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91.
《化学:亚洲杂志》2017,12(3):289-292
A rhodium‐catalyzed regioselective C−H olefination of indazole is described. This protocol relies on the use of an efficient and removable N ,N ‐diisopropylcarbamoyl directing group, which offers facile access to C7‐olefinated indazoles with high regioselectivity, ample substrate scope and broad functional group tolerance. 相似文献
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Emilie RipaudCharlotte Mallet Magali AllainPhilippe Leriche Pierre FrèreJean Roncali 《Tetrahedron letters》2011,52(49):6573-6577
Two triphenylamine derivatives bearing terminal perfluorophenyl groups have been synthesized. Their HOMO, LUMO levels and electronic band gap have been evaluated by spectroscopic and electrochemical measurements and rationalized with theoretical calculations. X-ray structure analysis of crystals allowed the observation of multiple intermolecular interactions due to the presence of the perfluorophenyl pendant groups. The multiplication of these interactions explains the differences between calculated (in gas phase) and observed (in solid states) structures. 相似文献
93.
Dheeraj K. SinghSunil K. Srivastava Prachi RaghuvanshRanjan K. Singh B.P. Asthana 《Vibrational Spectroscopy》2011,56(1):34-41
The Raman spectra of neat (C2H5)2CO (pentanone) and its binary mixtures with hydrogen donor solvent (CH3OH), [(C2H5)2CO + CH3OH] having different mole fractions of the reference system, (C2H5)2CO in the range 0.1-0.9 at a regular interval of 0.1 were recorded in the CO stretching region. In neat liquid, the Raman peak appears asymmetric. The asymmetric nature of the peak has been attributed to the CO stretching mode of the two conformers of (C2H5)2CO having C2 and C2v point groups and the corresponding bands at ∼1711 and ∼1718 cm−1, respectively. A careful analysis of the Iiso (isotropic component of the Raman scattered intensity) at different concentrations reveals that upon dilution with methanol, at mole fraction C = 0.6, an additional peak in the CO stretching region is observed at ∼1703 cm−1 which is attributed to the hydrogen bonding with methanol. A peculiar feature in this study is that upon dilution, the peak at ∼1718 cm−1 shows a minimum at C = 0.6, but on further dilution it shows a blue shift. However, the other peak at ∼1711 cm−1 shows a continuous red shift with dilution as well as a maximum at C = 0.7 in the linewidth vs. concentration plot, which is essentially due to competition between motional narrowing and diffusion phenomena. A significant amount of narrowing in the Raman band at ∼1718 cm−1 can be understood in terms of caging effect of the reference molecule by the solvent molecules at high dilution. A density functional theoretic (DFT) calculation on optimized geometries and vibrational frequencies of two conformers of neat (C2H5)2CO in C2 ad C2v forms and the complexes with one and two CH3OH molecules with both the conformers was performed. The experimental results and theoretical calculations together indicate a co-existence of two conformers as well as hydrogen bonded complex with methanol in the binary mixture, [(C2H5)2CO + CH3OH] at intermediate concentrations. 相似文献
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应用广义梯度近似(GGA) (PW91和PBE)、含动能密度的广义梯度近似(meta-GGA) (M06-L)、杂化泛函(hyper-GGA)(M06-2X、X3LYP和B3LYP)及其长程校正泛函LC-DFT(CAM-B3LYP、LC-ωPBE和ωB97X)和色散校正密度泛函(DFT-D)(ωB97X-D和B97-D),用多种基函数对15种不同强度的传统氢键和非传统氢键体系的结合能进行了系统的计算与分析.并与高精度的CCSD(T)/aug-cc-pVQZ结果比较发现:在上述各类泛函中,对于氢键结合能的计算M06-2X和ωB97X-D泛函较为精确与可靠,且没有必要使用过大的基函数,6-311++G(2d,2p)或aug-cc-pVDZ水平的基组就已足够,各类泛函所计算结合能的基组重叠误差(BSSE)均较小,除ωB97X和ωB97X-D外,其它9种泛函不经BSSE校正也能得到同样甚至更准确的结果. 相似文献
97.
采用元素分析、1H核磁共振谱(1H NMR)和电喷雾电离质谱研究了两个大环主体分子β-环糊精(β-CD)和18-冠-6 (18C6), 结果显示, 二者通过简单地混合形成了计量比为1:1的超分子包合物18C6-β-CD. 基于二维核磁共振谱(ROESY)的分析, 提出了分子间相互作用的可能位点: 18C6更倾向于驻留在β-CD的小口端. 用热重分析和气相色谱飞行时间质谱比较了包合作用前后热降解过程包括降解度和降解产物的差异性, 研究表明, 18C6的存在促使β-CD提前分解, 同时, 由于分子间相互作用, 导致二者分解产物中大碎片的相对含量大幅减小. 这些结果显示, 一个柔性大环分子18C6和一个刚性大环分子β-CD之间通过分子组装可以形成超分子包合物. 相似文献
98.
Structured water on apposing surfaces can generate significant energies due to reorganization and displacement of water as the surfaces encounter each other. Force measurements on a multitude of biological structures using the osmotic stress technique have elucidated commonalities that point toward an underlying hydration force. In this review, the forces of two contrasting systems are considered in detail: highly charged DNA and nonpolar, uncharged hydroxypropyl cellulose. Conditions for both net repulsion and attraction, along with the measured exclusion of chemically different solutes from these macromolecular surfaces, are explored and demonstrate common features consistent with a hydration force origin. Specifically, the observed interaction forces can be reduced to the effects of perturbing structured surface water. 相似文献
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