Diphenylantimony(V) oxo/chloro carboxylates and phosphinates: crystal structures of {SbPh2Cl[O2P(C6H11)2]}2O and [SbPh2(O2CPh)2]2O

Reaction of SbPh(2)Cl(3) (1 mol) with the silver salt of dicyclohexylphosphinic acid (2 mol) afforded {SbPh(2)Cl[O2P(C6H11)(2)]}O-2 1, a similar reaction with AgO2P(C8H15)(2) gave a product formulated as {SbPh(2)Cl[O2P(C8H15)(2)]}O-2 2. Similar reactions with silver carboxylates (1:3 stoichiometry) led to the crystalline derivatives [SbPh(2)(O(2)CR)(2)]O-2 (R = Ph 3, CHPh(2) 4, 2,4,6-Me(3)C(6)H(2) 5, 2-MeC(6)H(4) 6 or 4-MeC(6)H(4) 7), whereas the 1:2 reaction afforded crystalline SbPh(2)Cl(O(2)CR)(2) (R = Ph 8, 2-MeC(6)H(4) 9 or 4-MeC(6)H(4) 10). Interconversion of the previously known compounds [SbPh(2)(O(2)CMe)(2)]O and Sb(4)Ph(8)O(6) . 3MeCO(2)H was achieved and established by H-1 NMR spectroscopy. Compounds 1 and 3 were further characterized by X-ray diffraction; the antimony in 1 is six-co-ordinated with bridging phosphinates whereas in 3 it is seven-co-ordinated with chelating benzoates. Short Sb-O (oxo) distances (1.923 Angstrom) and near linearity at the bridging ox

Chelating and bridging bis(diphenylphosphino)aniline complexes of copper(I)

The ligand bis(diphenylphosphino)aniline (dppan) has been shown to be a versatile ligand sporting different coordination modes and geometries as dictated by copper(I) and the counter ion. The molecular structures of its Cu(I) complexes were characterized by X-ray crystallography. The ligand was found in a chelating mode and monomeric complexes were formed when the ligand to copper ratio was 2: 1 and the anion was non-coordinating. However, with thiocyanate as the counter anion, the ligand was found to adopt two different modes, with one ligand chelating and the other acting as a monodentate ligand. With CuX (X = Cl, Br), dppan formed a tetrameric complex when the ligand and metal were reacted in the ratio of 1:1. But reactions containing ligand and metal in the ratios of 1: 2 or 2: 1, resulted in the formation of a mixture of species in solution. Crystallization however, led to the isolation of the tetrameric complex. Variable temperature P-31{H-1} NMR spectra of the isolated tetramers did not show the presence of chelated structures in solution. Tetra-alkylammonium salts were added to solutions of various complexes of dppan and studied by P-31{H-1} NMR to probe the effect of anions on the stability of complexes in solution. The Cu-dppan complexes were robust and did not interconvert with other structures in solution unlike the bis(diphenylphosphino) isopropylamine complexes. (C) 2011 Elsevier B.V. All rights reserved.

Role of two consecutive alpha,beta-dehydrophenylalanines in peptide structure: Crystal and molecular structure of Boc-Leu-Delta Phe-Delta Phe-Ala-Phe-NHMe

An N-alpha-protected model pentapeptide containing two consecutive Delta Phe residues, Boc-Leu-Delta Phe-Delta Phe-Ala-Phe-NHMe, has been synthesized by solution methods and fully characterized. H-1-nmr studies provided evidence for the occurrence of a significant population of a conformer having three consecutive, intramolecularly II-bonded beta-bends in solution. The solid state structure has been determined by x-ray diffraction methods. The crystals grown from aqueous methanol are orthorhombic, space group P2(1)2(1)2(1),, a = 11.503(2), b = 16.554(2), c = 22.107(3) Angstrom, V = 4209(1) Angstrom,(3) and Z = 4. The x-ray data were collected on a CAD4 diffractometer using CuKalpha radiation (lambda = 1.5418 Angstrom). The structure was determined using direct methods and refined by full-matrix least-squares procedure. The R factor is 5.3%. The molecule is characterized by a right handed 3(10)-helical conformation ((phi) = -68.2 degrees (psi) = -26.3 degrees), which is made up of two consecutive type III beta-bends and one type I beta-bend. In the solid state the helical molecules are aligned head-to-tail, thus forming long rod like structures. A comparison with other peptide structures containing consecutive Delta Phe residues is also provided. The present study confirms that the -Delta Phe-Delta Phe-sequence can be accommodated in helical structures. (C) 1997 John Wiley & Sons, Inc.

