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11.
Shellhamer DF Davenport KJ Forberg HK Herrick MP Jones RN Rodriguez SJ Sanabria S Trager NN Weiss RJ Heasley VL Boatz JA 《The Journal of organic chemistry》2008,73(12):4532-4538
Reactions of chlorine (Cl(2)) with 4-halo-1,1,2-trifluorobut-1-enes (1, 2, or 3) give open-ion intermediates A and E that are in equilibrium. The open-chloronium ions (E) rearrange to a five-membered-ring halonium ion during ionic chlorination of 3 when the number-4 halo-substituent is iodine. Three-membered-ring bromonium and iodonium ions from alkenes 1, 2, or 3 are rather symmetrical and similar in structure. Quantum chemical calculations show that five-membered-ring halonium ion intermediates are 11 to 27 kcal/mol more stable than the three-membered-ring halonium ions or the open-ions A and E. The five-membered-ring intermediates lead to rearranged products. Rearranged products increase as the number-4 halogen (Z) becomes more nucleophilic (Z: Cl < Br < I). Open chloronium ions from ionic chlorination of terminal fluorovinyl alkenes are compared to the open ions generated by protons to similar alkenes. 相似文献
12.
Sandra L. Gmez Carlos M. Sanabria Alirio Palma Ali Bahsas Justo Cobo Christopher Glidewell 《Acta Crystallographica. Section C, Structural Chemistry》2009,65(9):o465-o469
In (2RS,4SR)‐7‐chloro‐2‐exo‐(2‐chloro‐6‐fluorophenyl)‐2,3,4,5‐tetrahydro‐1H‐1,4‐epoxy‐1‐benzazepine, C16H12Cl2FNO, (I), molecules are linked into chains by a single C—H...π(arene) hydrogen bond. (2RS,4SR)‐2‐exo‐(2‐Chloro‐6‐fluorophenyl)‐2,3,4,5‐tetrahydro‐1H‐1,4‐epoxy‐1‐benzazepine, C16H13ClFNO, (II), is isomorphous with compound (I) but not strictly isostructural with it, as the hydrogen‐bonded chains in (II) are linked into sheets by an aromatic π–π stacking interaction. The molecules of (2RS,4SR)‐7‐methyl‐2‐exo‐(4‐methylphenyl)‐2,3,4,5‐tetrahydro‐1H‐1,4‐epoxy‐1‐benzazepine, C18H19NO, (III), are linked into sheets by a combination of C—H...N and C—H...π(arene) hydrogen bonds. (2S,4R)‐2‐exo‐(2‐Chlorophenyl)‐2,3,4,5‐tetrahydro‐1H‐1,4‐epoxy‐1‐benzazepine, C16H14ClNO, (IV), crystallizes as a single enantiomer and the molecules are linked into a three‐dimensional framework structure by a combination of one C—H...O hydrogen bond and three C—H...π(arene) hydrogen bonds. 相似文献
13.
Alessio P Ferreira DM Job AE Aroca RF Riul A Constantino CJ Gonzalez ER 《Langmuir : the ACS journal of surfaces and colloids》2008,24(9):4729-4737
The synthesis of a poly(azo)urethane by fixing CO(2) in bis-epoxide followed by a polymerization reaction with an azodiamine is presented. Since isocyanate is not used in the process, it is termed "clean method" and the polymers obtained are named "NIPUs" (non-isocyanate polyurethanes). Langmuir films were formed at the air-water interface and were characterized by surface pressure vs mean molecular area per mer unit (Pi-A) isotherms. The Langmuir monolayers were further studied by running stability tests and cycles of compression/expansion (possible hysteresis) and by varying the compression speed of the monolayer formation, the subphase temperature, and the solvents used to prepare the spreading polymer solutions. The Langmuir-Blodgett (LB) technique was used to fabricate ultrathin films of a particular polymer (PAzoU). It is possible to grow homogeneous LB films of up to 15 layers as monitored using UV-vis absorption spectroscopy. Higher number of layers can be deposited when PAzoU is mixed with stearic acid, producing mixed LB films. Fourier transform infrared (FTIR) absorption spectroscopy and Raman scattering showed that the materials do not interact chemically in the mixed LB films. The atomic force microscopy (AFM) and micro-Raman technique (optical microscopy coupled to Raman spectrograph) revealed that mixed LB films present a phase separation distinguishable at micrometer or nanometer scale. Finally, mixed and neat LB films were successfully characterized using impedance spectroscopy at different temperatures, a property that may lead to future application as temperature sensors. Principal component analysis (PCA) was used to correlate the data. 相似文献
14.
