The N-Chlorination of Primary Amines Using FeCl3 and m-CPBA

Abstract

A simple and effective method for the synthesis of N,N-dichloroamines from primary amines was conducted successfully with m-CPBA as oxidant and FeCl3 as chlorine source at 0 °C. Moreover, N,N-dichloroamines could be converted into nitriles or N-chloroimines in good yields.

A Practical Oxidative Conversion of Aldehydes into N-Chloroaldimines

“…Subsequently, our attention was focused on searching for a suitable temperature for the chlorosubstitution reaction. It was observed that the highest yield was obtained when the reaction was carried out at 50 °C (Table 1, entry 7) and increasing or decreasing the temperature all showed a negative effect (Table 1, entries 5,6,8). We also found that appropriately extending the reaction time could contribute to a higher yield of desired product (Table 1, entries 9-11) and a slightly lower yield was obtained when the time was prolonged over 2 h (Table 1, entry 12).…”

“…In addition, isoxazole, an important structural feature of nucleozin, which is an effective anti-influenza drug, can be prepared by the ring formation between N-chloroaldimines and ethyl acetoacetate. [4][5][6] Due to the extensive applications of N-chloroaldimines, studying efficient strategies for their synthesis is considered highly desirable. The traditional method for preparation of N-chloroaldimines involved chloro-substitution of an aromatic oxime, which could be prepared by condensation between an aldehyde and hydroxylamine [Scheme 1, Eqn (1)].…”

“…For example, in 2014, Liu et al described a facile two-step method for the synthesis of N-chloroaldimines by chlorination of phenylmethanamine, followed by dehydrochlorination with Et 3 N in dichlomethane to yield the final products [Scheme 1, Eqn (2)]. 6 Another facile method for the synthesis of N-chloroaldimines was developed by Gaspa's group. 2…”

Applications of Oxone® in Organic Synthesis: An Emerging Green Reagent of Modern Era

“…Several methods have already been studied for the generation of N-chloroamines by using mchloroperbenzoic acid-FeCl 3 , Ca(OCl) 2 , Cl 2 À H 2 O, NCS, isocyanuric chloride and t BuOCl. [163][164][165][166] In this context, recently, Sriramoju et al reported an efficient and expedient methodology for the synthesis of N-chloroamines 195 a-o in low to excellent yields from a variety of amines 194 using oxone-KCl combination under mild reaction conditions as detailed in the Scheme 61. [167] A suitable mechanism for N-chlorination reactions which passes through the intermediate 196 to furnish the desired product 195 is described in the Scheme 62.…”

“…The N ‐chloroamines are imperative intermediates in synthetic organic chemistry for the preparation of nitriles, chloroimines, diazene N ‐oxides, diazirines, nitramides and aminoketones in addition to their applicability for Buchwald‐Hartwig type amination reactions. Several methods have already been studied for the generation of N ‐chloroamines by using m ‐chloroperbenzoic acid‐FeCl 3 , Ca(OCl) 2 , Cl 2 −H 2 O, NCS, isocyanuric chloride and t BuOCl [163–166] . In this context, recently, Sriramoju et al .…”