Synthesis and characterization of N,N'-aliphatic dicarboxylbis(hydrazones)

N,N'-Malonylbis-,N,N'-adipinylbis- and N,N'-sebacoylbis-(hydrazones) 1 of various aldehydes and ketones have been prepared and characterized by elemental analyses, melting points, and H-1 NMR and IR spectral data.

Synthesis and structures of oxyanion encapsulated copper(I)-dppm complexes (dppm = bis(diphenylphosphino) methane)

Copper(I)-dppm complexes encapsulating the oxyanions ClO4-, NO3-, CH3C6H4CO2-, SO42-, and WO42- have been synthesized either by reduction of the corresponding Cu(II) salts and treatment with dppm, or by treating the complex [Cu-2(dppm)(2)(dmcn)(3)](BF4)(2) (1) (dmcn = dimethyl cyanamide) with the respective anion. The isolated complexes [Cu-2(dppm)(2)(dmcn)(2)(ClO4)] (ClO4) (2), [Cu-2(dppm)(2)(dmcn)(2)(NO3)] (NO3) (3), Cu-2(dppm)(2)(NO3)(2) (4), [Cu-2(dppm)(2)(CH3C6H4CO2)(2)]dmcn.2THF (5), Cu-2(dppm)(2)(SO4) (6), and [Cu-3(dppm)(3)(Cl)(WO4)] 0.5H(2)O (7) have been characterized by IR, H-1 and P-31{H-1} NMR, UV-vis, and emission spectroscopy. The solid-state molecular structure of complexes 1, 2, 4, and 7 were determined by single-crystal X-ray diffraction. Pertinent crystal data are as follows: for 1, monoclinic P2(1)/c, a = 11.376(10) Angstrom, b = 42.503(7) Angstrom, c = 13.530(6) Angstrom, beta = 108.08(2)degrees, V = 6219(3) Angstrom(3), Z = 4; for 2, monoclinic P2(1)/c, a = 21.600(3) Angstrom, b = 12.968(3) Angstrom, c = 23.050(3) Angstrom, beta = 115.97(2)degrees, V = 5804(17) Angstrom(3), Z = 4; for 4, triclinic , a = 10.560(4) Angstrom, b = 10.553(3) Angstrom, c = 22.698(3) Angstrom, alpha = 96.08(2)degrees, beta = 96.03(2)degrees, gamma = 108.31(2)degrees, V = 2362(12) Angstrom(3), Z = 2; and for 7, orthorhombic P2(1)2(1)2(1), a = 14.407(4) Angstrom, b = 20.573(7) Angstrom, c = 24.176(6) Angstrom, V = 7166(4) Angstrom(3), Z = 4. Analyses of the crystallographic and spectroscopic data of these complexes reveal the nature of interactions between the Cu-I-dppm core and oxyanion. The anchoring of the oxyanion to the Cu-n(dppm)(n) unit is primarily through coordination to the metal, but the noncovalent C-H ... O interactions between the methylene and phenyl protons of the dppm and oxygen atoms of the oxyanion play a significant role. The solid-state emission spectra for complexes 1-6 are very similar but different from 7. In CDCl3 solution, addition of ClO4- or NO3- (as their tetrabutylammonium salts) to 1 establishes a rapid equilibrium between the anion-complexed and uncomplexed forms. The association constant values for ClO4- and NO3- have been estimated from the P-31{H-1} NMR spectra.

Synthesis and vesicle formation from dimeric pseudoglyceryl lipids with (CH2)(m) spacers: pronounced m-value dependence of thermal properties, vesicle fusion, and cholesterol complexation

