Controllable Selective Oxidation of Anilines to Azoxybenzenes and Nitrobenzenes by Regulating the Base
Shiyun Li1,2, Wei Zhao1, Lulu Wang1
1College of Chemical Engineering, Fuzhou University, Fuzhou 350108, China.
Abstract:
The importance of selectively oxidizing aniline into value-added chemicals azoxybenzene and nitrobenzene is well-recognized in organic synthesis. However, the lack of control over selectivity and the complex synthesis of costly catalysts significantly hinder these reactions' industrial applications. In this work, an environmentally friendly approach was developed for the selective oxidization of substituted anilines. This method involves adjusting the strength of alkalinity with peroxide as the oxidant, without the addition of any metals or additives. A mild base (NaF) facilitated azoxybenzene formation, while a stronger base (NaOMe) enabled the synthesis of nitroaromatics. These protocols are user-friendly and scalable, accommodating various substitution patterns and functional groups, yielding products with high to excellent yields. The findings of this work present a framework for investigating base catalysis in organic synthesis and provide a viable and effective approach for selectively oxidizing aniline.
Related Concept Videos
01:29Preparation of Amines: Reduction of Oximes and Nitro Compounds
Though catalytic hydrogenation can reduce nitrobenzenes, the reduction is nonselective in the presence of other functional groups. For instance, if nitrobenzene contains an aldehyde group,...
00:59Reactions at the Benzylic Position: Oxidation and Reduction
01:20Electrophilic Aromatic Substitution: Nitration of Benzene
01:46Oxidative Cleavage of Alkenes: Ozonolysis
Ozone is a symmetrical bent molecule stabilized by a resonance structure.
01:22Preparation of 1° Amines: Azide Synthesis
Azide ions act as good nucleophiles and react with unhindered alkyl halides to form alkyl azides. Alkyl azides do not participate in further nucleophilic substitution reactions, thereby eliminating the chances of polyalkylated products. Alkyl azides are reduced by hydride-based reducing agents, like lithium aluminum...
02:47Alkynes to Aldehydes and Ketones: Hydroboration-Oxidation
One of the convenient methods for the preparation of aldehydes and ketones is via hydration of alkynes. Hydroboration-oxidation of alkynes is an indirect hydration reaction in which an alkyne is treated with borane followed by oxidation with alkaline peroxide to form an enol that rapidly converts into an aldehyde or a ketone. Terminal alkynes form aldehydes, whereas internal alkynes give ketones as the final product.