Solvent‐mediated pseudo‐quadruple hydrogen‐bond motifs in three lamotrigine–carboxylic acid complexes

Lamotrigine, an antiepileptic drug, has been complexed with three aromatic carboxylic acids. All three compounds crystallize with the inclusion of N,N‐dimethylformamide (DMF) solvent, viz. lamotriginium [3,5‐diamino‐6‐(2,3‐dichlorophenyl)‐1,2,4‐triazin‐2‐ium] 4‐iodobenzoate N,N‐dimethylformamide monosolvate, C₉H₈Cl₂N₅⁺·C₇H₄IO₂⁻·C₃H₇NO, (I), lamotriginium 4‐methylbenzoate N,N‐dimethylformamide monosolvate, C₉H₇Cl₂N₅⁺·C₈H₈O₂⁻·C₃H₇NO, (II), and lamotriginium 3,5‐dinitro‐2‐hydroxybenzoate N,N‐dimethylformamide monosolvate, C₉H₈Cl₂N₅⁺·C₇H₃N₂O₇⁻·C₃H₇NO, (III). In all three structures, proton transfer takes place from the acid to the lamotrigine molecule. However, in (I) and (II), the acidic H atom is disordered over two sites and there is only partial transfer of the H atom from O to N. In (III), the corresponding H atom is ordered and complete proton transfer has occurred. Lamotrigine–lamotrigine, lamotrigine–acid and lamotrigine–solvent interactions are observed in all three structures and they thereby exhibit isostructurality. The DMF solvent extends the lamotrigine–lamotrigine dimers into a pseudo‐quadruple hydrogen‐bonding motif.     

Synthesis and Anticancer Evaluation of N-(Pyridin-3-yl)benzamide Derivatives

Russian Journal of Organic Chemistry - A series of N-[2-(4-methoxyanilino)-5-(3,4,5-trimethoxyphenyl)pyridin-3-yl]benzamides have been synthesized, and their structure was confirmed by 1H and 13C...     

Synthesis, structure and application of chiral copper(II) coordination polymers for asymmetric acylation

Chiral copper(II) coordination polymers 1a-c have been prepared by one-pot synthesis in high yield. Their single-crystal X-ray analysis showed that repeating units are connected to each other by carboxylate linker and copper(II) atoms are pentacoordinated with distorted square-pyramidal geometry for 1a-b and square-planar geometry for 1c. These polymers have catalyzed the kinetic resolution of secondary alcohols by acylation with up to 90% ee ( s = 50).     

A novel intramolecular Ugi 3CC for the synthesis of N-alkyl-3-oxo-2-aryl-1,2,3,4-tetrahydropyrazino[1,2-a]indole-1-carboxamides

An intramolecular Ugi reaction of 2-(2-formyl-1H-indol-1-yl)acetic acid with aryl amines and isocyanides has been developed to produce a novel class of N-alkyl-3-oxo-2-aryl-1,2,3,4-tetrahydropyrazino[1,2-a]indole-1-carboxamides in good yields. This is the first report on intramolecular Ugi three component reaction of 2-(2-formyl-1H-indol-1-yl)acetic acid, aryl amine, and isonitrile.     

New Synthesis of Analogues of the Antihypertensive Active Pharmaceutical Ingredient Irbesartan

A simple and new synthetic approach to various analogues of Irbesartan is described.     

