685-91-6Relevant articles and documents
Mechanistic Insights into Fe Catalyzed α-C?H Oxidations of Tertiary Amines
Legacy, Christopher J.,Hope, Taylor O.,Gagné, Yohann,Greenaway, Frederick T.,Frenette, Mathieu,Emmert, Marion H.
, p. 235 - 246 (2020/10/19)
We report detailed mechanistic investigations of an iron-based catalyst system, which allows the α-C?H oxidation of a wide variety of amines. In contrast to other catalysts that effect α-C?H oxidations of tertiary amines, the system under investigation exclusively employs peroxy esters as oxidants. More common oxidants (e. g. tBuOOH) previously reported to affect amine oxidations via free radical pathways do not provide amine α-C?H oxidation products in combination with the described catalyst system. The investigations described herein employ initial rate kinetics, kinetic profiling, DFT calculations as well as Eyring, kinetic isotope effect, Hammett, ligand coordination, and EPR studies to shed light on the Fe catalyst system. The obtained data suggest that the catalytic mechanism proceeds through C?H abstraction at a coordinated substrate molecule. This rate-determining step occurs either through an Fe(IV) oxo pathway or a 2-electron pathway at an Fe(II) intermediate with bound oxidant. DFT calculations indicate that the Fe(IV) oxo mechanism will be the preferred route of these two possibilities. We further show via kinetic profiling and EPR studies that catalyst activation follows a radical pathway, which is initiated by hydrolysis of PhCO3tBu to tBuOOH. Overall, the obtained mechanistic data support a non-classical, Fe catalyzed pathway that requires substrate binding, inducing selectivity for α-C?H functionalization.
Production method of N,N-diethyl acetamide
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Paragraph 0018; 0025; 0035; 0045; 0055; 0065; 0075, (2020/06/30)
The invention discloses a preparation method of N,N-dimethylformamide. The production method comprises the following steps: n a self-reflux reactor filled with a heterogeneous catalyst, firstly addingethyl acetate and ethylamine, carrying out heating to 30 DEG C within 10-20 minutes, then gradually adding ethanol within 20-30 minutes, then carrying out heating to 50-60 DEG C at a speed of 30-50 DEG C/h, performing reacting for 20-30 minutes, ending the reaction, and finally carrying out purifying to obtain N,N-diethyl acetamide. The obtained N,N-diethyl acetamide is high in yield, selectivityand purity, and the method is mild in reaction condition and easy to operate.
Amide Bond Formation Catalyzed by Recyclable Copper Nanoparticles Supported on Zeolite Y under Mild Conditions
Moglie, Yanina,Buxaderas, Eduardo,Mancini, Agustina,Alonso, Francisco,Radivoy, Gabriel
, p. 1487 - 1494 (2019/02/16)
A series of catalysts based on supported copper nanoparticles have been prepared and tested in the amide bond formation from tertiary amines and acid anhydrides, in the presence of tert-butyl hydroperoxide as an oxidant. Copper nanoparticles on zeolite Y (CuNPs/ZY) was found to be the most efficient catalyst for the synthesis of amides, working in acetonitrile as solvent, under ligand- and base-free conditions in air. The products were obtained in good to excellent yields and in short reaction times. The CuNPs/ZY system also exhibited higher catalytic activity than some commercially available copper and iron sources and it was reused in ten reaction cycles without any further pre-treatment. This methodology has been successfully scaled-up to a gram scale with no detriment to the yield.