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61.
Garcia Ruano JL Alemparte C Martin Castro AM Adams H Rodriguez Ramos JH 《The Journal of organic chemistry》2000,65(23):7938-7943
The behavior of (Z)-3-p-tolylsulfinylacrylonitrile (1) as a chiral dienophile has been evaluated from its reactions with furan and acyclic dienes. Electrostatic interactions of the cyano group with the sulfinyl one restrict the conformational mobility around the C-S bond, thus controlling the pi-facial selectivity, which is almost complete in all cases, the approach of the diene from the less-hindered face of the dienophile (that bearing the lone electron pair) in the predominant rotamer being the favored one. The regioselectivity is also completely controlled by the cyano group. Additionally, the reactivity of compound 1 as well as its endo-selectivity are both higher than those observed for the corresponding (Z)-3-sulfinylacrylates, thus proving the potential of sulfinylnitriles as chiral dienophiles. 相似文献
62.
Richard D. Adams Dean A. Katahira John P. Selegue 《Journal of organometallic chemistry》1981,213(1):259-270
The products (μ-H)[μ-η2-(CH3)2CHNHCNCH(CH3)2]Os3(CO)10, I, and (μ-H)- [μ-η2-(CH3)2CHNHCO]Os3(CO)9[CNCH(CH3)2], II have been obtained from the reaction of H2Os3(CO)10 with diisopropylcarbodiimine. Both products have been investigated by infrared and 1H NMR spectroscopies, and by single crystal X-ray diffraction analyses. For I: Space group, P21/c, a12.840(4), b 15.724(4), c 12.638(4) Å, β 106.91(2)°, V 2441(2) Å3, Z4, ? calc 2.66 g/cc. For 2869 reflections, R 0.051 and Rw 0.052. I contains an N-hydrido, N-isopropylamidinyl ligand bridging one edge of a triangular cluster of three osmium atoms. It was apparently formed by the incorporation of one carbodiimide molecule into the coordination sphere of the cluster followed by the transfer of one hydride ligand to one of the nitrogen atoms. For II: Space group P2 1/n;a 13.936(7), b 12.146(2), c 15.509(6) Å, β 105.20(4)°, V 2533(3) Å, Z 4, ?calc 2.57 g/cc. For 3065 reflections, R 0.052 and Rw 0.057. II contains an N-hydrido, N-isopropylformamido ligand bridging one edge of a triangular cluster of three osmium atoms and an isopropylisocyanide ligand. The molecule appears to have been formed by the cleavage of an NCH(CH3)2 moeity from one carbodiimide molecule and the transfer of it together with one hydride ligand to the carbon atom of a carbonyl group. The resultant formamido ligand bridges an edge of the cluster. The remaining fragment of the carbodiimide molecule bonds to one of the metal atoms of the cluster as a terminal isocyanide ligand. When heated, I loses one mole of carbon monoxide and forms the new cluster complex (μ-H)[μ3-η2-(CH3)2CHNHCNCH-(CH3)2]Os3(CO)9 III. On the basis of electron counting schemes, III is believed to contain a triply-bridging amidinyl ligand serving as a five electron donor. Most importantly, no II was formed from I indicating that it is not a precursor -to II. A mechanism for the formation of I and II is presented and discussed. 相似文献
63.
For Part II of our ongoing study, we present a strategy for stationary phase optimization for the capillary electrochromatographic (CEC) separation of the 12 methylated benzo[a]pyrene (MBAP) isomers. Utilizing the optimum mobile phase conditions from Part I of our study as a guide, seven commercially available stationary phases have been evaluated for their ability to separate highly hydrophobic MBAP isomers. Ranging in design from high-performance liquid chromatography (HPLC) to CEC application, each phase was slurry packed in house and tested for CEC suitability and performance. Several stationary phase parameters were investigated for their effects on MBAP separation including bonding type (monomeric or polymeric, % carbon loading, surface coverage), pore size, particle size, and type of alkyl substituent. In this manner, the present state of commercially available packings has been assessed in our laboratory. Utilizing the optimum polymeric C18-5 microm-100 A-PAH stationary phase, the effects of CEC packed bed length and capillary inside diameter (I.D.) were also evaluated. A 50 microm I.D. capillary, 25 cm packed bed length and 75% (v/v) acetonitrile, 12.5 mM Tris, pH 8.0, 20 degrees C at 30 kV, provided resolution of 11 out of 12 MBAP isomers thus showing the effectiveness of CEC for analysis of structurally similar methylated polyaromatic hydrocarbons. 相似文献
64.
Zhou L Thompson R Reamer RA Miller C Welch C Ellison DK Wyvratt JM 《Journal of chromatography. A》2003,987(1-2):409-420
The possible mechanisms for the chiral recognition of 2(S)-(3,5-bis-trifluoromethyl-phenyl)-2-[3(S)-(4-fluorophenyl)-4-(1H-[1,2,4]triazol-3-ylmethyl)-morpholin-2(R)-yloxy]-ethanol (compound A) and its enantiomer with native gamma-cyclodextrin (gamma-CD) were investigated using capillary electrophoresis (CE), reversed-phase liquid chromatography (RPLC), proton (1H), fluorine (19F) and carbon (13C) nuclear magnetic resonance spectroscopy (NMR), electrospray mass spectrometry (ESI-MS) and circular dichroism (CD). All experiments provided clear evidence of the formation of diastereomeric complexes between the enantiomers and gamma-CD. Proton, fluorine and carbon NMR spectra suggested that both aromatic rings, with mono-fluoro and bis-tri-fluoro functional groups, on the guest molecule were partially included into the cavity of the gamma-CD. ESI-MS spectra indicated that the diastereomeric complexes have a 1:1 stoichiometric ratio. The binding constants of the diastereomeric complexes obtained by CE, RPLC and CD were compared. The effects of the gamma-CD concentration, organic modifiers and temperature on the CE-chiral separation were also investigated. 相似文献
65.