Birefringence and stress growth in uniaxial extension of polymer solutions

Simultaneous measurements of extensional stresses and birefringence are rare, especially for polymer solutions. This paper reports such measurements using the filament stretch rheometer and a phase modulated birefringence system. Both the extensional viscosity and the birefringence increase monotonically with strain and reach a plateau. Estimates of this saturation value for birefringence, using Peterlin’s formula for birefringence of a fully extended polymer chain are in agreement with the experimental results. However, estimates of the saturation value of the extensional viscosity using Batchelor’s formula for suspensions of elongated fibres are much higher than observed. Reasons for the inability of the flow field to fully unravel the polymer chain are examined using published Brownian dynamics simulations. It is tentatively concluded that the polymer chain forms a folded structure. Such folded chains can exhibit saturation in birefringence even though the stress is less than that expected for a fully extended molecule.Simultaneous measurements of stress and birefringence during relaxation indicate that the birefringence decays much more slowly than the stress. The stress-birefringence data show a pronounced hysteresis as predicted by bead-rod models. The failure of the stress optic coefficient in strong flows is noted.Experiments were also performed wherein the strain was increased linearly with time, then held constant for a short period before being increased again. The response of the stress and birefringence in such experiments is dramatically different and can be traced to the different configurations obtained during stretching and relaxation. The results cast doubt on the appropriateness of pre-averaging the non-linear terms in constitutive equations.     

Three structures of dispirooxindole derivatives generated in situ through a three‐component one‐pot strategy with complete regio‐ and stereoselectivity

The challenging molecular architecture of spirooxindoles is appealing to chemists because it evokes novel synthetic strategies that address configurational demands and provides platforms for further reaction development. The [3+2] cycloaddition of the carbonyl ylide with arylideneoxindole via a five‐membered cyclic transition state gave a novel class of dispirooxindole derivatives, namely tert‐butyl 4′‐(4‐bromophenyl)‐1′′‐methyl‐2,2′′‐dioxo‐5′‐phenyl‐4′,5′‐dihydrodispiro[indoline‐3,2′‐furan‐3′,3′′‐indoline]‐1‐carboxylate, C₃₆H₃₁BrN₂O, (Ia), 5′‐(4‐bromophenyl)‐1,1′′‐dimethyl‐4′‐phenyl‐4′,5′‐dihydrodispiro[indoline‐3,2′‐furan‐3′,3′′‐indoline]‐2,2′′‐dione, C₃₂H₂₅BrN₂O₃, (Ib), and tert‐butyl 1′′‐methyl‐2,2′′‐dioxo‐4′‐phenyl‐5′‐(p‐tolyl)‐4′,5′‐dihydrodispiro[indoline‐3,2′‐furan‐3′,3′′‐indoline]‐1‐carboxylate, C₃₇H₃₄N₂O₅, (Ic). Crystal structure analyses of these dispirooxindoles revealed the formation of two diastereoisomers selectively and confirmed their relative stereochemistry (SSSR and RRRS). In all three structures, intramolecular C—H...O and π–π interactions between oxindole and dihydrofuran rings are the key factors governing the regio‐ and stereoselectivity, and in the absence of conventional hydrogen bonds, their crystal packings are strengthened by intermolecular C—H...π interactions.     

Preparation and characterization of polypropylene and waste tire powder modified by allylamine blends

Waste tire powder subjected to allylamine modification in the presence of ultraviolet (UV) radiation has been used to prepare polypropylene based thermoplastic vulcanizates with maleic anhydride polypropylene (MA‐PP) as compatibilizer. The effect of increasing the concentration of MA‐PP on performance characteristics like tensile strength, elongation and rheological properties have been investigated. X‐ray diffraction studies of the PP/waste tire powder blend indicate the disappearance of β crystalline peaks on addition of waste tire powder in the PP, whereas it is observed in the allylamine modified rubber powder loaded PP. Differential scanning calorimetry results further supported the above fact. The improvement in mechanical properties of the PP/allylamine modified rubber powder loaded thermoplastic vulcanizates has been explained in terms of βα transformation of PP crystals during straining of the samples and uniform dispersion of allylamine coated rubber powder in the PP matrix. The melt rheological properties of the thermoplastic vulcanizates loaded with modified rubber powder are higher than its counterpart due to the higher dispersion as a result of chemical interaction between the rubber powder surface with the MA‐PP. Copyright © 2008 John Wiley & Sons, Ltd.