Eight new dimeric lipids, in which the two Me2N+ ion headgroups are separated by a variable number of polymethylene units [-(CH2)(m)-], have been synthesized. The electron micrograph (TEM) and dynamic light scattering (DLS) of their aqueous dispersions confirmed the formation of vesicular-type aggregates. The vesicle sizes and morphologies were found to depend strongly on the m value, the method, and thermal history of the vesicle preparation. Information on the thermotropic properties of the resulting vesicles was obtained from microcalorimetry and temperature-dependent fluorescence anisotropy measurements. Interestingly, the T-m values for these vesicles revealed a nonlinear dependence on spacer chain length (m value). These vesicles were able to entrap riboflavin. The rates of permeation of the OH- ion under an imposed transmembrane pH gradient were also found to depend significantly on the m value. X-Ray diffraction of the cast films of the lipid dispersions elucidated the nature and the thickness of these membrane organizations, and it was revealed that these lipids organize in three different ways depending on the m value. The EPR spin-probe method with the doxylstearic acids 5NS, 12NS, and 16NS, spin-labeled at various positions of stearic acid, was used to establish, the chain-flexibility gradient and homogeneity of these bilayer assemblies. The apparent fusogenic propensities of these bipolar tetraether lipids were investigated in the presence of Na2SO4 with fluorescence-resonance energy-transfer fusion assay. Small unilamellar vesicles formed from 1 and three representative biscationic lipids were also studied with fluorescence anisotropy and H-1 NMR spectroscopic techniques in the absence and the presence of varying amounts of cholesterol.

Synthesis and Degradation of Sorbitol-Based Polymers

A new class of biodegradable copolyesters was synthesized by the catalyst-free melt condensation of sorbitol with citric acid, tartaric acid, and sebacic acid. The resulting polymers were designated as poly(sorbitol citric sebacate) p(SCS)] and poly(sorbitol tartaric sebacate) p(STS)]. The synthesized polymers were characterized by Fourier transform infrared spectroscopy, H-1-NMR spectroscopy, and differential scanning calorimetry analysis. Porous spongelike scaffolds were prepared with a salt-leaching technique and characterized with scanning electron microscopy. Tensile testing of the p(SCS) and p(STS) polymers showed that they exhibited a wide range of mechanical properties. The Young's modulus and tensile strengths of the polymers ranged from 1.06 +/- 0.12 to 462.65 +/- 34.21 MPa and from 0.45 +/- 0.04 to 20.32 +/- 2.54 MPa, respectively. In vitro degradation studies were performed on disc-shaped polymer samples. The half-life of the polymers ranged from 0.54 to 38.52 days. The percentage hydration of the polymers was in the range 9.36 +/- 1.26 to 78.25 +/- 1.91, with sol contents of 2-14%. At any given polymer composition, the Young's modulus and tensile strength of p(SCS) was higher than that of p(STS), whereas the degradation rates of p(SCS) was lower than that of p(STS). This was attributed to the structural difference between the citric and tartaric monomers and to the degree of crosslinking. (C) 2011 Wiley Periodicals, Inc. J Appl Polym Sci 121: 2861-2869, 2011

Synthesis, properties, and comparative analyses on the chain flexibility of an ultrastable vinyl polyperoxide

The most stable vinyl polyperoxide, namely, poly(indene peroxide) (PINDP), an alternating copolymer of indene and oxygen, was synthesized by the oxidative polymerization of indene. It was characterized by H-1-NMR and C-13-NMR, Fourier transform infrared, differential scanning calorimetry, direct pyrolysis mass spectrometry, and gas chromatography mass spectrometry studies. The overall activation energy for the degradation and the glass-transition temperature of PINDP were 47 kcal/mol and 327 K respectively, which were very high compared to those of other vinyl polyperoxides. (C) 2002 Wiley Periodicals, Inc.

A new polymeric flame retardant additive for vinyl polymers

Diethyl allyl phosphate (DEAP) monomer has been synthesized, and characterized, using H-1 NMR and direct ionization mass spectrometric (DI-MS) techniques. It was free-radically polymerized to yield the poly(diethyl allyl phosphate) (PDEAP). The direct pyrolysis-mass spectrometric (DP-MS) analysis of the PDEAP revealed that it undergoes thermal degradation to yield mainly the monomer. Utility of PDEAP as a potent flame-retardant additive in polystyrene (PS) and poly(methyl methacrylate) (PMMA) has also been established.

