Synthesis and characterization of supramolecular optically active bisamides derived from amino acids

The synthesis and phase transitional behaviour of three pairs of enantiomeric supramolecular hexacatenar liquid crystals (LCs) derived from natural α-amino acids such as l/d-alanine, l/d-leucine and l/d-valine are described. Their preparation with high enantiomeric purity was accomplished by condensing optically active (amino acid residue containing) trialkoxy amines with a 3,4,5-trialkoxy cinnamic acid core using a peptide coupling reagent namely, 2-(1H-benzotriazol-1-yl)-1,1,3,3-tetramethyl-uronium hexafluorophosphate (HBTU). The mesomorphic behaviour of these self-complementing mesogens was ascertained by polarising optical microscopy, differential scanning calorimetry and X-ray diffraction. The compounds exhibit columnar (Col) phase over a wide thermal range. Particularly, a pair of enantiomers derived from l/d-leucine residues notably stabilize hexagonal Col (Col_h) phase over a wide temperature range of ?5 °C to 180 °C. Circular dichroism (CD) and FTIR studies suggest the chiral (helical) organization of mesogens within the columns through intermolecular hydrogen bonding; thus, these enantiomers represent one of the rarely reported examples of LCs exhibiting supramolecular Col_h phase at room temperature. The gelation studies reveal the ability of these bisamides to form stable supramolecular gels in ethanol caused through H-bonding interactions.     

A convergent approach towards the synthesis of the 2-alkyl-substituted tetrahydroquinoline alkaloid (−)-cuspareine

A convergent approach towards the synthesis of the 2-alkyl-substituted tetrahydroquinoline alkaloid (?)-cuspareine via enantiospecific construction of the (R)-benzyl 2-formyl-3,4-dihydroquinoline-1(2H)-carboxylate. We have achieved an efficient enantiospecific synthesis of (?)-cuspareine starting from known key starting materials. The reactions employed for individual transformations are simple and high yielding, and the strategy could potentially be easily extended.     

Facile Synthesis of Novel Pentofuranose Analogs of Phospha Sugar Derivatives

Novel pentofuranose analogs of phospha sugar derivatives were synthesized starting from 1-phenyl-2-phospholene 1-oxide ( 1 ). First, the allylic oxidation of 1-phenyl-2-phospholene 1-oxide ( 1 ) with CrO 3 in Ac 2 O-AcOH or 3-hydroxy-1-phenyl-2-phospholene ( 2 ) with MnO 2 afforded 1-phenyl-4-oxo-2-phospholene 1-oxide ( 3 ). The C-5 alkylation of 3 in the presence of NaH by using benzyl bromide or methyl iodide as electrophiles afforded the target title compounds.     

SYNTHESIS OF SOME SULFUR-CONTAINING SPIROINDOLE DERIVATIVES

Abstract

The synthesis of some new sulfur-containing spiroindole derivatives is reported. Fluorinated 3′-aryl-2′-phenylimino-spiro[3H-indole-3,6′[4,5′-pyrazolin][4,3-d]thiazolo]2(1H)-ones were prepared by the reaction of 5-(2-oxo-3-indolinylidene)-3-aryl-2-phenylimino-4-thiazolidinones with hydrazine hydrate. The compounds have been characterized on the basis of elemental and spectral studies.     

Polyethylene glycol (PEG-400): An efficient one-pot green synthesis and anti-viral activity of novel α-diaminophosphonates

Abstract

An efficient and eco-friendly protocol has been accomplished for a series of novel α-diaminophosphonates by a one-pot, three-component system via Kabachnik-Fields reaction of 4,4′-methylenedianiline, a variety of aryl/heteroaryl aldehydes and diphenylphosphite employing polyethylene glycol (PEG-400) as a green solvent at 80?°C. All products were obtained in good to excellent yields (80–95%). The identity of the new synthesized compounds was confirmed by IR, ¹H, 13C, and 31P NMR, LC-MS and elemental analysis. In vivo anti-viral activity was evaluated against tobacco mosaic virus (TMV). Compounds 4b, 4c, 4j and 4k exhibited the highest anti-viral activities against tobacco mosaic virus (TMV) when compared with the standard drug ningnanmycin.     

Electrical,Mechanical, and Thermal Properties of Poly(4,4′-Cyclohexylidene Diphenylene-m-Benzene/Toluene-2,4-Disulfonate)

Abstract

The films of poly(4,4′-cyclohexylidene diphenylene-m-benzene disulfonate) (PSBB, 0.610 mm thick) and poly(4,4′-cyclohexylidene diphenylene-toluene-2,4-disulfonate) (PSBT, 0.537 mm thick) showed 8.23 ± 0.25 and 9.6 ± 0.245 kV, respectively, as the dielectric breakdown voltage (ac) in air at room temperature. The same films have 8.8 × 10¹¹ and 7.2 × 10¹⁴ ω°Cm volume resistivity. PSBB (40 μm thick) and PSBT (50 μm thick) films have tensile strengths of 1971 and 1677 kg/cm² and percent elongations of 1.3 and 1.2, respectively. The static hardnesses of PSBB (0.178 mm thick) and PSBT (0.190 mm thick) at three different loads (15–60 g) are 12.8–15.5 and 14.5–16.5 kg/mm², respectively. PSBB and PSBT are thermally stable up to about 355°C in an N₂ atmosphere and involve two-step degradation. DSC and DTA showed T _g at about 125–127 and 138–142°C, respectively, for PSBB and PSBT in N₂. PSBB and PSBT have comparable breakdown voltages and volume resistivity with some useful plastics whereas they have superior T _g and thermal stability with retention of excellent solubility in common solvents over polysulfonates without a cardo group. Thus, the cardo (cyclo-hexyl) group has enhanced thermal and mechanical properties with excellent solubility and easy processing.     

Synthesis and Characterization of Amphiphilic Block Copolymer by Block Copolymerization of Butadiene and Acrylamide using Macroazoinitiator

Abstract

Macroazoinitiator (MAI) was prepared from hydroxyl‐terminated polybutadiene (HTPB) and 4,4′‐azobis‐4‐cyanopentanoic acid by direct polycondensation in the presence of 1‐methyl‐2‐chloropyridinium iodide at room temperature. This MAI used for block copolymerization of AAm at 60°C gave the best results in chloroform but the formation of a crosslinked product could not be ruled out in dioxane. It was inferred that for production of a linear block copolymer, homogeneous reaction mixture was required.

The resulting products were characterized by spectral studies IR and NMR, viscosity measurements. Distinct phase segregation of hydrophobic and hydrophilic blocks was evident through DSC analysis.