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971.
Caiyun Xu Haihong Wu Zhanrong Zhang Bingxiao Zheng Jianxin Zhai Kaili Zhang Wei Wu Xuelei Mei Mingyuan He Buxing Han 《Chemical science》2022,13(6):1629
Effective hydrodeoxygenation (HDO) of aromatic alcohols is very attractive in both conventional organic synthesis and upgrading of biomass-derived molecules, but the selectivity of this reaction is usually low because of the competitive hydrogenation of the unsaturated aromatic ring and the hydroxyl group. The high activity of noble metal-based catalysts often leads to undesired side reactions (e.g., saturation of the aromatic ring) and excessive hydrogen consumption. Non-noble metal-based catalysts suffer from unsatisfied activity and selectivity and often require harsh reaction conditions. Herein, for the first time, we report chemoselective HDO of various aromatic alcohols with excellent selectivity, using porous carbon–nitrogen hybrid material-supported Co catalysts. The C–OH bonds were selectively cleaved while leaving the aromatic moiety intact, and in most cases the yields of targeted compounds reached above 99% and the catalyst could be readily recycled. Nitrogen doping on the carbon skeleton of the catalyst support (C–N matrix) significantly improved the yield of the targeted product. The presence of large pores and a high surface area also improved the catalyst efficiency. This work opens the way for efficient and selective HDO reactions of aromatic alcohols using non-noble metal catalysts.Porous carbon–nitrogen hybrid material-supported Co catalysts can effectively promote the chemoselective hydrodeoxygenation reaction of a various of aromatic alcohols in ethanol and hydrogen atmosphere, under relatively mild conditions. 相似文献
972.
973.
The new chiral β-aminoalcohols of indolinylmethanols ( 1 ) and their reduced derivatives ( 2 ) were synthesized from (S)-indoline-2-carboxylic acid. Both (R) and (S) enantiomers of the optically active secondary alcohols have been successfully obtained in high enantiomeric excess from the stereoselective addition of diethylzinc to the aldehydes catalyzed by the chiral aminoalcohols ( 1 and 2 ). The sense of the asymmetric induction and the degrees of enantioselectivities turned out to be highly dependent on the structure of the catalysts: The presence of the catalyst 1 afforded the (S)-configuration of the corresponding alcohols; on the other hand, the presence of 2 afforded the (R)-configuration of the alcohols in high enantiomeric selectivity. 相似文献
974.
With the rapid expansion of graphs and networks and the growing magnitude of data from all areas of science, effective treatment and compression schemes of context-dependent data is extremely desirable. A particularly interesting direction is to compress the data while keeping the “structural information” only and ignoring the concrete labelings. Under this direction, Choi and Szpankowski introduced the structures (unlabeled graphs) which allowed them to compute the structural entropy of the Erdős–Rényi random graph model. Moreover, they also provided an asymptotically optimal compression algorithm that (asymptotically) achieves this entropy limit and runs in expectation in linear time. In this paper, we consider the stochastic block models with an arbitrary number of parts. Indeed, we define a partitioned structural entropy for stochastic block models, which generalizes the structural entropy for unlabeled graphs and encodes the partition information as well. We then compute the partitioned structural entropy of the stochastic block models, and provide a compression scheme that asymptotically achieves this entropy limit. 相似文献
975.
Fumiyoshi Ikkai Mitsuhiro Shibayama Shunji Nomura Charles C. Han 《Journal of Polymer Science.Polymer Physics》1996,34(5):939-945
Mesoscopic structures of poly(vinyl alcohol)(SINGLEBOND)Congo red (PVA(SINGLEBOND) CR) complexes in aqueous solutions were investigated in terms of dynamic light scattering (DLS) technique. The intensity-intensity time correlation function, g(2)(t), was analyzed with an equation including a single and a stretched exponential function. Two diffusion coefficients, Df (fast) and Ds (slow) were evaluated. Df was converted to the apparent correlation length, ξapp, via the mode-mode coupling hypothesis. The estimated ξapp was insensitive to the sol(SINGLEBOND)to(SINGLEBOND)gel transition but decreased with CR concentration. This change may be related to the electrostatic screening effect. On the other hand, Ds oscillates with increasing CR concentration at a specific PVA concentration range. This explains well the reentrant sol(SINGLEBOND)gel(SINGLEBOND)sol(SINGLEBOND)gel transition behavior observed in the PVA(SINGLEBOND)CR systems. Ds seems to represent the mobility of the PVA(SINGLEBOND)CR complexes, which annihilates at the gel point. © 1996 John Wiley & Sons, Inc. 相似文献
976.
Silica-supported mono-metal (such as Ni, Cu) complexes and mixed metal (such as Cu/Zn, Cu/Cr) complexes of chitosan have been prepared. It is found that these non-noble metal complexes could be used as efficient catalysts for the hydrogenation of aromatic nitro compounds. The effects of type of metal, reaction temperature and pressure, solvent, nitrogen/metal molar ratio in the complex catalysts on the yields from nitrobenzene to aniline have been examined. It was also found that catalysts are active for the catalytic hydrogenation of other aromatic nitro compounds such as 2-nitroanisole, 2-nitroaniline, 2-nitrotoluene and 1-chloro-4-nitrobenzene. 相似文献
977.
In-Sook Han Lee Eun Hee Jeoung Chang Kiu Lee 《Journal of heterocyclic chemistry》1996,33(6):1711-1716
Benzimidazoles containing furyl and thienyl substituents at C-2 were prepared by condensation of o-phenylenediamine and corresponding carboxylic acids in the presence of polyphosphoric acid. The 2-heteroarylbenzimidazoles showed tautomerism in dimethyl sulfoxide solution while 2-phenylbenzimidazole did not. The tautomerism appeared to be taking place by intermolecular relay of protons between stacked molecules. 相似文献
978.
Hydroformylation of propylene has been conducted by a polymer-protected rhodium colloid catalyst with an activity of 130 mol butanal / g atom Rh·h. The neat colloid catalyst is stable enough for repeated use for 7 times lasting ∼50 h under the reaction condition (temperature: 363 K, pressure: 40 bar) with a total TON of 5,065 cycle / atom Rh. 相似文献
979.
980.