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71.
6-Trifluoromethyl-12-acylindolo[1,2-c]quinazolines are prepared in high yield through the palladium-catalyzed reaction of bis(o-trifluoroacetamidophenyl)acetylene with aryl or vinyl halides and triflates. The reaction, which tolerates a variety of important functional groups, probably involves the formation of a 3-acyl-2-(o-trifluoroacetamidophenyl)indole intermediate, followed by its cyclization to the indoloquinazoline product. [reaction: see text] 相似文献
72.
Abbotto A Beverina L Bozio R Facchetti A Ferrante C Pagani GA Pedron D Signorini R 《Chemical communications (Cambridge, England)》2003,(17):2144-2145
The first examples of heterocycle-based multi-branched dyes with efficient two-photon absorption (TPA) activity are reported; the novel chromophores exhibit large TPA cross sections (as high as 1600 x 10(-50) cm4 s photon(-1) molecule(-1), measured with 150 fs laser pulses at 800 nm); a strong cooperative enhancement in the branched systems with respect to the one-dimensional sub-units is found. 相似文献
73.
Herein, we report the 1,2-dialkylation of simple feedstock acrylates for the synthesis of valuable tertiary carboxylic acids by merging Giese-type radical addition with an Ireland–Claisen rearrangement. Key to success is the utilization of the reductive radical-polar crossover concept under photocatalytic reaction conditions to force the [3,3]-sigmatropic rearrangement after alkyl radical addition to allyl acrylates. Using readily available alkyl boronic acids as radical progenitors, this redox-neutral, transition-metal-free protocol allows the mild formation of two C(sp3)–C(sp3) bonds, thus providing rapid access to complex tertiary carboxylic acids in a single step. Moreover, this strategy enables the efficient synthesis of highly attractive α,α-dialkylated γ-amino butyric acids (GABAs) when α-silyl amines are used as radical precursors – a structural motif that was still inaccessible in related transformations. Depending on the nature of the radical precursors and their inherent oxidation potentials, either a photoredox-induced radical chain or a solely photoredox mechanism is proposed to be operative.A photocatalytic 1,2-dialkylation of α-substituted acrylates is enabled by a reaction cascade combining reductive radical-polar crossover with the established Ireland–Claisen rearrangement for the synthesis of valuable tertiary carboxylic acids. 相似文献
74.
Treatment of methyl 2-chloro-2-phenylhydrazonoacetate (1) with 1-phenylsulphonylpropyne (3) in the presence of triethylamine gives pyrazole derivatives due to cycloadditions of a nitrile imine intermediate with 3 and with its rearranged product phenylsulphonylallene (4). 相似文献
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77.
Abstract The compound 4-cyano-4′-(α,α,α-trifluoromethoxy)biphenyl (1OCBF3) has been synthesized. Unlike the fully protonated analogue, 4-cyano-4′-methoxybiphenyl (1OCB), it does not show a liquid crystalline phase on cooling from the melting point (51°C) to room temperature. The transition temperature to a monotropic nematic phase was obtained as approximately 0°C by determining the transition temperatures of mixtures with 1OCB. The structures, conformational properties and orientational ordering of both 1OCB and 1OCBF3 as solutes in a nematic solvent ZLI 1132 have been investigated via the 17 dipolar couplings obtained by analysing the proton and fluorine NMR spectra of these solutions. It is concluded that the major difference between the two molecules lies in the potential, V(φ2), governing rotation about the ring–oxygen bonds. In 1OCB the potential has the same form as in anisole, with a minimum when the C–O bond is in the plane of the attached ring (φ2 = 0°), and a maximum of about 15 kJ mol?1 when φ2 is 90°. In 1OCBF3 the barrier to rotation about the ring–O bond decreases substantially to being near zero. 相似文献
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79.
Paolo Muratore-Ginanneschi Carlos Mejía-Monasterio Luca Peliti 《Journal of statistical physics》2013,150(1):181-203
We derive the equations governing the protocols minimizing the heat released by a continuous-time Markov jump process on a one-dimensional countable state space during a transition between assigned initial and final probability distributions in a finite time horizon. In particular, we identify the hypotheses on the transition rates under which the optimal control strategy and the probability distribution of the Markov jump problem obey a system of differential equations of Hamilton-Jacobi-Bellman-type. As the state-space mesh tends to zero, these equations converge to those satisfied by the diffusion process minimizing the heat released in the Langevin formulation of the same problem. We also show that in full analogy with the continuum case, heat minimization is equivalent to entropy production minimization. Thus, our results may be interpreted as a refined version of the second law of thermodynamics. 相似文献
80.
Fabeni Pasquale Linari Roberto Pazzi Gian Paolo Ranfagni Anedio Salvini Luca 《辐射效应与固体损伤》2013,168(1):307-312
Abstract Time-resolved emissions of Csl:T1 are investigated. The system is laser-excited in the A-band at 308 nm and the emissions are observed in the range 370–650 nm, from 30 K to 300 K. Their analysis by means of a deconvolution permits the valuation of decay-times down to 1 ns. At every temperature many bands are observed and some of them show slow and fast components. The decay-times of the fast components are in the range 1–10 ns while the slow ones are even longer than 1 μs. In many cases intermediate decay-times of the order of 100 ns exist. The competition among the bands interests the application of this system as active material for tunable solid-state laser. 相似文献