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51.
Synthesis and Absolute Configuration of Clemastine and its Isomers. Condensation of 4-chloro-α-methylbenzhydrylalkohol ( 1 ) with 2-(2-chloroethyl)-1-methylpyrrolidine ( 2 ) gave an isomeric mixture of 2-[2-(p-chloro-α-methyl-=-phenylbenzyloxy)ethyl]-1-methylpyrrolidine ( 3 ) and 4-(p-chloro-=-phenylbenzyloxy)-1-methyl-hexahydroazepin ( 4 ). The separation of the four possible optically active isomers of 3 is described and their absolute configuration established by degradation to (R)- and (S)-1-methyl-2-pyrrolidineethanol ( 6 ), respectively, and by an X-ray cristallographic analysis of the quarternary methiodide of the isomer 3-A . Clemastine (3-A) is (+)-(2R)-2-[2-((αR)-(p-chloro-α-methyl-α-phenylbenzyloxy)ethyl)]-1-methylpyrrolidine. 相似文献
52.
In spite of the higher reactivity of styrene with respect to ethene for the alternating copolymerization with carbon monoxide, catalyzed by chiral (dihydrooxazole)(phosphino)palladium complexes, ethene is preferentially (and randomly) enchained in terpolymerization experiments; enantioface selection for styrene is comparably high in both copolymerization and terpolymerization processes. 相似文献
53.
Kolen'ko YV Kovnir KA Gavrilov AI Garshev AV Meskin PE Churagulov BR Bouchard M Colbeau-Justin C Lebedev OI Van Tendeloo G Yoshimura M 《The journal of physical chemistry. B》2005,109(43):20303-20309
Mesoporous nanosized TiO2 and Zn(x)Ti(1-x)O(2-x) solid solution having a Zn content below 10 mol % with a particles size between 13 and 17 nm are prepared by a template-free sol-gel method followed by high-temperature supercritical drying in 2-propanol. The structural, textural, and electronic properties of the obtained nanomaterials are methodically investigated by using XRD, SEM, TEM, ED, HREM, EDX, ICP-OES, N(2) adsorption-desorption, Raman spectroscopy, and diffuse reflectance UV-vis spectroscopy. It is shown that the proposed synthesis technique leads to the formation of a Zn(x)Ti(1-x)O(2-x) solid solution based on the anatase crystal structure rather than a two-phase sample. High-resolution electron microscopy and electron diffraction indicate that the distribution of zinc atoms over the anatase structure does not lead to a considerable deformation of the crystal structure. 相似文献
54.
Alex Berlin Neil Gilkes Douglas Kilburn Vera Maximenko Renata Bura Alexander Markov Anton Skomarovsky Alexander Gusakov Arkady Sinitsyn Oleg Okunev Irina Solovieva John N. Saddler 《Applied biochemistry and biotechnology》2006,130(1-3):528-545
Seven cellulase preparations from Penicillium and Trichoderma spp. were evaluated for their ability to hydrolyze the cellulose fraction of hardwoods (yellow poplar and red maple) pretreated by organosolv extraction, as well as model cellulosic substrates such as filter paper. There was no significant correlation among hydrolytic performance on pretreated hardwood, based on glucose release, and filter paper activity. However, performance on pretreated hardwood showed significant correlations to the levels of endogenous β-glucosidase and xylanase activities in the cellulase preparation. Accordingly, differences in performance were reduced or eliminated following supplementation with a crude β-glucosidase preparation containing both activities. These results complement a previous investigation using softwoods pretreated by either organosolv extraction or steam explosion. Cellulase preparations that performed best on hardwood also showed superior performance on the softwood substrates. 相似文献
55.
Ibrahim Y Alsharaeh E Dias K Meot-Ner Mautner M El-Shall MS 《Journal of the American Chemical Society》2004,126(40):12766-12767
We studied the stepwise hydration and solvent-mediated deprotonation of the benzene*+ cation (Bz*+) and found several unusual features. The solvent binding energies DeltaH on-1,n for the reactions Bz*+(H2O)n-1 + H2O --> Bz*+(H2O)n are nearly constant at 9 +/- 1 kcal mol-1 for n = 1 to 8. We observed a remarkable sudden decrease in the entropy of association accompanying the formation of Bz*+(H2O)7 and Bz*+(H2O)8, indicating strong orientational restraint in the hydration shells of these clusters consistent with the formation of cagelike structures. We observed the size-dependent deprotonation of Bz*+ in a cooperative multibody process, where n H2O molecules (n >/= 4) can remove a proton from Bz*+ to form protonated water clusters. We measured, for the first time, the temperature dependence of such a process and found a negative temperature coefficient of a magnitude unprecedented in any chemical reaction, of the form k = AT-67+/- 4, or in an Arrhenius form having an activation energy of -34 +/- 1 kcal mol-1. The temperature effect may be explained by Bz*+ and four H2O molecules needing to be assembled from gas-phase components to form the reactive species. Such large temperature effects may be therefore general in solvent cluster-mediated reactions. 相似文献
56.
