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991.
992.
A new one-pot Bischler–Napeiralski type cyclization reaction between pyridine-1,2-diamines and various carboxylic acids with
PPA as catalyst to prepare pyridobenzodiazepines is proposed. In the new synthetic route, the reaction time is only one-third
of the methods reported. The synthetic strategy provides an efficient way to prepare novel structurally diversified heterocyclic
compounds of pyridobenzodiazepine family with potential pharmaceutical or biological activities. 相似文献
993.
Two new noncentrosymmetric (NCS) solids were isolated via high-temperature, salt-inclusion reactions, Cs(2)Cu(7)(P(2)O(7))(4).6CsCl (1, CU-9) and Cs(2)Cu(5)(P(2)O(7))(3).3CsCl (2, CU-11). These copper(II) phosphates exhibit novel open-framework structures conceptually templated by extended Cs-Cl salt. The latter resides cooperatively in the channels upon the formation of the NCS Cu-P-O frameworks, leading to the formation of fascinating salt lattices centered by the NaCl-type core. These new discoveries are significant for they may give rise to a new route for the templated synthesis of NCS solids. We are to show here the structural correlation of the newly discovered hybrid solids, and the role of the chlorine atoms in the "intergrowth" of covalent/ionic sublattices. 相似文献
994.
Sun Q Tafesse L Limberis JT Islam K Kyle DJ 《Combinatorial chemistry & high throughput screening》2003,6(5):481-488
A biased chemical library containing 91 differentially substituted thiazolidinones was prepared in an effort to improve the pharmacology of a known anticonvulsant agent V102862. The collection was prepared in a single step multi-component condensation reaction that produced good yields and very high crude purity (75%-85%). Seven compounds, identified within the library were shown to be more potent than V102862, our parent reference compound, in an electrophysiological assay measuring sodium channel antagonism. The most potent compound, 3-(2-piperidinylethyl)-2-(3-(3-trifluoromethylphenoxy)phenyl)thiazolidinone, has a Ki of 90 nM. 相似文献
995.
Tamotsu Takahashi Masanori Ishikawa Shoquan Huo 《Journal of the American Chemical Society》2002,124(3):388-389
Reactions of zirconacyclopentadienes with dichlorocarbene afforded cyclopropanation products in good yields. In a similar manner, reactions of zirconacyclopentadienes with a Simmons-Smith type cyclopropanation reagent also gave vinylcyclopropanes in good yields after hydrolysis. Before hydrolysis, the formation of 1-zirconabicyclo[3.1.0]hexene was observed by 13C NMR spectroscopy. The 1-zirconabicyclo[3.1.0]hexene deriatives reacted with CO to produce 1,2,3,5-tetrasubstituted benzene derivatives in good yields via the C-C bond cleavage of the cyclopropane rings. This is in sharp contrast to the formation of usual 1,2,3,4-tetrasubstituted benzene derivatives from zirconacyclopentadienes. 相似文献
996.
Cell-surface carbohydrates are classified by the nature of their linkages to the protein as either N-linked or O-linked. O- and N-glycans are involved in a number of important biological functions. These activities can be lost on glycoprotein catabolism when these glycan linkages are enzymatically hydrolyzed. The design and synthesis of novel C-linked glycans should provide catabolically stable glycoproteins useful for understanding and regulating important biological processes. Our efforts are currently directed toward the synthesis of C-glycosides of ulosonic acids. This paper describes the first synthesis of a serine-based neuraminic acid C-glycoside. The protecting group chemistry required for both carbohydrate and peptide syntheses complicates this approach. Different protecting group strategies were investigated for use in the samarium diiodide mediated C-glycosylation reaction. The key elements of our synthetic approach involve the following: (i) the substitution of homoserine for serine in the C-glycosylation reaction to introduce a carbon in place of the O-glycosidic oxygen, (ii) the use of benzyloxycarbonyl as a homoserine protecting group, compatible with samarium diiodide mediated C-glycosylation reaction, and (iii) the reduction of the carbonyl group in homoserine early in the synthesis to improve C-glycosylation yield and to avoid lactone formation. Using this combined approach, we prepared 4-O-acetyl-4-[2-C-(1-methyl 5-acetamido 4,7,8,9-tetra-O-acetyl-2,6-anhydro-3,5-dideoxy-d-erythro-l-manno-nononate)]-2S-(benzyloxycarbonyl)amino-1-carboxylic acid (1), which will be used in peptide synthesis to prepare glycopeptides containing catabolically stable C-linked neuraminic acid. 相似文献
997.
The composition of the Peugeot automobile bumper was studied by using DSC. The effects on the DSC curve of quenching from the melt, heating rate, cooling rate, partial scanning, and partial scanning isothermal scanning were studied. The experimental results indicate that the sample is a blend of two polymers and it is identified as a blend of PP and HDPE by Barta's additive thermal analytical method and IR spectroscopy. A set of methods to determine the composition of polymeric materials is created by using DSC.
