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Relevant academic research and scientific papers

Selective Catalytic Oxidation of Arylamines to Azoxybenzenes with H2O2 over Zeolites

Catalytic version of the H2O2-TS-1 combination has been shown to display a good reaction selectivity in the liquid-phase oxidation of anilines to symmetrical azoxybenzenes.

Tandem selective reduction of nitroarenes catalyzed by palladium nanoclusters

We report a catalytic tandem reduction of nitroarenes by sodium borohydride (NaBH4) in aqueous solution under ambient conditions, which can selectively produce five categories of nitrogen-containing compounds: anilines, N-aryl hydroxylamines, azoxy-, azo- and hydrazo-compounds. The catalyst is in situ-generated ultrasmall palladium nanoclusters (Pd NCs, diameter of 1.3 ± 0.3 nm) from the reduction of Pd(OAc)2 by NaBH4. These highly active Pd NCs are stabilized by surface-coordinated nitroarenes, which inhibit the further growth and aggregation of Pd NCs. By controlling the concentration of Pd(OAc)2 (0.1-0.5 mol% of nitroarene) and NaBH4, the water/ethanol solvent ratio and the tandem reaction sequence, each of the five categories of N-containing compounds can be obtained with excellent yields (up to 98%) in less than 30 min at room temperature. This tunable catalytic tandem reaction works efficiently with a broad range of nitroarene substrates and offers a green and sustainable method for the rapid and large-scale production of valuable N-containing chemicals.

Method for synthesizing oxidized azo compound through selective oxidation of aromatic amine

The invention discloses a method for synthesizing an oxidized azo compound through selective oxidation of an aromatic amine, wherein an aromatic amine is used as a raw material, hydrogen peroxide is used as an oxidizing agent, a titanium-silicon molecular sieve or a metal modified titanium-silicon molecular sieve is used as a catalyst, and the aromatic amine is subjected to selective catalytic oxidation to prepare the corresponding oxidized azobenzene compound. According to the present invention, the method has advantages of environmental protection, good selectivity, high product yield, easyseparation and recycling of the catalyst, simple instrument required by the reaction, and easy operation.

Organocatalytic oxidation of substituted anilines to azoxybenzenes and nitro compounds: Mechanistic studies excluding the involvement of a dioxirane intermediate

An organocatalytic and environmentally friendly approach for the selective oxidation of substituted anilines was developed. Utilizing a 2,2,2-trifluoroacetophenone-mediated oxidation process, substituted anilines can be transformed into azoxybenzenes, while a simple treatment with MeCN and H2O2 leads to the corresponding nitro compounds, providing user-friendly protocols that can be easily scaled up. Various substitution patterns and functional groups were tolerated leading to products in high to excellent yields. Mechanistic studies utilizing HRMS provide clear evidence for the distinct mechanistic intermediates that are involved. This study constitutes an indirect proof excluding the involvement of a dioxirane intermediate in the green organocatalytic oxidation, utilizing 2,2,2-trifluoroacetophenone as the catalyst.

Switchable selectivity during oxidation of anilines in a ball mill

A solvent-free method for the direct oxidation of anilines to the corresponding azo and azoxy homocoupling products by using a planetary ball mill was developed. Various oxidants and grinding auxiliaries were tested and a variety of substituted anilines were investigated. It was possible to form chemoselectively either azo, azoxy, or the nitro compounds from reaction of aromatic anilines. The selectivity of the solvent-free reaction is switchable by applying a combination of oxidant and grinding auxiliary. Furthermore, a comparison with other methods of energy input (microwave, classical heating, and ultrasound) highlighted the advantages of the ball mill approach and its high energy efficiency. Grinding reactions: Highly efficient oxidative homocoupling of aromatic amines was performed under solvent-free conditions in a planetary ball mill (see scheme). The choice of solid oxidants and grinding auxiliaries allowed selective generation of the oxidized products. Other methods of energy input are compared with respect to reaction time and energy consumption.

