A Facile Route for the Synthesis of Novel Heterocyclic Prostaglandin F2α Analogs

A general synthetic approach has been developed for heterocyclic prostaglandins (PGF_2α type) starting from the key intermediate ( 6 ). (±) 6 was obtained from (±) ‐Corey lactone. The key intermediate (±) 6 was, in turn, converted in to several new heterocyclic prostaglandins consisting of furan and thiophene moieties in ω‐side chain in two to three steps. Horner–Wadsworth–Emmons reaction and Grignard reaction as the key reactions in these transformations.     

Structure and Bonding in Stannadiphospholes and their Dianions SnC2P2R2m (R=H,tBu m=0, −2): A Comparative Study with C5H5+ and C5H5− Analogues

The potential energy surfaces of both neutral and dianionic SnC₂P₂R₂ (R=H, tBu) ring systems have been explored at the B3PW91/LANL2DZ (Sn) and 6‐311+G* (other atoms) level. In the neutral isomers the global minimum is a nido structure in which a 1,2‐diphosphocyclobutadiene ring (1,2‐DPCB) is capped by the Sn. Interestingly, the structure established by X‐ray diffraction analysis, for R=tBu, is a 1,3‐DPCB ring capped by Sn and it is 2.4 kcal mol^?1 higher in energy than the 1,2‐DPCB ring isomer. This is possibly related to the kinetic stability of the 1,3‐DPCB ring, which might originate from the synthetic precursor ZrCp₂tBu₂C₂P₂. In the case of the dianionic isomers we observe only a 6π‐electron aromatic structure as the global minimum, similarly to the cases of our previously reported results with other types of heterodiphospholes. 1 , 4 , 19 The existence of large numbers of cluster‐type isomers in neutral and 6π‐planar structures in the dianions SnC₂P₂R₂^2? (R=H, tBu) is due to 3D aromaticity in neutral clusters and to 2D π aromaticity of the dianionic rings. Relative energies of positional isomers mainly depend on: 1) the valency and coordination number of the Sn centre, 2) individual bond strengths, and 3) the steric effect of tBu groups. A comparison of neutral stannadiphospholes with other structurally related C₅H₅⁺ analogues indicates that Sn might be a better isolobal analogue to P⁺ than to BH or CH⁺. The variation in global minima in these C₅H₅⁺ analogues is due to characteristic features such as 1) the different valencies of C, B, P and Sn, 2) the electron deficiency of B, 3) weaker pπ–pπ bonding by P and Sn atoms, and 4) the tendency of electropositive elements to donate electrons to nido clusters. Unlike the C₅H₅⁺ systems, all C₅H₅^? analogues have 6π‐planar aromatic structures as global minima. The differences in the relative ordering of the positional isomers and ligating properties are significant and depend on 1) the nature of the π orbitals involved, and 2) effective overlap of orbitals.     

The Equality Constrained Indefinite Least Squares Problem: Theory and Algorithms

We present theory and algorithms for the equality constrained indefinite least squares problem, which requires minimization of an indefinite quadratic form subject to a linear equality constraint. A generalized hyperbolic QR factorization is introduced and used in the derivation of perturbation bounds and to construct a numerical method. An alternative method is obtained by employing a generalized QR factorization in combination with a Cholesky factorization. Rounding error analysis is given to show that both methods have satisfactory numerical stability properties and numerical experiments are given for illustration. This work builds on recent work on the unconstrained indefinite least squares problem by Chandrasekaran, Gu, and Sayed and by the present authors.     

Bismuth triflate catalyzed prins‐type cyclization in ionic liquid: Synthesis of 4‐tetrahydropyranol derivatives

The reaction of aldehydes with homoallylic alcohols in the presence of catalytic amount of bismuth triflate in [bmim]PF₆generates 4‐tetrahydropyranol derivatives in excellent yield and with high diastereoselectivity. © 2008 Wiley Periodicals, Inc. Heteroatom Chem 19:104–106, 2008; Published online in Wiley InterScience ( www.interscience.wiley.com ). DOI 10.1002/hc.20403     

Synthesis,docking and ADME prediction of novel 1,2,3-triazole-tethered coumarin derivatives as potential neuroprotective agents

Research on Chemical Intermediates - In an attempt to find potential neuroprotective agents, a series of novel 3-(1-((1-(substituted phenyl)-1H-1,2,3-triazol-4-yl) methoxyimino)...     

