Direct resolution of (+/-)-ephedrine and atropine into their enantiomers by impregnated TLC

Direct resolution of (+/-)-ephedrine and atropine into their enantiomers was achieved by normal-phase thin layer chromatography on silica gel plates impregnated with optically pure L-tartaric acid and L-histidine, respectively, as chiral selectors. The mobile phases enabling successful resolution were different combinations of acetonitrile-methanol-water. The spots were detected with iodine vapours and the detection limits were 2 and 6 microg, respectively, in terms of the racemate. The effects of concentration of the impregnating reagent, temperature and pH on resolution have been studied.     

Syntheses and crystal structures of three novel Cu(II) coordination polymers of different dimensionality constructed from Cu(II) carboxylates (carboxylate = malonate (mal), 2 acetate (ac), fumarate (fum)) and conformationally flexible 1,4-bis(imidazole-1-yl-methylene)benzene (IX)

We herein report three new coordination polymers generated from Cu(II) carboxylates (mal, 2ac, fum) and conformationally flexible bifunctional IX as building blocks. All the three complexes adopt unique structures in the solid state. The complex [Cu₂(mal)₂(IX)₂(H₂O)₆]_n crystallizes as orthorhombic co-linear rods with space group P2(1) P2(1) P2(1). Each rod is further formed of two tightly intertwined strings. The second polymer [Cu₂(ac)₄(IX)₂]_n crystallizes with space group P1 which consists of two sets of intersecting 2D sheets composed of parallel rods which interpenetrate to form a fully interlocked 3D structure. In both these complexes IX coordinates in the anti mode. The third polymer [Cu₂(fum)₂(IX)₂(H₂O)₂]_n possesses a monoclinic crystal system with space group C₂/c and crystallizes as 1D straps. Cu–fum–Cu forms the base of the string which is alternatively garlanded by a macrocycle derived from Cu₂(IX)₂ unit, where IX coordinates in the syn fashion. The present study suggests that the use of a rigid building block with a flexible organic ligand leads to a better prediction of the final structure of the polymeric array.     

A rational study of crystal engineering of supramolecular assemblies of 1,2,4,5-benzenetetracarboxylic acid

Supramolecular assemblies of 1,2,4,5-benzenetetracarboxylic acid, 1, with aza donor molecules such as 1,10-phenanthroline, 2, 1,7-phenanthroline, 3, phenazine, 4, 4-(N,N-dimethylamino)pyridine, 5, 1,2-bis(4-pyridyl)ethene, 6, and 1,2-bis(4-pyridyl)ethane, 7, have been synthesized and characterized by single-crystal X-ray diffraction methods. All the complexes crystallize in the triclinic, Ponemacr; space group. In the complexes of 2 and 4, water is also present in the resultant assembly, but the complexes of 5, 6, and 7 crystallize without any water molecules or solvent of crystallization. However, 3 forms two types of complexes, a hydrate and a nonhydrate complex, depending upon whether water is used as a solvent or not. These assemblies divide into two classes, host-guest systems (with aza molecules being in the channels created by the acid molecules) and assemblies with infinite molecular tapes. While the assemblies of the compounds 2, 4, and 5 belong to the former class, the assemblies of compounds 6 and 7 form molecular tapes, which are arranged in two dimensions to form sheet structures. The two structures of 3, in fact, bridge the two classes with each one falling into different categories.     

Direct enantiomeric resolution of (+/-)-atenolol, (+/-)-metoprolol,and (+/-)-propranolol by impregnated TLC using L-aspartic acid as chiral selector

Resolution of three commonly used beta-blockers, (+/-)-atenolol, (+/-)-metoprolol and (+/-)-propranolol, into their enantiomers has been achieved using normal-phase TLC on silica gel plates impregnated with L-aspartic acid as the chiral selector. Different combinations of acetonitrile-methanol-water as mobile phase were found to be successful in resolving the enantiomers. The spots were detected with iodine and the detection limits were found to be 0.26 microg for atenolol and 0.23 microg for each of metoprolol and propranolol as racemate.     