Reduction of mononitroarenes by hydroxide ion in water catalyzed by β-cyclodextrin: enhanced reactivity of hydroxide ion

Ordinarily the reducing ability of HO- in water is extremely low as a result of its stabilization by hydration. Reductions by hydroxide ion have only been observed previously in aprotic organic solvents. We find that several mononitroarenes are reduced to azoxyarenes by NaOH in water in the presence of β-cyclodextrin. HO- acts as a one-electron reductant with enhanced reactivity.

Selective photoreduction of nitrophenyl ethers by amines in ternary β-cyclodextrin complexes. A spectroscopic and mechanistic study

The photoreduction of nitrophenyl ethers by amines has been studied in aqueous solution in the presence of β-cyclodextrin (β-CD), and in ternary β-cyclodextrin complexes in the solid state. NMR (NOESY) and induced circular dichroism (ICD) studies in solution suggest the operation of a cooperative effect by the amine in the complexation of the nitrophenyl ether by the β-CD, evidencing the existence of interactions between complementary groups that govern the structure of the ternary complexes. Irradiation of the solutions shows an inhibitory effect of the β-CD, together with a significant increase in the chimioselectivity of the photoreaction. This tendency is confirmed by irradiation of the solid ternary complexes that show a complete selectivity, only producing the nitroso derivative. A time-resolved diffuse reflectance laser flash photolysis (DRLFP) mechanistic study on the solid complexes has demonstrated that in the ternary β-CD complexes, the evolution of the first transient (assigned to the triplet excited state of the nitropheny ether) is completely different than in solution or in mechanical cellulose mixtures, this approach being a very valuable tool to investigate bimolecular photoinduced reactions difficult to study in solution due to the existence of other competitive processes.

Photosubstitution-photoreduction mechanistic duality in the SET photoreactions of nitrophenyl ethers with amines. The role of the steps that follow the ET

Nitrophenyl ethers are photoreduced by primary amines in water through a mechanism initiated by single electron transfer that is in direct competition with the single electron transfer photosubstitution mechanism (S(N)Ar*-SET). Our results indicate that the preferred pathway does not depend on the electron donor or proton donor ability of the amine. The key factor that determines the progress of the photoreaction is the structure of the carbon skeleton of the amine, particularly the type of hydrogens on the carbon α to the amino group. A mechanistic rationale that includes hydrogen atom transfer as a key step is discussed.

Catalytic selective oxidation of amines with hydroperoxides over molecular sieves: Investigations into the reaction of alkylamines, arylamines, allylamines and benzylamines with H2O2 and TBHP over TS-1 and CrS-2 as the new catalyst

The liquid phase oxidation of various substituted amines with dil H2O2 and tert-butyl hydroxyperoxide (TBHP) has been investigated over titanium and chromium silicates respectively. While TS-1/H2O2 combination exhibits a remarkable activity and selectivity in the oxidation of arylamines to produce the symmetrical azoxybenzenes, CrS-2 catalyzes the selective oxidation of various substituted amines to the corresponding nitro compounds by oxidation with 70% TBHP. The nature of the reactive intermediates during the oxidation of anilines to nitrobenzenes has been established using cyclic voltammetry experiments. Further, amines possessing α C-H bonds are selectively oxidized to either oximes or the carbonyl compounds on reaction with H2O2 catalyzed by TS-1.

FORMATION OF METHOXY-SUBSTITUTED AZOXYBENZENES IN THE REDUCTION OF NITROARENES IN BASIC METHANOL-TOLUENE SOLUTIONS

The reduction of nitroarenes in boiling methanol-toluene containing KOH affords high yields of the corresponding azoxy derivative and small amounts of other azoxy compounds containing one or more OCH3 groups linked to the aromatic rings.It has been proved that the reaction does not occur via formation of methoxy-nitroarenes and their further reduction.The reaction is proposed to involve: a) formation of a Meisenheimer complex by attack of the methoxide ion on the nitroarene; b) abstraction of a proton from the Meisenheimer complex by a methoxide ion to form a dianion; c) protonation of the dianion with concurrent elimination of OH to form the nitroso-methoxy arene which is finally reduced to the methoxy-azoxy derivative.It is proposed that the dianion is the electron-donating species to start the reduction of nitro- and nitrosoarenes.