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61.
Kaldor I Feldman PL Mook RA Ray JA Samano V Sefler AM Thompson JB Travis BR Boros EE 《The Journal of organic chemistry》2001,66(10):3495-3501
The quaternizations of dibenzoquinolizines 9 and 14 with 3-halo-1-propanols are highly cis-selective (94-100% cis), results consistent with the N-methylation of O-methylcapaurine (7b), but in contrast to the proposed trans-stereochemistry of dibenzo[a,h]quinolizine methiodide 10 and the analogous quaternizations of 1-benzyl- and 1-phenylisoquinoline congeners 5b and 5c. In this report, we describe stereoselective preparation of the unique cis-dibenzoquinolizinium propanols 15 and 16and their transformation into bis- and mixed-onium chlorofumarates 19, 20ab, and 26. Dibenzo[a,g]quinolizinium propanol 15 was prepared enantioselectively in three steps from dihydroisoquinoline 11. Asymmetric transfer hydrogenation of 11 in the presence of triethylamine/formic acid and Noyori's chiral ruthenium catalyst 12 produced R-(-)-5',8-dimethoxynorlaudanosine (13) in 98% yield and 87% ee. Pictet-Spengler cyclization of 13 in formalin/formic acid afforded the dibenzo[a,g]quinolizine 14 in 65% yield. Quaternization of 14 with 3-chloro-1-propanol under Finkelstein conditions generated cis-dibenzoquinolizinium propanol 15 in 85% yield with >94% cis-selectivity. The cis-dibenzo[a,h]quinolizinium propanol 16 was obtained as a single stereoisomer by reaction of the known tetramethoxyquinolizine 9 with neat 3-iodo-1-propanol. Bis-onium chlorofumarates 18 and 19 and the mixed-onium derivative 20ab were prepared by a pool synthesis procedure from (1R)-trans-6a, 16, and chlorofumaryl chloride (17). Mixed-onium alpha-chlorofumarate 26 was synthesized from (1S)-trans-6d, 15 and (+/-)-trans-2,3-dichlorosuccinic anhydride (22), employing a recently disclosed chlorofumarate mixed-diester synthesis. The title compounds (19, 20ab, and 26) displayed curare-like effects of ultrashort duration in rhesus monkeys. 相似文献
62.
The reaction of aromatic thiols with sulfur dichloride and sulfur monochloride to form the corresponding aromatic trisulfides, 2a-d, and tetrasulfides, 3a-d, has been optimized with respect to yield and purity. The use of pyridine as an amine base and the use of freshly distilled sulfur monochloride (S(2)Cl(2)) serve as important alterations to the synthetic method. Their physical properties have been characterized, revealing some discrepancies with the literature. 相似文献
63.
Streeter I Wain AJ Thompson M Compton RG 《The journal of physical chemistry. B》2005,109(25):12636-12649
An in situ electrochemical electron spin resonance (ESR) study on the electro-oxidation of para-chloroaniline, para-bromoaniline, and para-iodoaniline dissolved in acetonitrile at gold electrodes is reported. ESR spectra obtained using a tubular flow cell reveal the presence of a paramagnetic dimer product derived from para-aminodiphenylamine, during oxidative electrolysis, suggesting the coupling of reactive electrogenerated radical cations with neutral parent haloaniline molecules. The ESR signal intensity behaves in a manner expected for a radical species reacting with second-order kinetics, suggesting the paramagnetic dimer is, itself, unstable. The theory describing the ESR signal intensity flow rate behavior for this reaction mechanism is developed for the tubular arrangement and used to extract mechanistic and kinetic data from the experimental results for the cases of para-chloroaniline and para-bromoaniline. Further mechanistic aspects, including proton and halide ion expulsion during dimerization, are explored voltammetrically and with the aid of digital simulations using Digisim. Comparison of the ESR signal and voltammetric measurements suggests that an additional mechanism operates which does not lead to paramagnetic products. Additionally, the in situ electrolysis of N,N-dimethyl-para-bromoaniline is reported to generate the stable radical cation of N,N,N',N'-tetramethylbenzidine, and a mechanism of electro-oxidation is, thus, proposed. 相似文献
64.
The acidity functions of aqueous trifluoroacetic and trifluoromethanesulphonic acid mixtures, and aqueous hexafluoropropane-2, 2-diol solutions, have been determined by differential pulse polarography. The apparent shift of the half-wave potential for the ferrocene—ferricinium couple, as the solvent composition is changed, is used to indicate the change in potential of a glass electrode; acidity is measured as the HGF acidity function. The densities of two of these solvent systems as a function of composition are also reported. Trifluoromethanesulphonic acid—water mixtures represent the strongest aqueous acid solvent system so far studied. 相似文献
65.
S. H. Kim Eli M. Pearce T. K. Kwei 《Journal of polymer science. Part A, Polymer chemistry》1993,31(13):3167-3180
The precursor of polybenzimidazole (PBI), poly(3,3′-diamino-4,4′-benzidine isophthalamide) (PDABI), was synthesized from poly(3,3′-dinitro-4,4′-benzidine isophthalamide) (PDNBI) by reduction. With increasing temperature, the NH2 moiety which was protected by SnCl5?1 could cyclize and form PBI. Blends with polyamic acid (LaRC-TPI) were prepared. Clear blend films were prepared at up to 400°C. The IR spectra displayed shifts in the NH stretching band, thereby providing evidence for specific interactions related to the miscibility of their cured blends. © 1993 John Wiley & Sons, Inc. 相似文献
66.
