713-36-0Relevant articles and documents
Metal-Organic Framework-Confined Single-Site Base-Metal Catalyst for Chemoselective Hydrodeoxygenation of Carbonyls and Alcohols
Antil, Neha,Kumar, Ajay,Akhtar, Naved,Newar, Rajashree,Begum, Wahida,Manna, Kuntal
supporting information, p. 9029 - 9039 (2021/06/28)
Chemoselective deoxygenation of carbonyls and alcohols using hydrogen by heterogeneous base-metal catalysts is crucial for the sustainable production of fine chemicals and biofuels. We report an aluminum metal-organic framework (DUT-5) node support cobalt(II) hydride, which is a highly chemoselective and recyclable heterogeneous catalyst for deoxygenation of a range of aromatic and aliphatic ketones, aldehydes, and primary and secondary alcohols, including biomass-derived substrates under 1 bar H2. The single-site cobalt catalyst (DUT-5-CoH) was easily prepared by postsynthetic metalation of the secondary building units (SBUs) of DUT-5 with CoCl2 followed by the reaction of NaEt3BH. X-ray photoelectron spectroscopy and X-ray absorption near-edge spectroscopy (XANES) indicated the presence of CoII and AlIII centers in DUT-5-CoH and DUT-5-Co after catalysis. The coordination environment of the cobalt center of DUT-5-Co before and after catalysis was established by extended X-ray fine structure spectroscopy (EXAFS) and density functional theory. The kinetic and computational data suggest reversible carbonyl coordination to cobalt preceding the turnover-limiting step, which involves 1,2-insertion of the coordinated carbonyl into the cobalt-hydride bond. The unique coordination environment of the cobalt ion ligated by oxo-nodes within the porous framework and the rate independency on the pressure of H2 allow the deoxygenation reactions chemoselectively under ambient hydrogen pressure.
Method for reducing carbonyl reduction to methylene under illumination
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Paragraph 0033-0038; 0104-0108, (2021/09/29)
The invention belongs to the technical field of organic chemical synthesis. The method comprises the following steps: (1) mixing the carbonyl compound and the amine compound in a solvent, reacting 3 - 6 under the illumination of 380 - 456 nm, the reaction system is low in toxicity, high in atom utilization rate 12 - 24h. and production efficiency, safe and controllable in reaction process and capable of simplifying the operation in the preparation and production process. At the same time, the residue toxicity of the reaction is minimized, the pollution caused by the production process to the environment is reduced, and the steps and operations of removing residues after the reaction are simplified. In addition, the reactant feedstock is readily available. The reactant does not need additional modification before the reaction, can be directly used for preparing production, simplifies the operation steps, and shortens the reaction route. The production cost is obviously reduced.
Development of highly efficient Friedel-Crafts alkylations with alcohols using heterogeneous catalysts under continuous-flow conditions
Kobayashi, Shū,Koumura, Nagatoshi,Masuda, Koichiro,Okamoto, Yukiko,Onozawa, Shun-Ya
, p. 24424 - 24428 (2021/07/29)
The development of Friedel-Crafts alkylations with alcohols under continuous-flow conditions using heterogeneous catalysts is reported. The reactivities and durabilities of the examined catalysts were systematically investigated, which showed that montmorillonite clay is the best catalyst for these reactions. A high turnover frequency of 9.0 × 102h?1was recorded under continuous-flow conditions, and the continuous operation was successfully maintained over one week.
