86-52-2Relevant articles and documents
New synthesis process of naftifine drug intermediate N-methyl-1-naphthalenemethylamine
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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.
Manganese-salen catalyzed oxidative benzylic chlorination
Sasmal, Sheuli,Rana, Sujoy,Lahiri, Goutam Kumar,Maiti, Debabrata
, (2018/07/14)
Abstract: Metalloporphyrins are well-known to serve as the model for mimicking reactivities exhibited by cytochrome P450 hydroxylase. Recent developments on selective C–H halogenation using Mn-porphyrins provided the way for understanding the reactivity as well as mechanism of different halogenase enzymes. In this report, we demonstrated a method for benzylic C–H chlorination using easily prepared Mn(salen) complex as the catalyst, which shows a complementary reactivity of Mn-porphyrins. Here, NaOCl has been used as a chlorinating source as well as the oxidant. Efforts towards understanding the mechanism suggested the formation of the high-valent Mn(V)=O species which is believed to be the key intermediate to conduct this transformation. Graphical abstract: SYNOPSIS Mn(salen)-catalyzed selective benzylic chlorination protocol has been developed using aqueous NaOCl solution. Reactions proceeded efficiently at room temperature and displayed good functional group tolerance. The mechanistic investigation demonstrated that Mn (V) = O species is likely to be the key intermediate which is responsible to generate benzylic radical. EPR and ESI-MS studies confirmed the in situ formation of Mn(IV)-species.[Figure not available: see fulltext.].