M. D. Thompson J. S. Bradshaw S. F. Nielsen C. T. Bishop F. T. Cox P. E. Fore G. E. Maas R. M. Izatt J. J. Christensen 《Tetrahedron》1977,33(24):3313-3316
A series of macrocyclic ether-esters has been prepared by treating various glycols with adipoyl chloride and various substituted malonyl, succinyl and glutaryl chlorides. The prepared compounds include: 15-ethyl- and 15-phenyl-1,4,7,10,13-pentaoxacyclohexadecane-14,16-dione (5 and 6); 15-methyl-, 15-phenyl-, cis-cyclohexo-[o]-and benzo-[o]-1,4,7,10,13-pentaoxacycloheptadecane-14,17-dione (7–10); trans,trans-1,4,7,10,13,18,21,24,27,30-de-caoxacyclotetratriacontane-15, 32-diene-14,17,31,34-tetraone (11); 1,4,7,10,13-pentaoxacyclooctadecane-14,18-dione (12); 15,15,16,16,17,17-hexafluoro- and 16-methyl-1,4,7,10,13-pentaoxacyclooctadecane-14,18-dione (13 and 14); 1,4,7,10-tetraoxacyclohexadecane-11,16-dione (15); and 1,4,7,10,13-pentaoxacyclononadecane-14,19-dione (16). 相似文献
67.
Elena Levi Eli Lancry Yossi Gofer Doron Aurbach 《Journal of Solid State Electrochemistry》2006,10(3):176-184
A crystallographic approach was applied to elucidate the influence of the nature of the surface films on the electrochemical
behavior of Li and Mg intercalation compounds. This paper presents two examples: (1) protection of graphite electrodes by
Li2CO3 surface films, and (2) the unique electrochemical behavior of Mg-containing Chevrel phases (MgCP) obtained by different synthetic
routes. In the former case, the elucidation of the protection mechanism and the explanation of the high performance of such
protected electrodes are based on the analysis of possible Li-ion motion in the carbonate crystal structure. In the latter
case, a combination of synthesis, electrochemistry and XRD analysis was used to explain an unusual phenomenon: the difference
between the excellent electrochemical behavior of the Chevrel phase (CP) based on Cu-leached Cu2Mo6S8 (CuCP), and the poor electrochemical activity of the high-temperature synthesized MgCP, with the same phase composition.
It is shown that this phenomenon is caused by MgO formation on the surface of the latter material. The different surface chemistry
of the MgCPs obtained by the two different synthetic routes was substantiated by revealing the correlation between the electrochemical
activity and the chemical stability of these materials under ambient atmosphere conditions.
Dedicated to Prof. Mikhail A. Vorotyntsev on the occasion of his 60th birthday. 相似文献
68.
High nuclearity paramagnetic, spin-coupled transition metal clusters and grids are fascinating chemists and physicists partly because of their structural beauty, and the challenge of creating them, but also because of their novel physical properties. Magnetic interactions between the spin centers are a primary focus. This review will examine a selection of Mn(II) polynuclear grids and clusters, with nuclearities in the range Mn4 to Mn9. Theoretical treatments of the magnetic properties are discussed, and approaches to solving the exchange problem for ‘large’ spin systems related to computational difficulties. A freely available software package (MAGMUN4.1) is presented as a means of dealing simply with spin-coupled clusters in general, and symmetry reduction methods are discussed briefly as a means of dealing with ‘large’ spin systems. 相似文献
69.
Thompson WH 《The Journal of chemical physics》2004,120(17):8125-8133
The time-dependent fluorescence of a model diatomic molecule with a charge-transfer electronic transition in confined solvents has been simulated. The effect of confining the solvent is examined by comparing results for solutions contained within hydrophobic spherical cavities of varying size (radii of 10-20 angstroms). In previous work [J. Chem. Phys. 118, 6618 (2002)] it was found that the solute position in the cavity critically affects the absorption and fluorescence spectra and their dependence on cavity size. Here we examine the effect of cavity size on the time-dependent fluorescence, a common experimental probe of solvent dynamics. The present results confirm a prediction that motion of the solute in the cavity after excitation can be important in the time-dependent fluorescence. The effects of solvent density are also considered. The results are discussed in the context of interpreting time-dependent fluorescence measurements of confined solvent systems. 相似文献
70.
Current methods of analysis for ethylene oxide (EO) in medical devices include headspace and simulated-use extractions followed by gas chromatography with either a packed or a capillary column. The quantitation limits are about 0.5-1.0 microg/g for a packed column and about 0.1-0.2 microg/g for a capillary column. The current allowable levels of EO on medical devices sterilized with EO gas as outlined in International Organization for Standardization (ISO) 10993-7 may be significantly reduced from current levels by applying the ISO Draft International Standard 10993-17 method for establishing allowable limits. This may require EO test methods with detection and quantitation limits that are much lower than those of the currently available methods. This paper describes a new method that was developed for the determination of low-level EO by solid-phase microextraction using the direct-immersion method. Factors such as temperature and stirring were found to affect absorption efficiency and absorption time. A low extraction temperature (about 6 degrees C) was found to be more efficient than room-temperature extraction. Stirring was found to reduce absorption time by about 50%. Under these conditions, detection and quantitation limits of 0.002 and 0.009 microg/g, respectively, were obtained by using a capillary column. As a result, this method makes compliance with lower EO limits feasible. 相似文献