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991.
Ivachtchenko AV Kobak VV Ilyn AP Khvat AV Kysil VM Williams CT Kuzovkova JA Kravchenko DV 《Journal of combinatorial chemistry》2005,7(2):227-235
Two efficient strategies for solution-phase parallel synthesis of libraries of quinoline derivatives are described. The first synthetic pathway features the Pfitzinger reaction of isatin with diethyl malonate and sulfochlorination of the resulting 2-oxo-1,2-dihydroquinoline-4-carboxylate followed by generation of sulfonamide library. The second strategy employs the unusual behavior of 5-sulfamoylisatins in Pfitzinger reactions, which results in formation of 6-sulfamoyl-4-carboxyquinolines instead of the anticipated 2-oxo-1,2-dihydroquinoline structures. The obtained carboxylates appeared to be convenient synthetic intermediates for the generation of the corresponding carboxamide libraries. Using these reagents, the parallel solution-phase synthesis of more than 500 substituted quinoline and 2-oxo-1,2-dihydroquinoline derivatives has been accomplished on the 50-100-mg scale. Simple manual techniques for parallel reactions using special CombiSyn synthesizers were coupled with easy purification procedures to give high-purity final products. The scope and limitations of the developed approaches are discussed. 相似文献
992.
Dmitry Yu. Naumov Marina I. Naumova Natalia V. Kuratieva Elena V. Boldyreva Judith A. K. Howard 《Acta Crystallographica. Section C, Structural Chemistry》2002,58(5):i55-i60
Copper(II) hypophosphite has been shown to exist as several polymorphs. The crystal structures of monoclinic α‐, orthorhombic β‐ and orthorhombic γ‐Cu(H2PO2)2 have been determined at different temperatures. The geometry of the hypophosphite anion in all three polymorphs is very close to the idealized one, with point symmetry mm2. Despite having different space groups, the structures of the α‐ and β‐polymorphs are very similar. The polymeric layers formed by the Cu atoms and the hypophosphite ions, which are identical in the α‐ and β‐polymorphs, stack in the third dimension in different ways. Each hypophosphite anion is coordinated to three Cu atoms. On cooling, a minimum amount of contraction was observed in the direction normal to the layers. The structure of the polymeric layers in the γ‐polymorph is quite different. There are two symmetry‐independent hypophosphite anions; the first is coordinated to two Cu atoms, while the second is coordinated to four Cu atoms. In all three polymorphs, the Cu atoms are coordinated by six O atoms of six hypophosphite anions, forming tetragonal bipyramids; in the α‐ and β‐polymorphs, there are four short and two long Cu—O distances, while in the γ‐polymorph, there are four long and two short Cu—O distances. 相似文献
993.
Dmitry V. Moiseev Brian R. James 《Phosphorus, sulfur, and silicon and the related elements》2020,195(9):687-712
AbstractTetrakis(hydroxymethyl)phosphonium (HOCH2)4P+ salts, particularly the chloride (THPC) and sulfate (THPS), are among the most accessible organophosphorus compounds that can be made quantitatively from PH3 and formaldehyde in aqueous media under ambient conditions. These phosphonium salts are air-stable, and are widely used as reactants in organic syntheses, as well as in textile or oil industries. Synthesis of tris(hydroxymethyl)phosphine (THP), an active component of the salts, is more complicated because direct synthesis from PH3 and CH2O requires either pressure and high temperature, at which THP rearranges into bis(hydroxymethyl)methylphosphine oxide, CH3P(O)(CH2OH)2, or a metal catalyst that is usually difficult or impossible to recover. Syntheses of THP based on neutralization of the salts are more convenient but require pH control and additional steps to separate THP from CH2O. This review summarizes literature data on syntheses and purification of the salts and THP, and side reactions such as thermal rearrangement and oxidation. 相似文献
994.
Alexander R Kudinov Dmitry A LoginovZoya A Starikova Pavel V Petrovskii 《Journal of organometallic chemistry》2002,649(2):136-140
New dicationic triple-decker complexes with a bridging boratabenzene ligand [Cp*Fe(μ-η:η-C5H5BMe)ML]X2 (ML=CoCp*, 6(CF3SO3)2; RhCp, 7(BF4)2; IrCp, 8(CF3SO3)2; Ru(η-C6H6), 9(CF3SO3)2; Ru(η-C6H3Me3-1,3,5), 10(CF3SO3)2; Ru(η-C6Me6), 11(CF3SO3)2) were synthesized by stacking reactions of Cp*Fe(η-C5H5BMe) (2) with the corresponding half-sandwich fragments [ML]2+. The structure of 10(CF3SO3)2 was determined by X-ray diffraction study. 相似文献
995.
