- A green and recyclable ligand-free copper (I) catalysis system for amination of halonitrobenzenes in aqueous ammonia solution
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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.
- Li, Yan,Shi, Ruhui,Lin, Weiwei,Cheng, Haiyang,Zhang, Chao,Arai, Masahiko,Zhao, Fengyu
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- Micro-reaction preparation process 2 -amino -5 - nitrotoluene carbonitrile (by machine translation)
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The invention discloses a micro-reaction preparation process, 2 - amino -5 -nitrobenzaldehyde. The process comprises the following steps: a. heating o-chlorobenzonitrile to liquid through a water bath; b. adding liquid o-chloronitrile - organic inert solvent solution and mixed acid in step a to an organic inert solvent; c, conveying o-chlorobenzonitrile to the micro reaction module through a high-pressure infusion pump; dwell 60 - 150S discharging the reaction product unitarily by a temperature control system. b. A 55 - 75 °C temperature control system The reaction product is washed to neutrality by a sodium hydroxide solution and distilled water; e, the solvent, obtained 2 - chlorine -5 - nitrosobutyronitrile; f. in step e is 2 - added -5 - to a high-pressure reaction kettle; and then the 2 - high -5 -pressure reaction kettle is used for pressure relief to collect excess liquid ammonia and separating chlorobenzene and reaction products 2.5h; and the solvent is distilled and recovered by a compression pump; and chlorobenzene and reaction products are separated. J. The reaction product in step i is washed and then dried. (by machine translation)
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Paragraph 0026; 0032-0037; 0038; 0044-0049; 0050; 0056-0061
(2019/08/01)
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- Synthetic process of 2-cyano-4-nitroaniline
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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.
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Paragraph 0024
(2016/10/24)
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- Facile and efficient synthesis and biological evaluation of 4-anilinoquinazoline derivatives as EGFR inhibitors
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Series of 4-anilinoquinazoline derivatives were conveniently and efficiently synthesized and their antitumor activities were evaluated by MTT assay in three human cancer cell lines: H1975, HepG2 and SMMC-7721. New compounds 19a-19h were designed and synthesized to seek for powerful EGFR inhibitors and to explore whether methyl group at C-2 position of quinazoline ring has a positive effect on EGFR inhibition. All the compounds of 19a-19h were found potent against all three cell lines and five compounds (19c, 19d, and 19f-19h) were found more potent against H1975 than gefitinib. SAR studies revealed that methyl group at C-2 position of quinazoline ring could significantly improve the antitumor potency of 4-anilinoquinazolines. The same conclusion was also drawn according to the results of Western blotting analysis. Among all the tested compounds, 19g exhibited extremely potent against H1975 with an IC50 value of 0.11 μM, remarkably lower than that of gefitinib (1.23 μM). The results of western blotting analysis showed that compounds 19c and 19g could notably inhibit the expression of phosphorylated EGFR, especially 19g, almost inhibited completely.
- Wang, Zheng,Wu, Xue,Wang, Li,Zhang, Jiao,Liu, Jianli,Song, Zhongxing,Tang, Zhishu
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p. 2589 - 2593
(2016/05/09)
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- Steric-Hindrance-Induced Regio- and Chemoselective Oxidation of Aromatic Amines
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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.
- Patil, Vilas Venunath,Shankarling, Ganapati Subray
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p. 7876 - 7883
(2015/09/01)
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- Detosylation of 3-amino-1-tosylindole-2-carbonitriles using DBU and thiophenol
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Attempted detosylation of the 3-amino-1-(p-tosylamino)indole-2-carbonitriles 4a-c using either K2CO3 in EtOH or DBU in PhH at reflux gives unexpectedly the 3-(N-p-tosylamino)indole-2-carbonitriles 5a-c, respectively in high yields. Nevertheless, treatment of 1-(p-tosylamino)indoles 4a-c with thiophenol and DBU in PhH at reflux gives the detosylated 3-aminoindole-2-carbonitriles 5a-c. Reaction mechanisms supporting the tosyl migration (4→5) and the reductive detosylation (4→2) are proposed. All new compounds are fully characterised.
- Michaelidou, Sophia S.,Koutentis, Panayiotis A.
