86-52-2Relevant articles and documents
New synthesis process of naftifine drug intermediate N-methyl-1-naphthalenemethylamine
-
Paragraph 0024-0033, (2021/03/30)
The invention discloses a new synthesis process of a naftifine drug intermediate N-methyl-1-naphthalenemethylamine. The process includes: adding phosphoric acid, concentrated hydrochloric acid, industrial naphthalene, paraformaldehyde and a catalyst, performing heating, introducing HCL gas, and carrying out reaction to obtain a 1-chloromethylnaphthalene crude product; performing cooling, dropwiseadding the 1-chloromethylnaphthalene crude product into a methanolamine solution, and carrying out reaction to obtain an N-methyl-1-naphthalenemethylamine crude product; performing evaporating to remove the redundant methanolamine solution, adjusting the alkali with a sodium hydroxide aqueous solution, conducting washing with water for layering, adding water and dichloromethane into an organic layer, adjusting the pH value with hydrochloric acid, performing layering, taking the water layer, and adjusting alkali with a sodium hydroxide solution to obtain a crude product, and carrying out reduced pressure rectification to obtain a finished product. According to the method, the N-methyl-1-naphthalenemethylamine finished product is successfully synthesized directly in a one-pot mode, the situation that the product yield is reduced due to the fact that a lot of residues are generated is avoided, meanwhile, the safety risk in the rectification process is avoided, the purity of the crude product is greatly improved, the cost is low, and the production safety is high.
N -Hydroxyphthalimide/benzoquinone-catalyzed chlorination of hydrocarbon C-H bond using N -chlorosuccinimide
Li, Zi-Hao,Fiser, Béla,Jiang, Biao-Lin,Li, Jian-Wei,Xu, Bao-Hua,Zhang, Suo-Jiang
supporting information, p. 3403 - 3408 (2019/04/01)
The direct chlorination of C-H bonds has received considerable attention in recent years. In this work, a metal-free protocol for hydrocarbon C-H bond chlorination with commercially available N-chlorosuccinimide (NCS) catalyzed by N-hydroxyphthalimide (NHPI) with 2,3-dicyano-5,6-dichlorobenzoquinone (DDQ) functioning as an external radical initiator is presented. Aliphatic and benzylic substituents and also heteroaromatic ones were found to be well tolerated. Both the experiments and theoretical analysis indicate that the reaction goes through a process wherein NHPI functions as a catalyst rather than as an initiator. On the other hand, the hydrogen abstraction of the C-H bond conducted by a PINO species rather than the highly reactive N-centered radicals rationalizes the high chemoselectivity of the monochlorination obtained by this protocol as the latter is reactive towards the C(sp3)-H bonds of the monochlorides. The present results could hold promise for further development of a nitroxy-radical system for the highly selective functionalization of the aliphatic and benzylic hydrocarbon C-H.
Enantioselective, Lewis Base-Catalyzed Sulfenocyclization of Polyenes
Tao, Zhonglin,Robb, Kevin A.,Zhao, Kuo,Denmark, Scott E.
supporting information, p. 3569 - 3573 (2018/03/21)
A sulfenium-ion-initiated, catalytic, enantioselective polyene cyclization is described. Homogeranylarenes and ortho-geranylphenols undergo polycyclization in good yield, diastereoselectivity, and enantioselectivity. The stereodetermining step is the generation of an enantiomerically enriched thiiranium ion from a terminal alkene and a sulfenylating agent in the presence of a chiral Lewis basic catalyst. The use of hexafluoroisopropyl alcohol as the solvent is crucial to obtain good yields. The thioether moiety resulting from the reaction can be subsequently transformed into diverse oxygen and carbon functionality postcyclization. The utility of this method is demonstrated by the enantioselective syntheses of (+)-ferruginol and (+)-hinokiol.