High-performance liquid chromatographic separation of bile acids and bile alcohols diastereoisomeric at C-25

The high-performance liquid chromatographic separation of the 25R and 25S diastereoisomers of the bile alcohols 5 beta-cholestane-3 alpha,7 alpha,26-triol and 5 beta-cholestane-3 alpha,7 alpha, 12 alpha, 26-tetrol and the bile acids, 3 alpha,7 alpha-dihydroxy-5 beta-cholestane-26-oic acid and 3 alpha,7 alpha,12 alpha-trihydroxy-5 beta-cholestane-26-oic acid is described. A Radial-Pak microBondapak C18 reversed-phase cartridge was used for the separations and elutions were carried out with acetonitrile-water-methanol-acetic acid mixtures. All eight diastereoisomeric compounds showed baseline separation when up to 200 micrograms of the isomeric mixtures were injected into the column and the method can be used for isolation of pure diastereoisomers of these bile acids and bile alcohols.     

Syntheses of poly[N-(1-pyrenyl)acetyl ethylenimine] [pyrene-substituted linear poly(ethylenimine)] and poly[methyl 2-(1-pyrenyl)acetamidopropenoate] [pyrene-substituted poly(dehydroalanine methyl ester)]

The syntheses of two new pyrene-containing monomers—2-(1-pyrenyl)methyl-2-oxazoline ( 6 ) and methyl 2-(1-pyrenyl)acetamidopropenoate ( 12 )—and their polymerization are described. Cationic isomerization polymerization of 6 with ethylene glycol ditosylate initiator gave poly[N-(1-pyrenyl)acetyl ethylenimine] ( 7 ) and free-radical polymerization of 12 with AIBN initiator gave poly[methyl 2-(1-pyrenyl)acetamidopropenoate] ( 15 ). The monomer model compounds of the two polymers, namely, N,N-diethyl(1-pyrenyl)acetamide ( 9 ) and methyl 2-methyl-2-(1-pyrenyl)acetamidopropanoate ( 14 ), were also synthesized. The polymers were characterized by elemental analysis, IR spectroscopy, and a comparison of their ¹H-NMR spectra with those of the respective monomer model compounds.     

Pyridine mediated supramolecular assemblies of 3,5-dinitro substituted benzoic acid, benzamide and benzonitrile

Synthesis and characterization of molecular assemblies of pyridine adducts, 1a, 2a and 3a, of 3,5-dinitrobenzoic acid, 1, 3,5-dinitrobenzamide, 2 and 3,5-dinitrobenzonitrile, 3, respectively, have been reported. All these adducts were obtained by crystallization of 1, 2 and 3 from pyridine. However, crystallization of 1 from pyridine in the presence of benzene resulted in the formation of a pyridinium adduct, 1b, along with a water molecule. All the adducts crystallize in a 1:1 molecular ratio except 1a, which forms a 1:2 adduct, as characterized by single crystal X-ray diffraction method. The adducts crystallize in different space groups—1a, orthorhombic, Pna2₁; 1b, monoclinic, P2₁; 2a, monoclinc, C2/c; 3a, triclinic, . In two-dimensional arrangement, 1a, 1b and 3a form sheet structures. In 1a, within the two-dimensional sheets, large cavities are formed, which are occupied by pyridine molecules. In 1b, the sheets are catenated to form a chicken-wire network. However, 2a formed a crossed ribbon packing pattern with empty channels in the three-dimensional structure.     

Complexes of quinolone drugs norfloxacin and ciprofloxacin with alkaline earth metal perchlorates

The interaction of quinolone drugs Norfloxacin (NR) and Ciprofloxacin (CP) with magnesium, calcium and barium perchlorates was investigated. Solid complexes, obtained as products of this interaction, were isolated and characterized by elemental and thermal analysis, FT-IR spectral and electrical conductivity measurements. The spectral studies of the isolated complexes suggest that NR and CP act as bidentate ligands that bind through one carboxylic oxygen atom and the exocyclic carbonyl oxygen atom. The obtained results indicate the formation of the complexes of the following formulas: [M(CP)₂](ClO₄)₂·xH₂O and [M(NR)₂](ClO₄)₂·xH₂O, where M = Mg(II), Ca(II), and Ba(II).     

Cu-assisted C–N bond formations in six-membered N-heterocycle synthesis

Abstract

One of the highly emerging and important aspect of organic chemistry is the metal-catalyzed synthesis of the heterocycles. The methodologies used earlier for its synthesis were less approachable to the organic chemist because of their high cost, highly specified instrumentation and inconvenient methods. For both the stereoselective and regioselective synthesis of six-membered nitrogen-containing heterocycles, cyclic reactions that are Cu-catalyzed have known to be very efficient. The presented review covers the varied applications of Cu as a catalyst and its importance in the formation of six-membered nitrogen-containing heterocycles. The fascinating research that has been done in this area is also enclosed in this review.