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experimental part
p. 3016 - 3023
(2010/06/14)
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- The conversion of 2-cyano cyanothioformanilides into 3-aminoindole-2- carbonitriles using triphenylphosphine
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2-Cyano cyanothioformanilide 3a reacts with triphenylphosphine in the presence of water to give 2-(cyanomethyleneamino)benzonitrile 4a, 2-(cyanomethylamino)benzonitrile 5, 3-aminoindole-2-carbonitrile 2a and (2-cyanoindol-3-yl)iminotriphenylphosphorane 6a. In the presence of p-toluenesulfonic acid in MeOH the reaction between 2-cyano cyanothioformanilide 3a and triphenylphosphine (2 equiv) gives 3-aminoindole-2-carbonitrile 2a in 90% yield. Under the same conditions 2-(cyanomethyleneamino)benzonitrile 4a gives anthranilonitrile 8a, 3-aminoindole-2-carbonitrile 2a and N-(2-cyanophenyl)formamide 9. In addition, substituted 2-cyano cyanothioformanilides 3b-f react with triphenylphosphine and p-toluenesulfonic acid in MeOH to give 3-aminoindole-2-carbonitriles 2b-f in 63-75% yields. Under analogous conditions 2-cyano-4,5-dimethoxyphenyl cyanothioformanilide 2g gives only 4,5-dimethoxyanthranilonitrile 8g and 4,6,7-trimethoxyquinazoline-2- carbonitrile 14g, but in refluxing dry PhMe in the absence of p-toluenesulfonic acid 2-cyano-4,5-dimethoxyphenyl cyanothioformanilide 3g, (2-cyano-5,6- dimethoxyindol-3-yl)iminotriphenylphosphorane 6g and 2-(cyanomethyleneamino)-4, 5-dimethoxybenzonitrile 4g are obtained. The structure of 2- (cyanomethyleneamino)-4,5-dimethoxybenzonitrile 4g is supported unambiguously via independent synthesis and comparison to the isomeric 6,7- dimethoxyquinazoline-2-carbonitrile 15. All new compounds are fully characterised and a tentative mechanism for the transformation of 2-cyano cyanothioformanilides to indoles is proposed.
- Koutentis, Panayiotis A.,Michaelidou, Sophia S.
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scheme or table
p. 6032 - 6039
(2010/09/11)
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- The conversion of 2-(4-chloro-5H-1,2,3-dithiazolylideneamino)benzonitriles into 3-aminoindole-2-carbonitriles using triphenylphosphine
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2-(4-Chloro-5H-1,2,3-dithiazolylideneamino)benzonitrile 1a reacts with triphenylphosphine (4 equiv) in the presence of water (2 equiv) to afford anthranilonitrile 2a, 3-aminoindole-2-carbonitrile 3a and (2-cyanoindol-3-yl)iminotriphenylphosphorane 4a, tog
- Michaelidou, Sophia S.,Koutentis, Panayiotis A.
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experimental part
p. 8428 - 8433
(2009/12/26)
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- Acetonitrile-mediated synthesis of 2,4-dichloroquinoline from 2-ethynylaniline and 2,4-dichloroquinazoline from anthranilonitrile
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2,4-Dichloroquinolines and 2,4-dichloroquinazolines were synthesized from 2-ethynylanilines and anthranilonitriles, respectively, using diphosgene in acetonitrile and heating at 130 °C or 150 °C for 12 hours. This reaction was applied to the synthesis of 4,6-dichloropyrazolo[3,4-d]pyrimidine (dichloro-9H-isopurine). The postulated mechanism is also described. Georg Thieme Verlag Stuttgart.