HPLC determination of four active saponins from Panax notoginseng in rat serum and its application to pharmacokinetic studies 总被引:1,自引:0,他引:1
Four main active saponins (ginsenosides Rg1, Rb1, Rd and notoginsenoside R1) in Panax notoginseng in rat serum after oral and intravenous administration of total saponins of P. notoginseng (PNS) to rats were determined using a simple and sensitive high-performance chromatographic method. The serum samples were pretreated with solid-phase extraction before analysis. The calibration curves for the four saponins were linear in the given concentration ranges. The intra-day and inter-day assay coefficients in serum were less than 10.0% and the recoveries of the method were higher than 80.0% in the high, middle and low concentrations. This method was applied to study the pharmacokinetics following oral and intravenous administration of PNS. 相似文献
66.
A series of di‐ and tetraamide derivatives of DOTA were synthesized, and their lanthanide(III) complexes were examined by multinuclear 1H‐, 13C‐, and 17O‐NMR spectroscopy, and compared with literature data of similar, known complexes (Table). All ligands formed structures similar to the parent [LnIII(DOTA)]? complexes, with four N‐atoms and four O‐atoms from DOTA and one O‐atom from the inner‐sphere water molecules. Interestingly, the lifetimes τM of the inner‐sphere, metal‐bound water molecules vary widely, ranging from nano‐ to milliseconds, depending on the identity of the pendent amide side chains. In general, positively charged [LnIII(DOTA‐tetraamide)]3+ complexes display the longest residence times (high τM values), while complexes with additional charged functional groups on the extended amides display much smaller τM values, even when the side groups are not directly coordinated to the central Ln3+ ions. The design of novel [LnIII(DOTA‐tetraamide)]3+ complexes with a wide, tunable range of τM values is of prime importance for the application of fast‐responding, paramagnetic chemical‐exchange‐saturation‐transfer (PARACEST) imaging agents used for the study of physiological and metabolic processes. 相似文献
67.
Mohammed A. Bari Siddiqui Shakeel Ahmed Musaed S. Al-Gharami Chistopher F. Dean 《Reaction Kinetics and Catalysis Letters》2007,91(1):61-67
Sulfur reduction ability of alumina supported zinc, gallium and zinc-gallium additives for fluid catalytic cracking catalysts
was evaluated in a micro-activity test unit (MAT). Gallium/alumina showed the highest sulfur reduction of 31%, but the cracking
activity of the catalyst was decreased. Zinc-gallium/alumina reduced sulfur in 24 wt.% without decreasing the base catalyst
activity. 相似文献
68.
Peptides represent an extensive class of biologically active molecules. They may be used as leads in the development of novel therapeutic agents provided the pharmacophoric information present within them can be translated into non-peptide analogs that lack the peptide backbone and are stable to proteolysis. This is the rationale for peptidomimetic drug design. Frequently, the -turn has been implicated as a conformation important for biological recognition of peptides. Empirical evidence from known peptidomimetics, coupled with a theoretical model of peptide binding and the observation that glycine and proline residues are common within the -turn, has suggested the design of molecules to mimic placement of between two and four of the side-chains. The moderate number of different -turn conformations, combined with the combinatoric nature of side-chain selection complicates the procedure. In this paper, cluster analysis has been used to classify the arrangement of C_ atoms about the various fragments of the -turn. Recombination of the observed patterns provides a general model for the -turn which may be used as an effective screen for potential peptidomimetic scaffolds in chemical databases. 相似文献
69.
Jamin Huang Dean F. Bushey Michael D. Graves Brenda F. Johnson Dianne D. Singleton 《Journal of heterocyclic chemistry》1987,24(1):1-7
A series of 3-substituted-5-methoxy-1,3,4-oxadiazol-2-ones were prepared from aldehydes, ketones, phenylacetic acids, and 1,2- and 1,3-diketones. Conditions for the formation of these oxadiazolones from the precursor N-carbamoyl chlorides depended on the structure, and varied from spontaneous ring closure to those requiring bases. Variation in the N-3 substituents sometimes produced mixtures of isomers which were separated and identified. These molecules were prepared in order to study the effect of the N-3 substituent variation on the biological properties of oxadiazolones. 相似文献
70.
Charles J. Colbourn Dean G. Hoffman Kevin T. Phelps Vojtěch Rödl Peter M. Winkler 《Combinatorica》1991,11(3):207-218
We prove that the number oft-wise balanced designs of ordern is asymptotically
, provided that blocks of sizet are permitted. In the process, we prove that the number oft-profiles (multisets of block sizes) is bounded below by
and above by
for constants c2>c1>0. 相似文献