In this paper we explore several issues surrounding the catalytic reduction of dinitrogen by molybdenum compounds that contain the [(HIPTNCH2CH2)3N]3- ligand (where HIPT = 3,5-(2,4,6-i-Pr3C6H2)2C6H3). Four additional plausible intermediates in the catalytic dinitrogen reduction have now been crystallographically characterized; they are MoN= NH (Mo = [(HIPTNCH2CH2)3N]Mo), [Mo=NNH2][BAr'4] (Ar' = 3,5-(CF3)2C6H3), [Mo=NH][BAr'4], and Mo(NH3). We also have crystallographically characterized a 2,6-lutidine complex, Mo(2,6-Lut)+, which is formed upon treatment of MoH with [2,6-LutH][B(C6F5)4]. We focus on the synthesis of compounds that have not yet been isolated, which include Mo=NNH2, Mo=NH, and Mo(NH2). Mo=NNH2, formed by reduction of [Mo=NNH2]+, has not been observed. It decomposes to give mixtures that contain two or more of the following: MoN=NH, Mo triple bond N, Mo(NH3)+, Mo(NH3), and ammonia. Mo=NH, which can be prepared by reduction of [Mo=NH]+, is stable for long periods in the presence of a small amount of CrCp*2, but in the absence of CrCp*2, and in the presence of Mo=NH+ as a catalyst, Mo=NH is slowly converted into a mixture of Mo triple bond N and Mo(NH2). Mo(NH2) can be produced independently by deprotonation of Mo(NH3)+ with LiN(SiMe3)2 in THF, but it decomposes to Mo triple bond N upon attempted isolation. Although catalytic reduction of dinitrogen could involve up to 14 intermediates in a "linear" sequence that involves addition of "external" protons and/or electrons, it seems likely now that several of these intermediates, along with ammonia and/or dihydrogen, can be produced in several reactions between intermediates that themselves behave as proton and/or electron sources. 相似文献
996.
The structure of the laser-light-induced metastable state MS(1) of the [Ru(NO(2))(4)(OH)(NO)](2)(-) anion in K(2)[Ru(NO(2))(4)(OH)(NO)] was determined by X-ray analysis at 50 K of a crystal with a 16% excited-state population. Results of an independent determination of the ground-state structure were used in the analysis. The most pronounced geometrical change upon excitation was an increase of the Ru-(NO) distance by 0.097(11) ?, significantly larger than the change of the corresponding distance in sodium nitroprusside (Pressprich, M. R.; White, M. A.; Vekhter, Y.; Coppens, P. J. Am. Chem. Soc. 1994, 116, 5233-5238). A decrease in the angleRu-(N-O) angle from 174.0(2) to 169(1) degrees was observed. The diffraction results provide evidence that the photoinduced state MS(1) of the transition metal nitrosyl complexes is a linkage isomer in which the NO group is attached to the metal atom through the oxygen, instead of through the nitrogen atom, rather than an electronic excited state as reported previously. 相似文献
997.
[reaction: see text]. Formation of a cross-linked, porous supramolecular polymer leads to instant entrapment of organic guest species. These can be stored and then released upon changing solvent polarity, temperature, pH, and concentration. 相似文献
998.
Modular aptameric sensors 总被引:7,自引:0,他引:7
We report the first examples of modular aptameric sensors, which transduce recognition events into fluorescence changes through allosteric regulation of noncovalent interactions with a fluorophore. These sensors consist of: (a) a reporting domain, which signals the binding event of an analyte through binding to a fluorophore; (b) a recognition domain, which binds the analyte; and (c) a communication module, which serves as a conduit between recognition and signaling domains. We tested recognition regions specific for ATP, FMN, and theophylline in combinations with malachite green binding aptamer as a signaling domain. In each case, we were able to obtain a functional sensor capable of responding to an increase in analyte concentration with an increase in fluorescence. Similar constructs that consist only of natural RNA could be expressed in cells and used as sensors for intracellular imaging. 相似文献
999.
We establish, through coarse-grained computation, a connection between traditional, continuum numerical algorithms (initial value problems as well as fixed point algorithms), and atomistic simulations of the Larson model of micelle formation. The procedure hinges on the (expected) evolution of a few slow, coarse-grained mesoscopic observables of the Monte Carlo simulation, and on (computational) time scale separation between these and the remaining "slaved," fast variables. Short bursts of appropriately initialized atomistic simulation are used to estimate the (coarse grained, deterministic) local dynamics of the evolution of the observables. These estimates are then in turn used to accelerate the evolution to computational stationarity through traditional continuum algorithms (forward Euler integration, Newton-Raphson fixed point computation). This "equation-free" framework, bypassing the derivation of explicit, closed equations for the observables (e.g., equations of state), may provide a computational bridge between direct atomistic/stochastic simulation and the analysis of its macroscopic, system-level consequences. 相似文献
1000.