- Lee, Jae Hak,Lee, Byoung Se,Shin, Hyunik,Nam, Do Hyun,Chi, Dae Yoon
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- Nitroarylamines via the Vicarious Nucleophilic Substitution of Hydrogen: Amination, Alkylamination, and Arylamination of Nitroarenes with Sulfenamides
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A new reaction of sulfenamides with electrophilic arenes under basic conditions is described. The σ adducts formed from nitroarenes and the anions of sulfenamides undergo elimination of thiol to produce the corresponding o- and/or p-nitroanilines. This reaction is analogous to the known alkylation and hydroxylation of nitroarenes via the vicarious nucleophilic substitution of hydrogen (VNS). The reaction gives access to a wide range of substituted nitroanilines, nitronaphthylamines, and aminoheterocycles. By means of the reaction with N-alkyl- and N-arylsulfenamides, it is possible to obtain N-alkylnitroanilines and nitrodiarylamines. By varying the structure of sulfenamide and the reaction conditions, particularly the nature and concentration of the base, it is possible to control the orientation of animation.
- Makosza, Mieczyslaw,Bialecki, Maciej
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p. 4878 - 4888
(2007/10/03)
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- Dye mixture containing at least four diazo dyes having the same color with a diaminopyridine coupling component
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Dye mixtures comprising at least 4 dyes of the same color having the formula STR1 where D is the radical of a diazo component of the aminoanthraquinone, aniline, aminothiophene, aminothiazole, aminoisothiazole, aminothiadiazole or aminobenzisothiazole series, one of X1 and X2 is substituted or unsubstituted phenylamino while the other is a radical of the formula NH--L--O--R, where L is substited or unsubstituted C2 -C8 -alkylene, and R is hydrogen, C1 -C4 or C1 -C3 -alkanoyl, are useful for dyeing or printing textile materials.
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- Reactions of 3-Amino-2,1-benzothiazole and 3-Aminoindazole with Nitrosonium Hydrogen Sulfate and Nitric Acid in Concentrated Sulfuric Acid
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Successive treatment of 3-amino-2,1-benzothiazole in concentrated sulfuric acid by nitrosonium hydrogen sulfate and nitric acid results in formation of 2,1-benzothiazole-3-diazonium ion which undergoes nitration to yield 7-nitro-2,1-benzothiazole-3-diazonium ion as the sole product. A similar reaction with 3-amino-1H-indazole yields preferentially 7-nitro- and 1-nitro-1H-indazole-3-diazonium ions, the 7-nitro isomer prevailing. Nitration of the nondiazotized amines under the same conditions affords mainly corresponding 5-nitro derivatives. The diazonium salts formed as the major and minor products were identified by 13C and 1H NMR spectroscopy and by diazo coupling products.
- Gorelik,Lomzakova,Khamidova,Kuznetsova
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p. 1682 - 1689
(2007/10/03)
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- Process for the preparation of aromatic amines
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Electrophilic aromatic compounds can be reacted with sulphenamides in the presence of bases to form the corresponding aromatic amines.
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- Gamma-Glutamyl-4-azoanilides
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The present invention provides gamma-glutamyl-4-azoanilides, processes for their preparation and their use as substrates for gamma-glutamyl transferase determination, of the formula STR1 wherein X is alkyl, --(CH2)m --COOH or --O--(CH2)n --COOH wherein m is 0-4 and n is 1-4; R is optionally substituted p-nitrophenyl; an optionally substituted thiophene residue; an optionally substituted thiazole residue; an optionally substituted benzothiazole residue; an optionally substituted benzoisothiazole residue; an N-alkylthiazole residue; or an optionally substituted 1,3,5-thiodiazole residue; as well as the alkali metal, alkaline earth metal and ammonium salts thereof.
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- Direct Amination of Nitrobenzenes by Vicarious Nucleophilic Substitution
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4-Amino-1,2,4-triazole reacts at 25 deg C with nitrobenzene and some substituted nitrobenzenes in the presence of potassium tert-butoxide in Me2SO to give 4-nitroanilines in good yields.The reaction represents an extension of Makosza's vicarious substitution to a convenient nitrogen nucleophile.
- Katritzky, Alan R.,Laurenzo, Kathleen S.
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p. 5039 - 5040
(2007/10/02)
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- Azo pigments derived from 2-hydroxy-3-carboxynaphthalene containing a substituted or unsubstituted phthalimide
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Azo pigments derived from 2-hydroxy-3-carboxy-naphthalene and containing a substituted or unsubstituted phthalimide radical. The majority give red colorations and due to their excellent fastness properties are particularly valuable for use in surface coatings and resins.
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