Synthesis, X-ray crystal structure, DNA binding, antioxidant and cytotoxicity studies of Ni(II) and Pd(II) thiosemicarbazone complexes

New complexes, [Ni(HL)(PPh3)]Cl (1), [Pd(L)(PPh3)](2), and [Pd(L)(AsPh3)](3), were synthesized from the reactions of 4-chloro-5-methyl-salicylaldehyde thiosemicarbazone [H2L] with [NiCl2(PPh3)(2)], [PdCl2(PPh3)(2)] and [PdCl2(AsPh3)(2)]. They were characterized by IR, electronic, H-1-NMR spectral data. Further, the structures of the complexes have been determined by single crystal X-ray diffraction. While the thiosemicarbazone coordinated as binegative tridentate (ONS) in complexes 2 and 3, it is coordinated as mono negative tridentate (ONS) in 1. The interactions of the new complexes with calf thymus DNA was examined by absorption and emission spectra, and viscosity measurements. Moreover, the antioxidant properties of the new complexes have also been tested against DPPH radical in which complex 1 exhibited better activity than that of the other two complexes 2 and 3. The in vitro cytotoxicity of complexes 1-3 against A549 and HepG2 cell lines was assayed, and the new complexes exhibited higher cytotoxic activity with lower IC50 values indicating their efficiency in killing the cancer cells even at very low concentrations.

Design, synthesis of some new (2-aminothiazol-4-yl)methylester derivatives as possible antimicrobial and antitubercular agents

A series of (2-aminothiazol-4-yl)methylester (5a-t) derivatives were synthesized in good yields and characterized by H-1 NMR, C-13 NMR, mass spectral and elemental analyses. The crystal structure of 5a was evidenced by X-ray diffraction study. The compounds were evaluated for their preliminary in vitro antibacterial, antifungal activity and were screened for antitubercular activity against Mycobacterium tuberculosis H37Rv strain. The synthesized compounds displayed interesting antimicrobial activity. (C) 2012 Elsevier Masson SAS. All rights reserved.

Homo- or Heterosynthon? A Crystallographic Study on a Series of New Cocrystals Derived from Pyrazinecarboxamide and Various Carboxylic Acids Equipped with Additional Hydrogen Bonding Sites

Four new cocrystals of a well studied active pharmaceutical ingredient (API), namely, pyrazinecarboxamide (PZA), with various monocarboxylic acids equipped with additional hydrogen bonding sites such as vanillic acid (VA), gallic acid (GA), 1-hydroxy-2-naphthoic acid (1HNA), and indole-2-carboxylic acid (I2CA) have been successfully prepared and characterized by FTIR, H-1 NMR, differential scanning calorimetry (DSC), and single crystal and powder X-ray diffraction (SXRD and PXRD, respectively) techniques. In the majority of the cases, preferential occurrence amide amide and acid acid homosynthons has been observed. Since the heterosynthon is energetically preferred to homosynthon, such unusual occurrence of homosynthon in these cocrystals is intriguing.

Thermal degradation kinetics of thermoresponsive poly(N-isopropylacrylamide-co-N,N-dimethylacrylamide) copolymers prepared via RAFT polymerization

Reversible addition-fragmentation chain transfer polymerization at 70 A degrees C in N,N-dimethylformamide was used to prepare poly(N-isopropylacrylamide-co-N,N-dimethylacrylamide) copolymers in various compositions to afford well-defined polymers with pre-determined molecular weight, narrow molecular weight distribution, and precise chain end structure. The copolymer compositions were determined by H-1 NMR spectroscopy. The reactivity ratios of N-isopropylacrylamide (NIPAM) and N,N-dimethylacrylamide (DMA) were calculated as r (NIPAM) = 0.838 and r (DMA) = 1.105, respectively, by the extended Kelen-Tudos method at high conversions. The lower critical solution temperature of PNIPAM can be altered by changing the DMA content in the copolymer chain. Differential scanning calorimetry and thermogravimetric analysis at different heating rates were carried out on these copolymers to understand the nature of thermal degradation and to determine its kinetics. Different kinetic models were applied to estimate various parameters like the activation energy, the order, and the frequency factor. These studies are important to understand the solid state polymer degradation of N-alkyl substituted polymers, which show great potential in the preparation of miscible polymer blends due to their ability to interact through hydrogen bonding.