Marcolan M Martins PA Pedrosa VA Rodrigues MR de Oliveira HP Codognoto L 《Journal of fluorescence》2011,21(2):733-738
A simple, rapid and effective analytical method based on fluorescence spectroscopy for the determination of coumarin in pharmaceutical
formulations without pre-treatment or pre-concentration step was development. Coumarin had maximum excitation and emission
at 310 nm and 390 nm, respectively. Optimum conditions for the detection of coumarin were investigated. Under optimized conditions,
we observed a linear behavior for the sign of coumarin in the concentration range of 2.5 × 10−6 to 1.0 × 10−4 mol L−1, with linearity of 0.998 and sensitivity of 2.9 × 1010 u.a/mol L−1. The proposed method was validated in terms of accuracy, precision and specificity of coumarin using the standard addition
and external calibration. It was noted that the results support (P < 0.05), indicating that the matrices were not an interference in the determination of coumarin by fluorescence spectroscopy.
The results were favorable compared with those obtained by reference chromatographic methods. 相似文献
15.
16.
The water solubility of 1,3,5,7-tetra azatricyclo[3.3.1.13,7]decane, hexamethylenetetramine (HMT) or urotropine was determined at temperatures between 275.15 K and 313.15 K. Van’t Hoff graphs of ln msat versus 1/T gave three different straight lines, suggesting the existence of three different forms of the substance in the temperature region studied.
Previous work reported both increasing and decreasing solubility with temperature. This work found the solubility does not have a simple behavior. 相似文献
17.
Priscila García-Fernndez M. Santos D. García-Puente P. F. Gonzlez-Díaz 《Optics Communications》1982,40(6):451-454
By using the Laplace transform method we obtain exact analytical solutions for the time development of the photon density matrix in anti-Stokes luminescence. The cases of cooperative and sequential mechanism are separately considered. 相似文献
18.
The aim of this work is to study the effect of the preparation conditions of Ru/CeO2 catalyst (calcination temperature and/or reduction) over the performance in the partial hydrogenation of benzene reaction in the presence of TiCl3. The catalysts were prepared through chlorinated precursors by incipient wetness impregnation method. The reaction occurred in three-phase reactional medium in presence of water at 373 K and 5.0 MPa. Temperature programmed reduction (TPR) profiles of calcinated catalysts indicate the presence of oxidated ruthenium. X-ray photoelectron spectroscopy (XPS) analysis confirms this supposition, showing that the ruthenium appears in the form of RuO2 for the sample calcinated at 673 K, while for the reduced solid at 773 K, the Ru appears in the metallic state. However, the calcination step followed or not by reduction, strongly hinders the catalytic performance. In its turn, the direct reduction leads to a more active Ru/CeO2 catalysts, as well as higher cyclohexene yields throughout all the reaction. 相似文献
19.
The crystalline structure of Ca10?xSrx(AsO4)6(OH)2 has been studied, and the lattice parameters determined. It has been found that the unit cell expands with x. Geometric parameters of the unit cell, which are defined in relation to the hindered rotation of the OH group around the c axis, have been also obtained. From the ir data, the torsional potential function has been calculated in first and second approximations. A method for computing that function in any order approximation is given. A semiempirical curve is found, relating the stretching and torsional motions for both the OH and OD groups. 相似文献
20.