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31.
Mesylate derivatives of 3-aryl-3-hydroxy-beta-lactams and thiolactams react in DMSO-d(6) by first-order processes to give alcohol products. Substituent effect studies implicate carbocation intermediates (ion-pairs) that are captured by DMSO-d(6) to give transient oxosulfonium ions. Rapid reaction of the oxosulfonium ions with trace amounts of water leads to the alcohol product and regenerates DMSO-d(6). H(2)(17)O labeling studies show that (17)O is incorporated into the DMSO. The mesylate derivatives of endo- and exo-2-hydroxy-2-phenylbicyclo[2.2.1]heptan-3-one also react in DMSO-d(6) to give the alcohol products. Ion-pair intermediates that capture DMSO giving unstable oxosulfonium ions are again proposed. Exo-2-phenyl-endo-bicyclo[2.2.1]heptyl trifluoroacetate readily eliminates trifluoroacetic acid in DMSO-d(6) via a cationic mechanism involving loss of the endo-trifluoroacetate leaving group as well as an exo-hydrogen. The O-methyl oxime derivative of alpha-chloro-alpha,alpha-diphenylacetophenone reacts in DMSO-d(6) to give 1-methoxy-2,3-diphenylindole, a product derived from cyclization of a cationic intermediate. A common ion rate suppression provides further evidence for a cationic mechanism. The triflate derivative of pivaloin reacts by a cationic mechanism in DMSO-d(6) to give rearranged products. The rate is even faster than in highly ionizing solvents such as trifluoroethanol or trifluoroacetic acid. 1-Adamantyl mesylate reacts in DMSO-d(6) by a first-order process (Y(OMs) = -4.00) to give a long-lived oxosulfonium ion, 1-Ad-OS(CD(3))(2)(+), which can be characterized spectroscopically. This oxosulfonium ion reacts only slowly with water at elevated temperatures to give 1-adamantanol. DMSO is therefore a viable solvent for k(s), k(C), and k(Delta) cationic processes. 相似文献
32.
Miguel A. Vzquez Segura Josefa Donoso Francisco Muoz INS Fernandez
de
Pirola Francisco Garcia Blanco Gerardo R. Echevarria 《Photochemistry and photobiology》1993,57(Z1):923-928
Abstract— Absorption and fluorescence spectra of 5′-deoxypyridoxal (DPL) in various pure solvents and mixtures were recorded both at room temperature and over the range10–65°C. The areas under the absorption bands were analyzed to obtain the mole fraction (fN, fz) of two tautomers (the zwitterionic, Z, and neutral, N, forms) in the ground state. The following spectral parameters were determined from the fluorescence spectra: Stokes shift (Δv), fluorescence quantum yield of the neutral form (QN), fluorescence ratio of the neutral to the zwitterionic form (øN/øZ) and the rate constant of tautomerization (k1) from Z to N in the excited state. Some of these parameters (fN, Δv, QN, k1) were found to depend on the proton donor character of the solvent, whereas others (øN/øZ) depended on its dipole moment. Thus, the absorption and fluorescence spectra of DPL allow one to obtain information on the polarity and the concentration of –OH groups on its environment. 相似文献
33.
Blanco M Coello J Iturriaga H Maspoch S Pou N 《Fresenius' Journal of Analytical Chemistry》2000,368(5):534-539
A near infrared diffuse reflectance spectroscopy (NIRS) procedure for the quantitative control analysis of the active compound (otilonium bromide) in a pharmaceutical preparation in three steps of the production process (blended product, cores and coated tablets) and a methodology for its validation are proposed. The analytical procedure is composed by two consecutive steps. First, the sample is identified by comparing its spectrum with a second derivative spectral library. If the sample is positively identified, the active compound is quantified by using a previously established partial least squares (PLS) calibration model. The procedure was validated by studying repeatability, intermediate precision, accuracy and linearity. To this end, an adaptation of ICH (International Conference on Harmonisation) validation methodology to an NIR multivariate calibration procedure is proposed. The relative standard error of prediction (RSEP) was < or = 1% and the suitability of the procedure for control analysis was confirmed by the results obtained analysing new production samples produced over a three-month period. 相似文献
34.