Zusammenfassung Mittels DSC wurde die Zusammensetzung von Peugeout KfzStoßstangen untersucht. Der Einfluß von Abschrecken aus der Schmelze, von Aufheizgeschwindigkeit, Kühlgeschwindigkeit, partiellem Scanning und partiellem Scanning isothermem Scanning auf den Verlauf der DSC-Kurve wurde untersucht. Die experimentellen Daten ergaben ein Gemisch aus zwei Polymeren, das mit Hilfe des additiven thermischen Analysenverfahrens nach Barta und mittels IR-Spektroskopie als ein Gemisch aus PP und HDPE identifiziert werden konnte. Eine Reihe von Verfahren zur Bestimmung der Zusammensetzung polymerer Materialien unter Anwendung von DSC wurde ausgearbeitet.相似文献
998.
n—Butyl Pyridinium Nitrate as a Reusable Ionic Liquid Medium for Knoevenagel Condensation 总被引:9,自引:0,他引:9
YiQunLI XinMingXU MeiYunZHOU 《中国化学快报》2003,14(5):448-450
The Knoevenagel condensation of carbonyl substrates with active methylenecompounds proceeds smoothly with ammonium acetate as catalyst in n-butyl pyridinium nitrate to afford the desired products of good purity in moderate yields. 相似文献
999.
Tang Q Carrington PE Horng YC Maroney MJ Ragsdale SW Bocian DF 《Journal of the American Chemical Society》2002,124(44):13242-13256
Methyl-coenzyme M reductase (MCR) catalyzes methane formation from methyl-coenzyme M (methyl-SCoM) and N-7-mercaptoheptanoylthreonine phosphate (CoBSH). MCR contains a nickel hydrocorphin cofactor at its active site, called cofactor F(430). Here we present evidence that the macrocyclic ligand participates in the redox chemistry involved in catalysis. The active form of MCR, the red1 state, is generated by reducing another spectroscopically distinct form called ox1 with titanium(III) citrate. Previous electron paramagnetic resonance (EPR) and (14)N electron nuclear double resonance (ENDOR) studies indicate that both the ox1 and red1 states are best described as formally Ni(I) species on the basis of the character of the orbital containing the spin in the two EPR-active species. Herein, X-ray absorption spectroscopic (XAS) and resonance Raman (RR) studies are reported for the inactive (EPR-silent) forms and the red1 and ox1 states of MCR. RR spectra are also reported for isolated cofactor F(430) in the reduced, resting, and oxidized states; selected RR data are reported for the (15)N and (64)Ni isotopomers of the cofactor, both in the intact enzyme and in solution. Small Ni K-edge energy shifts indicate that minimal electron density changes occur at the Ni center during redox cycling of the enzyme. Titrations with Ti(III) indicate a 3-electron reduction of free cofactor F(430) to generate a stable Ni(I) state and a 2-electron reduction of Ni(I)-ox1 to Ni(I)-red1. Analyses of the XANES and EXAFS data reveal that both the ox1 and red1 forms are best described as hexacoordinate and that the main difference between ox1 and red1 is the absence of an axial thiolate ligand in the red1 state. The RR data indicate that cofactor F(430) undergoes a significant conformational change when it binds to MCR. Furthermore, the vibrational characteristics of the ox1 state and red1 states are significantly different, especially in hydrocorphin ring modes with appreciable C=N stretching character. It is proposed that these differences arise from a 2-electron reduction of the hydrocorphin ring upon conversion to the red1 form. Presumably, the ring-reduction and ligand-exchange reactions reported herein underlie the enhanced activity of MCR(red1), the only form of MCR that can react productively with the methyl group of methyl-SCoM. 相似文献
1000.
Shaffer AW Worden JG Huo Q 《Langmuir : the ACS journal of surfaces and colloids》2004,20(19):8343-8351
Gold nanoparticles offer tremendous potential in the areas of nanoelectronics, bio- and chemosensors, and catalysis. However, before these applications are realized, the surface functionality of nanoparticles must be better controlled. Our lab has recently reported a novel synthetic approach for making monofunctionalized nanoparticles through a solid phase place exchange reaction. Monofunctionalized gold nanoparticles may also be prepared through a solution phase place exchange reaction. In this study, we compared the efficiency of these two separate approaches toward controlled functionalization of gold nanoparticles by (1)H NMR, Fourier transform infrared (FT-IR), and transmission electron microscopy (TEM) analysis. We found that the solid phase place exchange approach is much more efficient at producing monofunctionalized gold nanoparticles. (1)H NMR data were used to give a semiquantitative count of substituted bifunctional ligands, and FT-IR spectra supported these findings. Furthermore, we used a diamine coupling reaction of nanoparticles to show the presence of single or multiple functional groups on the nanoparticle surface by TEM analysis. 相似文献