NH₄I/tert-Butyl Hydroperoxide-Promoted Oxidative C–N Cleavage of Tertiary Amines Leading to Nitroaromatic Compounds

Abstract

A NH4I/ tert-butyl hydroperoxide-promoted oxidation of tertiary N-aryl- N,N-dialkylamines in DMSO has been developed to access nitroaromatic compounds. This methodology involves sequential N-dealkylation reactions in one-pot and a radical pathway is proposed.

Copper‐Catalyzed Cascade N‐Dealkylation/N‐Methyl Oxidation of Aromatic Amines by Using TEMPO and Oxygen as Oxidants

“…The N ‐dealkylation transformation are usually accomplished through the following processes: 1) formation/decomposition of carbinolamine or its analogues using cytochromes P‐450, [8] Fe, [9] Cu, [10] Ru, [11] N ‐oxide, [12] nitroxyl radical, [13] dicyanonaphthalene, [14] rose Bengal [15] and iodine‐calcium (Scheme 1c, Path 1); [16] 2) formation/hydrolysis of imine intermediates using Cu, [6g] Fe, [6e] Ir, [17a] m‐chloronitrobenzene, [6j] oxoiminium ions (Scheme 1c, Path 2); [17b] and 3) formation of the N‐oxide intermediates employing peroxide and then decomposed through path 2 and 1 (Scheme 1c, Path 3) [18] . In 2017, the direct transformation from N,N ‐dimethylaniline to N ‐phenylformamide was reported by the Shao's group [19] …”

“…For the CF 3 ‐substituted arylamine 1 k , the poor yield was obtained due to low conversion of 1 k . This strategy could be also applied to the synthesis of mutagenic active molecule 2 d in 61 % yield [21] . Various halogen substituted tertiary amines were also smoothly converted into the corresponding N ‐phenylformamides ( 2 g – 2 j ).…”

“…Another possible way is that N ‐methylaniline goes through SET and PT to generate N ‐methyl radical, followed by aerobic oxidation to form 2 a [23] . In addition, intermediate e might be oxidized by TEMPO to form 2 a [19] …”

Difluoroalkylation of Anilines via Photoinduced Methods

“…Once again, deactivated anilines provide the difluoroalkylated product in low yield (18 and 19). On the other hand, the installation of the difluoroalkylated ester was amenable to 2,6-disubstituted aryl (20) and alkyl (21) anilines. Finally, the difluoroalkylation of N,N-dimethylnaphthalen-1-amine provided 22 in 61% yield.…”

Synthesis and characterization of a triphenylamine-dibenzosuberenone-based conjugated organic material and an investigation of its photovoltaic properties

“…7,8 Although dibenzosuberenone has many dibenzo derivatives, the 2,3;4,5-dibenzotropone (5H-dibenzo[a,d] [7]annulen-5-one) form has been utilized most in organic synthesis due to its symmetrical structure. This core skeleton is widely used, especially in materials chemistry, in photovoltaic applications, as a light-emitting diode, as an organic light-emitting diodes (OLED) in organic electronic applications, and in field-effect transistors, [9][10][11] as well as in new bipolar molecular materials with high optoelectronic performances. 12,13 In addition, the core skeleton has found various applications in polymer synthesis [14][15][16][17][18] and in metal-ligand complexes and in the formation of coordination cages.…”