Vinyl Sulfonate Esters: Efficient Chain Transfer Agents for the 3D Printing of Tough Photopolymers without Retardation

The formation of networks through light‐initiated radical polymerization allows little freedom for tailored network design. The resulting inhomogeneous network architectures and brittle material behavior of such glassy‐type networks limit the commercial application of photopolymers in 3D printing, biomedicine, and microelectronics. An ester‐activated vinyl sulfonate ester (EVS) is presented for the rapid formation of tailored methacrylate‐based networks. The chain transfer step induced by EVS reduces the kinetic chain length of the photopolymer, thus shifting the gel point to higher conversion, which results in reduced shrinkage stress and higher overall conversion. The resulting, more homogeneous network is responsible for the high toughness of the material. The unique property of EVS to promote nearly retardation‐free polymerization can be attributed to the fact that after the transfer step no polymerizable double bond is formed, as is usually seen in classical chain transfer agents. Laser flash photolysis, theoretical calculations, and photoreactor studies were used to elucidate the fast chain transfer reaction and exceptional regulating ability of EVS. Final photopolymer networks exhibit improved mechanical performance making EVS an outstanding candidate for the 3D printing of tough photopolymers.     

Photopolymerization of bis-aromatic and alicyclic based solid urethane acrylate macromonomer in the presence of large excess of reactive diluent

A solid urethane acrylate macromonomer with bis-aromatic as well as alicyclic moieties was synthesized and the kinetics of photopolymerization reactions were studied in the presence of varying concentration of photoinitiator and large excess of reactive diluent using photo DSC. The studies show that the rate of maximum polymerization was found to increase with increase in concentration of photoinitiator while a decrease was observed by an increase in temperature. The final conversion showed a decrease at highest isothermal condition due to vitrification. Estimation of kinetic parameters including applicability of autocatalytic and modified autocatalytic models were investigated by nonlinear regression. It was observed that the modified models gave a better fit with the experimental data and kinetic parameters showed a decrease with increase in temperature and an increase with increase in concentration of photoinitiator.     

Sensitive extractive spectrophotometric methods for the determination of trazodone hydrochloride in pharmaceutical formulations

Two simple, rapid and sensitive extractive spectrophotometric methods have been developed for the assay of trazodone hydrochloride (TRH) in pure and pharmaceutical formulations. These methods are based on the formation of chloroform soluble ion-association complexes of TRH with bromothymol blue (BTB) and with bromocresol purple (BCP) in KCl-HCl buffer of pH 2.0 (for BTB) and in NaOAc-AcOH buffer of pH of 3.6 (for BCP) with absorption maximum at 423 nm and at 408 nm for BTB and BCP, respectively. Reaction conditions were optimized to obtain the maximum color intensity. The absorbance was found to increase linearly with increase in concentration of TRH, which was corroborated by the calculated correlation coefficient values (0.9996, 0.9945). The systems obeyed Beer's law in the range of 0.2-14.5 and 0.2-14.1 microg/ml for BTB and BCP, respectively. Various analytical parameters have been evaluated and the results have been validated by statistical data. No interference was observed from common excipients present in pharmaceutical formulations. The proposed methods are simple, accurate and suitable for quality control applications.     

Solvent extraction of Hf(IV) from mixed electrolyte solutions into di-2-ethylhexylphosphoric acid (HDEHP)

Extraction of hafnium(IV) from aqueous sulfuric and sulfuric-nitric acid solutions into di-2-ethylhexylphosphoric acid (HDEHP) in xylene has been investigated. The Hf(IV) species extracted from 5M sulfuric acid was found to be HfY₂(HY₂)₂ where Y and HY₂ represent the anions of monomeric HY and dimeric H₂Y₂ forms of HDEHP, respectively. In the presence of nitrate ion the species extracted are found to be Hf(NO₃)Y(HY₂)₂ and Hf(NO₃)₂)(HY₂)₂. But when the aqueous phase is 3.0M HNO₃+2.5M H₂SO₄ only one species, Hf(NO₃)₂(HY₂)₂ was extrated. No synergism was observed from 5M H₂SO₄ by HDEHP with the addition of thenoyltrifluoracetone (HTTA).