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71.
A two-step short and efficient strategy for the synthesis of substituted piperidones and piperidines in high diastereoselectivity (only trans-configuration), by employing cascade type reaction using BF3·Et2O or by carrying out one pot deprotection of tBoc group followed by intramolecular aza-Michael addition of α,β-unsaturated beta keto esters has been developed. Using a similar strategy a short access to hydroxy pipecolic acid is also described. Very simple and rapid experimental procedures involving mild conditions and only one or two chromatographic purifications are the main features of the process. 相似文献
72.
The kinetics of dissociation of tris-2,2′-bipyridyl-iron(II) complex ion have been examined in aqueous acetic acid solutions. The reaction is first order in the complex ion; the dependence of rate on H+ is somewhat like that observed in aqueous solutions approaching a limiting value at higher H+ concentrations. The influence of solvent composition on the reaction rate under acid-dependent and acid-independent conditions shows an initial retardation by acetic acid. The argument of ion-pair formation based on decrease of dielectric constant proposed to explain the kinetics in other aqueous solvent media was found useless to explain the behavior in acetic acid solutions. Other solvent parameters also did not provide satisfactory correlation with the kinetic results, thus, indicating the operation of more complex microscopic solute-solvent and solvent-solvent interactions. While solvent effects play some part in the rate process, the rate of reaction would tend to zero in the absence of H2O and H+. This interesting observation proved useful in proposing a reaction mechanism that is consistent with the rate behavior over the entire range of solvent composition. The activity of water in the reaction medium is controlled by the content of acetic acid which can effect the structure of water through operation of hydrophobic forces and formation of hydrates. While acetic acid cannot possibly fulfill the role of water in occupying the vacated coordination position, the anomalous rise in rate even under some water deficient conditions seems to be related to the coordinating ability of HSO4? derived from H2SO4 present in the solution. 相似文献
73.
Finite clusters of atoms or molecules, typically composed of about 50 particles (and often as few as 13 or even less) have
proved to be useful prototypes of systems undergoing phase transitions. Analogues of the solid-liquid melting transition,
surface melting, structural phase transitions and the glass transition have been observed in cluster systems. The methods
of nonlinear dynamics can be applied to systems of this size, and these have helped elucidate the nature of the microscopic
dynamics, which, as a function of internal energy (or ‘temperature’) can be in a solidlike, liquidlike, or even gaseous state.
The Lyapunov exponents show a characteristic behaviour as a function of energy, and provide a reliable signature of the solid-liquid
melting phase transition. The behaviour of such indices at other phase transitions has only partially been explored. These
and related applications are reviewed in the present article. 相似文献
74.
Catalytic Reduction of p‐Nitrophenol and Hexacyanoferrate (III) by Borohydride Using Green Synthesized Gold Nanoparticles
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G. Bhagavanth Reddy D. Ramakrishna A. Madhusudhan D. Ayodhya M. Venkatesham G. Veerabhadram 《中国化学会会志》2015,62(5):420-428
A simple and green approach for the synthesis of well‐stabilized gold nanoparticles (AuNPs) using gum Acacia (GA) is presented here. The gum acacia acts as the reductant and stabilizer. The synthesized gold nanoparticles were characterized by using ultraviolet visible (UV‐Vis), fourier transform infrared spectroscopy (FTIR), x‐ray diffraction (XRD), dynamic light scattering (DLS) and transmission electron microscopy (TEM) techniques. The UV‐Vis study revealed a distinct surface plasmon resonance at 520 – 550 nm, due to the formation of AuNPs. FTIR analysis showed the evidence that –OH groups present in the gum matrix were responsible in reducing the tetra chloroauric acid into AuNPs. XRD studies confirmed the formation of well crystalline nanoparticles with fcc structure and the particle size ranges from 4 – 29 nm, as indicated by TEM analysis. The synthesized gold nanoparticles exhibited homogeneous catalytic activity. The two model reactions studied were the reduction of p‐nitro phenol and the reduction of hexacyanoferrate (III) by borohydride ions. Both the reactions were monitored by UV‐Vis spectroscopy. The kinetic investigations were carried out for the AuNPs‐catalyzed reactions at different temperatures and different amount of catalyst. 相似文献
75.
