102113-98-4Relevant articles and documents
Probing the Influence of PAd-DalPhos Ancillary Ligand Structure on Nickel-Catalyzed Ammonia Cross-Coupling
Lavoie, Christopher M.,Tassone, Joseph P.,Ferguson, Michael J.,Zhou, Yuqiao,Johnson, Erin R.,Stradiotto, Mark
, p. 4015 - 4023 (2018)
We report herein on the results of our combined experimental/computational study regarding the catalytic performance of PAd-DalPhos (L1) in nickel-catalyzed ammonia arylation for primary aniline synthesis. Primary arylamine C-N reductive eliminations occurring from arylnickel(II) parent amido complexes of the type (L)Ni(Ph)(NH2) were modeled by use of density-functional theory (DFT) methods, for a series of L1 derivatives. The dual aims were to assess the effect of structural modifications to L1 on potentially rate-limiting C-N reductive elimination and to identify promising candidates for experimental inquiry. Increasing the steric demand of the Paryl groups from o-tolyl (in L1) to mesityl (in L16) resulted in a significant lowering of the barrier to C-N reductive elimination (ΔG?RE), which can be attributed in part to interactions between the ligand Paryl groups and the nickel-bound amido ligand, as observed in noncovalent interaction (NCI) plots of the reductive elimination transition-state structures. Despite the favorability of L16 predicted on the basis of computational analysis focusing on C-N reductive elimination, this ancillary ligand performed poorly in experimental testing versus L1, suggesting that in practice the significant steric demands of L16 may discourage the formation of key catalytic intermediates. Modifications to the steric profile of the Paryl groups in L1 led to dramatic changes in catalytic performance, with the presence of an o-methyl proving to be important, among the L1 variants tested, in achieving useful catalytic performance in the Ni-catalyzed monoarylation of ammonia.
Preparation method of bis (4-biphenyl) amine
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Paragraph 0034; 0053-0068, (2022/03/27)
The invention provides a preparation method of di (4-biphenyl) amine, which comprises the following steps: synthesizing an intermediate di (4-biphenyl) acetamide, and removing acetyl of the intermediate to obtain a target product. The preparation method comprises the following steps: 1) mixing 4-bromobiphenyl, acetamide, a catalyst, a nitrogen-containing ligand L, alkali 1 and a solvent 1, and heating to react; 2) after the reaction, cooling the reaction system to room temperature, washing with water, separating liquid, and concentrating an organic phase to obtain a crude product of bis (4-biphenyl) acetamide; 3) loading the di (4-biphenyl) acetamide crude product with column chromatography silicon dioxide, and purifying with a column chromatography separation and purification method to obtain di (4-biphenyl) acetamide; 4) mixing di (4-biphenyl) acetamide, alkali 2 and a solvent 2, and heating to react; and 5) after the reaction, cooling the reaction system to room temperature, and carrying out suction filtration, water washing and drying to obtain di (4-biphenyl) amine. The invention belongs to the field of fine chemical engineering, and the preparation method is economical, safe, environment-friendly, efficient and suitable for industrial production.
Organic compound and electronic device and device containing the same
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Paragraph 0216-0219, (2021/09/11)
The invention relates to the technical field of organic electroluminescent materials, in particular to an organic electroluminescent material 9 with 10 -9 dihydro 9 -10 -dimethyl and oxanthrene and arylamine groups, an electronic device containing the compound and a device. The organic electroluminescent device has lower driving voltage. Higher luminous efficiency and longer service life.