排序方式: 共有51条查询结果,搜索用时 15 毫秒
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van Eis MJ van Der Linde BS de Kanter FJ de Wolf WH Bickelhaupt F 《The Journal of organic chemistry》2000,65(14):4348-4354
In contrast to the terminal phosphinidene complex PhPW(CO)(5) (2), which adds to [5]metacyclophane (1) in a 1,4-fashion, dichlorocarbene preferentially adds in a 1,2-fashion to the formal "anti-Bredt" type double bond of the aromatic ring of 1 to afford the norcaradiene 11b, which immediately rearranges to the bridged cycloheptatriene 12b and further by a [1,5] sigmatropic chlorine migration to the isomeric 13b as the first observable product. More slowly, the latter isomerizes via a dissociative mechanism to give 15b. A computational study supports the notion that the [1,5] chlorine migration in the rearrangement 12b --> 13b, for which an activation barrier of 70.2 kJ mol(-)(1) was calculated, is essentially concerted with minor charge separation. In contrast, the analogous [1,5] chlorine migration in the flat model compound 7,7-dichlorocycloheptatriene (12a) displays features of a dissociative pathway. 相似文献
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G. Ooms C. Poelma P. Poesio MJ.B.M. Pourquie J. Westerweel 《International Journal of Multiphase Flow》2008
In an earlier publication some of the authors presented a theoretical model for the calculation of the influence of particle inertia and gravity on the turbulence in a stationary particle-laden flow. In the present publication the model is extended for application to a decaying suspension. Also a comparison is given between predictions made with the model and experimental data (own data and data reported in the literature) on a decaying turbulent flow with particles in a water tunnel or in a wind tunnel. For most of the experiments a prediction with reasonable accuracy and an interpretation is possible by means of the model. 相似文献
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We analyse the evolution of a two-stage chemical reaction betweentwo neighbouring plumes of reactants. Under the assumption thatthe plumes are approximately Gaussian we derive a system ofordinary differential equations for the total amount, the centroidand the variance of each reactant. We compare the solution ofthese equations with full numerical simulation of the reaction.Excellent agreement is obtained, with solution of the near-Gaussianmodel requiring considerably less computational effort thanthe full simulations. Of key importance is the yield of thereaction, and we discuss this feature in particular. 相似文献
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Ivan Earnest Jaroslav Kalvoda Eric Francotte Grety Rihs Hans Fritz Marcel J. J. Blommers Fritz Raschdorf Christoph Sigel Manfred Mutter 《Helvetica chimica acta》1993,76(4):1539-1563
The 8-amino-5,6,7,8-tetrahydronaphth-2-oic acid ( 1 ), 8-(aminomethyl)-5,6,7,8-tetrahydronaphth-2-oic acid ( 2 ), and 8-(aminomethyl)naphth-2-oic acid ( 3 ) were synthesized in their protected forms as turn-inducing dipeptide mimics. Two of them ( 2 and 3 ) were incorporated into a novel type of cyclic, peptide-based structures (see 21 and 34 – 36 ) designed as templates for the synthesis of TASP molecules. 相似文献
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