17420-30-3Relevant articles and documents
A green and recyclable ligand-free copper (I) catalysis system for amination of halonitrobenzenes in aqueous ammonia solution
Li, Yan,Shi, Ruhui,Lin, Weiwei,Cheng, Haiyang,Zhang, Chao,Arai, Masahiko,Zhao, Fengyu
, (2019/06/18)
The amination of halonitrobenzenes is an important reaction to produce the corresponding nitroanilines. Direct amination of p-chloronitrobenzene (p-CNB) to p-nitroaniline (p-NAN) with aqueous NH3 solution was investigated over various transition metal salts in the absence of ligand, inorganic base and organic solvent. It was found that CuI is the most effective catalyst with respect to p-CNB conversion, p-NAN selectivity (≈ 100%) and the post-reaction separation and recycling. A high p-NAN yield of 97% could be obtained at 200 °C in 6.5 h with molar ratios of NH3/p-CNB and CuI/p-CNB of 21 and 0.1, respectively. A possible reaction mechanism was proposed, in which NH3 was not only a substrate but also a ligand to coordinate with CuI and formed a water-soluble Cu complex, and then it started the catalytic cycle. The influence of reaction variables such as NH3 concentration, CuI concentration, temperature and time on the p-CNB conversion and the p-NAN selectivity was examined. At room temperature the desired product of p-NAN is insoluble in water but the Cu complex catalyst is water-soluble and so the aqueous phase including the catalyst and NH3 can be easily separated and reused for the subsequent reaction runs. The green and sustainable system is effective for the conversion of diverse halonitrobenzenes to nitroanilines.
Synthetic process of 2-cyano-4-nitroaniline
-
Paragraph 0024, (2016/10/24)
The invention relates to a synthetic process of 2-cyano-4-nitroaniline, comprising the following steps: putting chlorobenzonitrile into a sulfuric acid medium, dropwise adding mixed acid for nitration, adding water for elutriation of a nitrated object, then filtering the nitrated object, dissolving a nitrated material in chlorobenzene, performing an ammonolysis reaction by nitre-chlorine mixed fluid and liquid ammonia, then distilling to recycle a solvent, performing suction filtration, and washing to be neutral, thus obtaining a wet product. The process is simple in step and easy to control, the obtained product is high in yield, high in purity and stable in quality, and has an environmental index capable of meeting the market need, the cost is low, sewage is little, energy consumption is reduced, and the synthetic process is a production process low in energy consumption and low in pollution.
Steric-Hindrance-Induced Regio- and Chemoselective Oxidation of Aromatic Amines
Patil, Vilas Venunath,Shankarling, Ganapati Subray
, p. 7876 - 7883 (2015/09/01)
Unusual regio- and chemoselective oxidation of aromatic amines hindered with ortho substituents (except -NH2, -NHCH3, and -OH) to the corresponding nitro compounds is described by use of nonanebis(peroxoic acid). The mechanistic investigation for selective oxidation of amines ortho-substituted with -NH2 or -OH showed the involvement of H-bonding between the ortho hydrogen of the adjacent -XH group (where X = NH, NR, or O) and an oxygen atom from the diperoxy acid. Various mono- and diamines are oxidized into corresponding mononitro derivatives in high yield and purity without employing any protection strategies. The protocol was also found to successful on the gram scale.
