6628-04-2Relevant articles and documents
Structural and Reactivity Comparisons of JosiPhos CyPF-Cy and a Simplified Variant ("CyPBn-Cy") in Nickel-Catalyzed C(sp2)-N Cross-Couplings
Bodé, Nicholas E.,Ferguson, Michael J.,Stradiotto, Mark,Tassone, Joseph P.
, p. 2915 - 2922 (2021/08/27)
The synthesis and characterization of the new complexes (CyPBn-Cy)NiCl2 and (CyPBn-Cy)Ni(o-tol)Cl are reported (CyPBn-Cy = o-di(cyclohexyl)phosphino-benzyl-di(cyclohexyl)phosphine), along with a head-to-head structural and reactivity comparison of (L)Ni(o-tol)Cl precatalyst complexes (L = JosiPhos CyPF-Cy and CyPBn-Cy) in the Ni-catalyzed cross-couplings of (hetero)aryl chlorides or phenol-derived electrophiles with ammonia or furfurylamine. The structures of these precatalysts were found not to differ significantly (e.g., coordination geometry and % buried volume), and these similarities were, generally speaking, reflected in the observed catalytic behavior of these precatalysts, with notable exceptions including reactions involving the hindered electrophile 2-chloro-m-xylene, where (CyPBn-Cy)Ni(o-tol)Cl proved superior; the N-arylation of furfurylamine by use of 1-(N,N-diethylcarbamoyl)-naphthalene, where CyPF-Cy proved to be the preferred ligand; and monoarylation (CyPBn-Cy) versus diarylation (CyPF-Cy) selectivity in the cross-coupling of furfurylamine with 2-chloro-6-methoxypyridine. In studying the time-course of the cross-coupling of furfurylamine and 1-chloronaphthalene, significantly faster conversion to product and higher overall yield were noted when using CyPBn-Cy. These results confirm that CyPBn-Cy can be viewed as being competitive with, and complementary to, the well-established JosiPhos ligand CyPF-Cy in this class of Ni-catalyzed cross-couplings.
Preparation method of dequalinium chloride
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Paragraph 0040; 0043; 0047; 0050; 0054; 0057; 0061; 0064, (2020/05/01)
The invention relates to a preparation method of dequalinium chloride. The method comprises the following steps: reacting 2-methyl-4-chloroquinoline, used as a starting material, with p-methoxybenzylamine to obtain an amination intermediate II, carrying out a debenzylation reaction on the intermediate to obtain 2-methyl-4-aminoquinaldine, then reacting the 2-methyl-4-aminoquinaldine with 1,10-diiododecane to obtain dequalinium iodide, continuously reacting the dequalinium iodide with hydrochloric acid to obtain dequalinium chloride, and finally recrystallizing with a mixed solvent to obtain refined dequalinium chloride. The preparation method of the dequalinium chloride does not adopt a highly toxic solvent nitrobenzene, and adopts a nontoxic or low-toxicity solvent, and the reaction temperature is reduced in the reaction process, so the method is environmentally friendly, and the reaction conditions are simple; and the refined dequalinium chloride product is prepared through recrystallization using the mixed solvent, so impurities in the dequalinium chloride process are controllable, the yield and purity of the prepared dequalinium chloride are high, the product quality is stable,and the method is suitable for industrial production.
Nickel-Catalyzed Synthesis of Primary Aryl and Heteroaryl Amines via C-O Bond Cleavage
Yue, Huifeng,Guo, Lin,Liu, Xiangqian,Rueping, Magnus
supporting information, p. 1788 - 1791 (2017/04/11)
A nickel-catalyzed protocol for the conversion of aryl and heteroaryl alcohol derivatives to primary and secondary aromatic amines via C(sp2)-O bond cleavage is described. The new amination protocol can be applied to a range of substrates bearing diverse functional groups and uses readily available benzophenone imines as an effective nitrogen source.