Dual Role of Acetate as a Nucleophile and as an Internal Base in Cycloplatination Reaction of sym-N,N `,N `'-Triarylguanidines

Reaction of cis-Cl2Pt(S(O)Me-2)(2)] with 1 equiv of sym-N,N',N `'-triarylguanidines, ArN=C(NHAr)(2) (sym = symmetrical; Ar = 2-MeC6H4 (LH22-tolyl), 2-(MeO)C6H4 (LH22-anisyl), 4-MeC6H4 (LH24-tolyl), 2,5-Me2C6H3 (LH22,5-xylyl), and 2,6-Me2C6H3 (LH22,6-xylyl)) in toluene under reflux condition for 3 h afforded cis- or trans-Cl2Pt(S(O)Me-2)(ArN=C(NHAr)(2))] (Ar = 2-MeC6H4 (1), 2-(MeO)C6H4 (2), 4-MeC6H4 (3), 2,5-h Me2C6H3 (4), and 2,6-Me2C6H3 (5), respectively) in 83-96% yield. Reaction of cis-Cl2Pt(S(O)Me-2)(2)] with 1 equiv of LH22-tolyl and LH24-tolyl in the presence of 1 equiv of NaOAc in methanol under reflux condition for 3 h afforded acetate-substituted products, cis-(AcO)ClPt(S(O)Me-2)(ArN=C(NHAr)(2))] (Ar = 2-MeC6H4 (6) and 4-MeC6H4 (7)) in 83% and 84% yields, respectively. Reaction of cis-Cl2Pt(S(O)Me-2)(2)] with 1 equiv of LH22-anisyl and LH22-tolyl in the presence of 1 equiv of NaOAc in methanol under reflux condition for 3 and 12 h afforded six-membered C,N] platinacycles, Pt{kappa(2)(C,N)-C6H3R-3(NHC(NHAr)(=NAr))-2}Cl(S(O)Me-2)] (Ar = 2-RC6H4; R = OMe (8) and Me (9)), in 92% and 79% yields, respectively. The new complexes have been characterized by analytical and spectroscopic techniques, and further the molecular structures of 1, 2, 4, 5, 6, and 8 have been determined by single-crystal X-ray diffraction. The platinum atom in 1, 4, and 5 exhibited the trans configuration, while that in 2, 6, and 8 exhibited the cis configuration. Complex 6 is shown to be the precursor for 9, and the former is suggested to transform to the latter possibly via an intramolecular C-H activation followed by elimination of AcOH. The solution behavior of new complexes has been studied by multinuclear NMR (H-1, Pt-195, and C-13) spectroscopy. The new complexes exist exclusively as a single isomer (trans (1 and 5) and cis (6 and 7)), a mixture of cis and trans isomers with the former isomer being predominant in the case of 2 and the latter isomer being predominant in the case of 3. Complex 5 in the trans form revealed the presence of one isomer at 0.007 mM concentration and two isomers in about 1.00:0.12 ratio at 0.154 mM concentration as revealed by H-1 NMR spectroscopy, and this has been ascribed to the restricted Pt-S bond rotation at higher concentration. Platinacycle 8 exists as one isomer, while 9 exists as a mixture of seven isomers in solution. The influence of steric factor, pi-acceptor property of the guanidine, subtle solid-state packing forces upon the configuration of the platinum atom, and the number of isomers in solution have been outlined. Factors that accelerate or slow down the cycloplatination reaction, the role of NaOAc, and a plausible mechanism of this reaction have been discussed.

Discrimination of alpha-Amino Acids Using Green Tea Flavonoid (-)-Epigallocatechin Gallate as a Chiral Solvating Agent

We report a special, hitherto-unexplored property of (-)-epigallocatechin gallate (EGCG) as a chiral solvating agent for enantiodiscrimination of alpha-amino acids in the polar solvent DMSO. This phenomenon has been investigated by H-1 NMR spectroscopy. The mechanism of the interaction property of EGCG with alpha-amino acids has been understood as arising out of hydrogen-bonded noncovalent interactions, where the -OH groups of two phenyl rings of EGCG play dominant roles. The conversion of the enantiomeric mixture into diastereomers yielded well-resolved peaks for D and L amino acids permitting the precise measurement of enantiomeric composition. Often one encounters complex situations when the spectra are severely overlapped or partially resolved hampering the testing of enantiopurity and the precise measurement of enantiomeric excess (ee). Though higher concentration of EGCG yielded better discrimination, the use of lower concentration being economical, we have exploited an appropriate 2D NMR experiment in overcoming such problems. Thus, in the present study we have successfully demonstrated the utility of the bioflavonoid (-)-EGCG, a natural product as a chiral solvating agent for the discrimination of large number of alpha-amino acids in a polar solvent DMSO. Another significant advantage of this new chiral sensing agent is that it is a natural product and does not require tedious multistep synthesis unlike many other chiral auxiliaries.