature, but they afforded the 1:1 cocrystal 3 by melt cocrystallization at 110–115 °C. Both BA+FBAm ( 4 ) and BA+BAm ( 5 ) reacted to give new crystalline phases upon heating, but the structures of these products could not be determined owing to a lack of diffraction‐quality single crystals. The stronger COOH and CONH₂ hydrogen‐bonding groups of FBA and FBAm yielded the equimolar cocrystal 6 at room temperature, and heating of these solids to 90–100 °C gave a new crystalline phase. The X‐ray crystal structures of 1 , 2 , 3 , and 6 are sustained by the acid–acid/amide–amide homosynthons or acid–amide heterosynthon, with additional stabilization from phenyl–perfluorophenyl stacking in 1 and 3 . The temperature required for complete transformation into the cocrystal was monitored by in situ variable‐temperature powder X‐ray diffraction (VT‐PXRD), and formation of the cocrystal was confirmed by matching the experimental peak profile with the simulated diffraction pattern. The reactivity of H‐bonding groups and the temperature for cocrystallization are in good agreement with the donor and acceptor strengths of the COOH and CONH₂ groups. It was necessary to determine the exact temperature range for quantitative cocrystallization in each case because excessive heating caused undesirable phase transitions.     

HPTLC Method for Determination of 20-Hydroxyecdysone in Sida rhombifolia L. and Dietary Supplements

Naturally occurring 20-hydroxyecdysone is an important anabolic ecdysteroid. A simple thin-layer chromatography method to quantitate 20-hydroxyecdysone in methanolic extract of the whole plant material of Sida rhombifolia L. was developed. This method was successfully applied for quantitative evaluation of dietary supplements. The separation was achieved on glass TLC plates coated with silica gel 60F254, using chloroform: methanol (8:2 v/v) as developing solvent. Densitometric evaluation of 20-hydroxyecdysone was performed at 250 nm in reflectance/absorbance mode. The calibration was in the range of 200–1,000 ng spot^?1 and correlation coefficient for the calibration curve was >0.999. In addition, for six different Sida species unique fingerprints were obtained on the HPTLC plate.     

Design and Synthesis of Some New Benzimidazole Containing Pyrazoles and Pyrazolyl Thiazoles as Potential Antimicrobial Agents

A new class of bis heterocycles‐benzimidazolyl pyrazoles were prepared from the Michael acceptor (E)‐3‐(1H‐benzimidazol‐2‐yl)‐1‐aryl‐prop‐2‐en‐1‐one. The thiamide group was exploited to develop thiazole ring on treatment with p‐fluorophenacyl bromide to get tris heterocycles. All the lead compounds were tested for antimicrobial activity. The compound 7d having nitro substituent on the aromatic ring showed greater antimicrobial activity particularly against Pseudomonas aeruginosa and Penicillium chrysogenum.     

Rapid analysis of lignans from leaves of Podophyllum peltatum L. samples using UPLC‐UV‐MS

A new rapid UPLC‐UV‐MS method has been developed that permits the analysis of four lignans (4′‐O‐demethylpodophyllotoxin, podophyllotoxin, α‐peltatin and β‐peltatin) in P. peltatum L. Podophyllotoxin is a natural lignan that is being used as a precursor for the semi‐synthetic anti‐cancer drugs etoposide, teniposide and etopophos. The chromatographic separation was achieved using a reversed‐phase C₁₈ column with a mobile phase of water and acetonitrile, both containing 0.05% formic acid. Analyses of P. peltatum leaves collected from different colonies within a single site indicated a significant variation in 4′‐O‐demethylpodophyllotoxin, α‐peltatin, podophyllotoxin and β‐peltatin content. Within 3.0 min four main lignans could be separated with detection limits of 0.1, 0.3, 0.3 and 0.2 μg/mL, respectively. 4′‐O‐demethylpodophyllotoxin and α‐peltatin appeared most prominently among the lignans obtained. The podophyllotoxin content was found in the range of 0.004–0.77% from 16 samples collected from 6 colonies within the same site. The content of podophyllotoxin is directly proportional to the content of 4′‐O‐demethylpodophyllotoxin and inversely proportional to α‐peltatin and β‐peltatin content. LC‐mass spectrometry coupled with electrospray ionization (ESI) interface method is described for the identification of four lignans in various populations of plant samples. By applying principal component analysis and hierarchical cluster analysis, Podophyllum samples collected from various colonies within a location were distinguished. Copyright © 2011 John Wiley & Sons, Ltd.     

Analysis of suddenly started laminar flow in the entrance region of a circular tube

Suddenly started laminar flow in the entrance region of a circular tube, with constant inlet velocity, is investigated analytically by using integral momentum approach. A closed form solution to the integral momentum equation is obtained by the method of characteristics to determine boundary layer thickness, entrance length, velocity profile, and pressure gradient.Nomenclature M(, , ) a function - N(, , ) a function - p pressure - p* p/1/2U ², dimensionless pressure - Q(, , ) a function - R radius of the tube - r radial distance - Re 2RU/, Reynolds number - t time - U inlet velocity, constant for all time, uniform over the cross section - u velocity in the boundary layer - u* u/U, dimensionless velocity - u ₁ velocity in the inviscid core - x axial distance - y distance perpendicular to the axis of the tube - y* y/R, dimensionless distance perpendicular to the axis - boundary layer thickness - * displacement thickness - /R, dimensionless boundary layer thickness - momentum thickness - absolute viscosity of the fluid - /, kinematic viscosity of the fluid - x/(R Re), dimensionless axial distance - density of the fluid - tU/(R Re), dimensionless time - _w wall shear stress     

Phosphomolybdic Acid (PMA)–SiO2 as a Heterogeneous Solid Acid Catalyst for the One‐Pot Synthesis of 2H‐Indazolo[1,2‐b]phthalazine‐triones

Phosphomolybdic acid (PMA)–SiO₂ was found to be an efficient catalyst for the three‐component condensation reaction of phthalhydrazide, 1,3‐diketone, and aldehydes to produce 2H‐indazolo[1,2‐b]phthalazine‐triones in excellent yields. The catalyst can be recovered and reused without significant loss of activity.     

Determination of Shikimic Acid in Fruits of Illicium Species and Various Other Plant Samples by LC–UV and LC–ESI–MS

A simple and specific analytical method for the quantitative determination of shikimic acid from the methanol extract of the fruits of Illicium species and from various plant samples was developed. The LC–UV separation was achieved by reversed-phase chromatography on a C18 column with potassium dihydrogen phosphate and methanol as the mobile phase. In the LC–MS method, the separation was achieved by a C12 column using water and acetonitrile, both containing 0.1% acetic acid as the mobile phase. The methods were successfully used to study the percentage compositions of shikimic acid present in nine species of Illicium and various other plant samples. The detector response was linear with concentrations of shikimic acid in the range from 1.0–500.0 μg mL^?1 by LC–UV and 100–1000 ng mL^?1 by LC–MS. Mass spectrometry coupled with electrospray ionization interface is described for the identification of shikimic acid in various plant samples. This method involved the use of the [M-H]^? ions of shikimic acid at m/z 173.0455 (calculated mass) in the negative ion mode with extractive ion monitoring.