Elizabeth P.G. Arêas José A.G. Arêas James Hamburger Warner L. Peticolas Paulo S. Santos 《Journal of colloid and interface science》1996,180(2):578
A remarkably high viscosity has been induced in protein aqueous solutions by the addition of certain structurally related organic solvents. The effect has been observed for lysozyme aqueous solutions containing tetramethylurea (TMU), dimethylsulfoxide (DMSO), dimethylformamide, and hexamethylphosphortriamide. The effect has also been induced in ferrocytochrome c aqueous solutions by TMU. Critical concentrations for both the protein and organic solvent were verified for the onset of the viscosity increase. A common feature of the solvents which were able to induce the effect is a dipolar moiety (C=O, S → O and P → O) and a nonpolar region represented by the methyl groups. The resulting fluids show an extremely restricted flow and a typical non-Newtonian, pseudoplastic behavior. Use was made of1H nuclear magnetic resonance (NMR) and Raman spectroscopy to characterize protein structural modifications and of13C NMR to investigate changes in relaxation times and chemical shifts in the solvent/water solutions. A systematic rheological characterization of the systems was undertaken for some of the solvents, and unusual patterns of viscous effects were identified for the solvent/water systems both with and without protein. The process was found to be at least partially reversible, as concluded from the recovered original solution rheological characteristics and the original protein1H NMR spectrum, after eliminating the organic solvent by ultrafiltration. The whole process was characterized as consisting of two mutually independent stages. The first involves an extensive conformational transition of the polypeptide backbone, from a predominantly α-helical to increased random coiled and β-sheet structures, with the occurrence of nonorthodox protein secondary structures at regions above the solvent critical point. The second stage consists of short-lived interchain contacts leading to an entanglement of the macromolecular system as a whole. A microphase reversion in the organic solvent/water mixture, supported by13C NMR and rheological results, is proposed as the driving force causing the observed behavior. 相似文献
35.
Jeremy P. Scott Deborah C. Hammond Elizabeth M. Beck Karel M.J. Brands Antony J. Davies Ulf-H. Dolling Derek J. Kennedy 《Tetrahedron letters》2004,45(17):3345-3348
The efficient preparation of 4-aryl-4-phenylsulfonyl cyclohexanones, containing a quaternary sulfone-bearing carbon centre, is described. Their synthesis proceeds in 38-78% overall yield by way of three steps: (i) sulfinate alkylation; (ii) methylenation; and (iii) regioselective Diels-Alder condensation with 2-trimethylsiloxybutadiene. The scope and limitations of the one-pot Mannich-type methylenation described were examined. 相似文献
36.
Elizabeth W. Baumann 《Analytica chimica acta》1978,99(2):247-253
Sulfate-selective electrodes can be fabricated from commercial platinum electrodes by coating them with a mixture of Aliquat-336 and trifluoroacetyl-p-butylbenzene in polyvinyl chloride matrix. Adding a solid, sparingly soluble sulfate such as that of strontium, lead, barium, or 2-aminoperimidine (2-AP) improves the selectivity for sulfate relative to nitrate. The 2-AP electrode shows the best physical stability and is described in detail. The order ofanion interference is ClO4->Cl->NO3->H2PO4->F-. The useful pH range is 4–9. The response is Nernstian from 10-5 to 10-1 M in sodium sulfate solutions. 相似文献
37.
