127-19-5Relevant articles and documents
Lewis Acidic Boranes, Lewis Bases, and Equilibrium Constants: A Reliable Scaffold for a Quantitative Lewis Acidity/Basicity Scale
Mayer, Robert J.,Hampel, Nathalie,Ofial, Armin R.
supporting information, p. 4070 - 4080 (2021/01/29)
A quantitative Lewis acidity/basicity scale toward boron-centered Lewis acids has been developed based on a set of 90 experimental equilibrium constants for the reactions of triarylboranes with various O-, N-, S-, and P-centered Lewis bases in dichloromethane at 20 °C. Analysis with the linear free energy relationship log KB=LAB+LBB allows equilibrium constants, KB, to be calculated for any type of borane/Lewis base combination through the sum of two descriptors, one for Lewis acidity (LAB) and one for Lewis basicity (LBB). The resulting Lewis acidity/basicity scale is independent of fixed reference acids/bases and valid for various types of trivalent boron-centered Lewis acids. It is demonstrated that the newly developed Lewis acidity/basicity scale is easily extendable through linear relationships with quantum-chemically calculated or common physical–organic descriptors and known thermodynamic data (ΔH (Formula presented.)). Furthermore, this experimental platform can be utilized for the rational development of borane-catalyzed reactions.
PRODUCTION METHOD OF N,N-DIMETHYLAMIDE
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Paragraph 0037-0042; 0046-0054, (2020/08/26)
PROBLEM TO BE SOLVED: To provide a production method with which N,N-dimethylamide can be produced by making a nitrile and methanol react with each other in gas phase. SOLUTION: A production method of N,N-dimethylamide for producing N,N-dimethylamide by making a nitrile and methanol react with each other in gas phase in the presence of a catalyst is disclosed, in which the nitrile is acetonitrile or propionitrile and the catalyst is an alloy containing copper and aluminum. Preferably acetonitrile is used as the nitrile. SELECTED DRAWING: None COPYRIGHT: (C)2020,JPOandINPIT
Formation of carbon–nitrogen bonds in carbon monoxide electrolysis
Jouny, Matthew,Lv, Jing-Jing,Cheng, Tao,Ko, Byung Hee,Zhu, Jun-Jie,Goddard, William A.,Jiao, Feng
, p. 846 - 851 (2019/09/03)
The electroreduction of CO2 is a promising technology for carbon utilization. Although electrolysis of CO2 or CO2-derived CO can generate important industrial multicarbon feedstocks such as ethylene, ethanol, n-propanol and acetate, most efforts have been devoted to promoting C–C bond formation. Here, we demonstrate that C–N bonds can be formed through co-electrolysis of CO and NH3 with acetamide selectivity of nearly 40% at industrially relevant reaction rates. Full-solvent quantum mechanical calculations show that acetamide forms through nucleophilic addition of NH3 to a surface-bound ketene intermediate, a step that is in competition with OH– addition, which leads to acetate. The C–N formation mechanism was successfully extended to a series of amide products through amine nucleophilic attack on the ketene intermediate. This strategy enables us to form carbon–heteroatom bonds through the electroreduction of CO, expanding the scope of products available from CO2 reduction.