Uwe Klingebiel Dieter Bentmann Anton Meller 《Monatshefte für Chemie / Chemical Monthly》1978,109(5):1067-1073
Aminofluorosilanes react with lithiated amines undergoing LiF-elimination and substitution (1). The acyclic silicon-nitrogen-compound2 is isolated in the reaction with a difluorosilane after renewed lithiation.2 is cyclisated in the reaction with butyllithium by butane- and LiF-elimination (3). Aminofluorosilanes with bulky (4) or mesomeric stabilized (5) ligands form stable lithioaminofluorosilanes, which react with fluorosilanes giving substitution products (6, 7).6 and7 react with the lithium salt oftert-butylamin in a molar ratio of 12 to give8 and9 by intramolecular cyclisation.—The mass,1H and19F nmr spectra of the compounds are reported. 相似文献
57.
Summary Betaine borate undergoes a phase transition of strongly second order at 142.5 K. Crystals below this temperature belong to the ferroelastic Aizu species mmmF2/m. The crystal structures of both phases have been determined. Paraelastic phase: Pmcn,a=7.769(1),b=9.873(2),c=11.974(2)Å,Z=4,T=293K,R=0.041 for 519 unique observed reflections. Ferroelastic phase: P21/c,a=7.615(5),b=9.872(3),c=11.947(5)Å, =92.98(8)°,Z=4,T=130K,R=0.083 for 507 unique observed reflections. In both structures the betaine molecules are connected to B(OH)3-groups via hydrogen bonds to form chains running parallel[001]. These chains are associated to each other by van der Waals forces. 相似文献
58.
This article is concerned with the oscillatory properties of the eigenfunctions of a class of singular Sturm—Liouville problems—(p y)+q y=w y on (a, b), where the weight functionw vanishes on a subinterval of positive measure, or where the weight functionw changes sign on (a, b).This work was supported by the Applied Mathematical Sciences Research Program (KC-04-02) of the Office of Energy Research of the U.S. Department of Energy under Contract W-31-109-Eng-38. 相似文献
59.
A mixed ligand 12 complex of copper(II) azide with 3,5-lutidine, namely di-(1,1)-azido-di(0,0)-nitrato)tetrakis(3,5-lutidine)dicopper(II) has been prepared and characterized by X-ray crystallographic and spectroscopic methods. The dimeric molecule, which possesses a crystallographic inversion center, contains two(1,1) bridging azido ligands. Each copper(II) atom in the cyclic Cu2N2 unit is further coordinated by two oxygen atoms from two(0,0-nitrato) bridges at Cu-O distances of 2.465(3) and 2.568(3) Å and two nitrogen atoms from the lutidine molecules [Cu-N=2.003(3) and 2.012(3) Å] to give a distorted tetragonal bipyramid. Both azido ligands are linear [N-N-N angle=179.0(4) and asymmetric N-N=1.207(4) and N-N=1.135(5) Å]. The azido bridges produce a rather short Cu Cu distance of 3.013(2) Å. Infrared and electronic data are presented and discussed. 相似文献
60.
Within the resolution of the identity (RI) method, the convergence of the Hartree-Fock (HF) total molecular energy and the multipole moments in the course of the combined regular expansion of the molecular and auxiliary (RI) basis sets is studied. Dunning's cc-pVXZ series is used for both the molecular and the RI basis sets. The results show the calculated quantities converge to the HF limit when both the molecular and the RI basis sets are expanded from correlation-consistent polarized valence double zeta to correlation-consistent polarized valence sextuple zeta. Combinations of molecular/RI basis sets sufficient for convergence of the total energy and of the multipole moments at various accuracy levels have been determined. A measure of the RI basis set incompleteness is suggested and discussed. As it is significantly faster than the standard HF algorithm for small and midsize molecules, the RI-HF method, together with appropriate expanding series of both molecular and RI basis sets, provide an efficient tool to estimate and control the error of the Hartree-Fock calculations due to the finite basis set. 相似文献