Adhesive transfer of thin viscoelastic films 总被引:1,自引:0,他引:1
Shull KR Martin EF Drzal PL Hersam MC Markowitz AR McSwain RL 《Langmuir : the ACS journal of surfaces and colloids》2005,21(1):178-186
Micellar suspensions of acrylic diblock copolymers are excellent model materials for studying the adhesive transfer of viscoelastic solids. The micellar structure is maintained in films with a variety of thicknesses, giving films with a well-defined structure and viscoelastic character. Thin films were cast onto elastomeric silicone substrates from micellar suspensions in butanol, and the adhesive interactions between these coated elastomeric substrates and a rigid indenter were quantified. By controlling the adhesive properties of the film/indenter and film/substrate interfaces we were able to obtain very clean transfer of the film from the substrate to the portion of the glass indenter with which the film was in contact. Adhesive failure at the film/substrate interface occurs when the film/indenter interface is able to support an applied energy release rate that is sufficient to result in cavity nucleation at the film/substrate interface. Cavity formation is rapidly followed by delamination of the entire region under the indenter. The final stage in the transfer process involves the failure of the film that bridges the indenter and the elastomeric substrate. This film is remarkably robust and is extended to three times its original width prior to failure. Failure of this film occurs at the periphery of the indenter, giving a transferred film that conforms to the original contact area between the indenter and the coated substrate. 相似文献
38.
The presence of a micellar medium of cetylpyridinium bromide (CPB) causes, in relation to the aqueous medium, important bathochromic shifts in the excitation spectra of a considerable number of polycyclic aromatic hydrocarbons (PAHs). Furthermore, the CPB acts as a quencher, provoking inhibitions of the fluorescence intensity emitted by PAHs. The micellar inhibition factors show that, generally, the quenching affects alternant hydrocarbons to a greater extent. Some interesting relationships between the hydrocarbon structure and both the characteristic wavelengths of fluorescence spectra and the values of Deltalambda are established. 相似文献
39.
Two new ligands consisting of bis(oxime) amine units tethered by a bridge have been synthesized. Their nickel chloride and nickel nitrate complexes have also been synthesized and characterized by X-ray crystallography, FTIR, mass spectrometry, and elemental analysis. One of these ligands, L1 (N,N,N',N'-tetra(1-propan-2-onyl oxime)-diamino-m-xylene), is always dinucleating, while the other ligand, L2 (N,N,N',N'-tetra(1-propan-2-onyl-oxime)-1,3-diaminopropane), shows an unusual anion dependence on the nuclearity. When nickel chloride is used, the ligand acts in a dinucleating manner and coordinates two nickels; however, when nickel nitrate is used, the ligand acts in a monodentate fashion and coordinates only one nickel. Once the mononuclear complex is formed, it is not possible to add a second nickel if Ni(NO(3))(2) is used as the nickel source; it is possible, however, to add a second nickel if NiCl(2) is used as the nickel source. The dinuclear complex can be converted to the mononuclear one by either using silver nitrate to exchange the chloride anions for nitrates or by dissolving the complex in water. Ni(2)(L1)Cl(4)(DMF)(2).DMF: orthorhombic, P2(1)2(1)2(1), a = 12.2524(11) A, b = 16.6145(15) A, c = 20.1234(19) A, V = 4096.5(6) A(3), Z = 4. [Ni(2)(L2)Cl(4)(DMF)](2).2DMF: triclinic, P-1, a = 12.5347(5) A, b = 12.5403(5) A, c = 14.3504(6) A, alpha = 67.348(1) degrees , beta = 69.705(1) degrees , gamma = 81.549(1) degrees , V = 1952.25(14) A(3), Z = 1. Ni(L2).(NO(3))(2): monoclinic, P2(1)/n, a = 9.6738(3) A, b = 30.2229(9) A, c = 15.8238(5) A, beta = 97.995(1) degrees , V = 4581.4(2) A(3), Z = 8. 相似文献
40.
The reaction of epibromohydrin with hydroxyquinazolin-2-(1H)one derivatives. Novel oxazine formation
Mary Lou Cotter Victor Bandurco Elizabeth Wong Zoltan G. Hajos 《Journal of heterocyclic chemistry》1979,16(3):623-624
Epibromohydrin was found to react with 7-hydroxy-2-methylpyrrolo[1,2-c]quinazolin-5(6H)-one ( 4 ) in the presence of sodium hydroxide to form the novel oxazine 5 . The structure of compound 5 was proven by cmr and pmr analysis. 相似文献