A series of novel imidazo[1,2-b]isoxazoles 3 and their Mannich bases 4–6 were synthesized via convenient reactions. The reaction of 3-aminoisoxazole 1 with substituted phenacyl bromides 2 in dry ethanol afforded the corresponding 6-methyl-3-aryl imidazo[1,2-b]isoxazoles 3 in good yields.Compounds 3 on treatment with 37% formaline and secondary amines furnished the corresponding novel Mannich bases viz., 6-methyl-3-aryl-2-(morpholine/pyrrolidin-1-yl/piperidin-1-yl)-methyl-imidazo[1,2-b]isoxazoles 4–6. 相似文献
76.
A Convenient and Facile Synthesis of Isoxazolyl‐chromeno[4,3,2‐de]pyrimido[4,5‐h][1,6]napthyridinones
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Eligeti Rajanarendar Saini Ramakrishna Baireddy Kishore 《Journal of heterocyclic chemistry》2014,51(5):1415-1420
The ceric ammonium nitrate‐catalyzed synthesis of (E)‐5‐amino‐N‐(3‐methyl‐5‐styrylisoxazol‐4‐yl)‐2‐arylchromeno[4,3,2‐de][1,6]napthyridin‐4‐carboxamides 5 was simply achieved upon the one‐pot four‐component reaction of isoxazolyl cyanoacetamide 1 with malononitrile 2 , 2‐hydroxy acetophenone 3 , and aromatic aldehydes 4 in ethanol. Compounds 5 on heating with acetic anhydride underwent tandem N‐acetylation and cyclocondensation involving intramolecular cyclization to afford the title compounds (E)‐11‐methyl‐12‐(3‐methyl‐5‐styrylisoxazol‐4‐yl)‐2‐arylchromeno[4,3,2‐de][1,6]napthyridin‐13(12H)‐ones 6 in good yields. The chemical structures have been confirmed by analytical and spectral analyses. 相似文献
77.
Shahin A Joshi YM Ramakrishna SA 《Langmuir : the ACS journal of surfaces and colloids》2011,27(23):14045-14052
Aqueous suspensions of Laponite, a system composed of disklike nanoparticles, are found to develop optical birefringence over several days, well after the suspensions solidified because of jamming. The optical anisotropy is particularly enhanced near the air-Laponite suspension interface over length scales of several millimeters, which is beyond 5 orders of magnitude larger than the particle length scale, suggestive of large-scale ordering influenced by the interface. The orientational order increases with time and is always greater for higher concentration of salt, higher concentration of Laponite, and higher temperatures of the suspension. Although weakly birefringent, Laponite suspensions covered by paraffin oil do not show any enhancement in optical anisotropy near the interface compared to that in the bulk. We suggest that the expedited structure formation near the air interface propagating progressively inside the sample is responsible for the observed behavior. We discuss the observed nematic ordering in the context of glass-like and gel-like microstructure associated with aqueous Laponite suspensions. 相似文献
78.
We show, using semiclassical methods, that as a symmetry is broken, the transition between universality classes for the spectral
correlations of quantum chaotic systems is governed by the same parametrization as in the theory of random matrices. The theory
is quantitatively verified for the kicked rotor quantum map. We also provide an explicit substantiation of the random matrix
hypothesis, namely that in the symmetry-adapted basis the symmetry-violating operator is random. 相似文献
79.
Ramakrishna Balasubramanian Madan M. Oberai 《Zeitschrift für Angewandte Mathematik und Physik (ZAMP)》1970,21(6):1097-1101
Zusammenfassung Eine Kombination der Lees-Methode und des Mott-Smith Ansatzes wird auf zwei Probleme der Couette-Strömung zwischen zwei Zylindern angewandt. Es werden Ausdrücke hergeleitet für das Moment im Fall, dass ein Zylinder rotiert, und für den Wärmefluss im Fall, dass beide Zylinder stationär sind, aber verschiedene Temperatur haben; diese Ausdrücke sind für alle Werte der Knudsenzahl gültig. 相似文献
80.