cas 99-30-9, 2,6-Dichloro-4-nitroaniline | Articles data

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Activator free, expeditious and eco-friendly chlorination of activated arenes by N-chloro-N-(phenylsulfonyl)benzene sulfonamide (NCBSI)
N-Chloro-N-(phenylsulfonyl)benzene sulfonamide (NCBSI) has been explored for the first time as a chlorinating reagent for direct chlorination of various activated arenes and heterocycles without any activator. A comparative in-silico study was performed to determine the electrophilic character for NCBSI and commercially available N-chloro reagents to reveal the reactivity on a theoretical viewpoint. The reagent was prepared by an improved method avoiding the use of hazardous t-butyl hypochlorite. This reagent was proved to be very reactive compared to other N-chloro reagents. The precursor of the reagent N-(phenylsulfonyl)benzene sulfonamide was recovered from aqueous spent, which can be recycled to synthesize NCBSI. The eco-friendly protocol was equally applicable for the synthesis of industrially important chloroxylenol as an antibacterial agent.
Misal, Balu,Palav, Amey,Ganwir, Prerna,Chaturbhuj, Ganesh
supporting information

(2021/01/04)

Synthesis method of 2, 6-dichloro-4-aminophenol
The invention discloses a synthesis method of 2, 6-dichloro-4-aminophenol, and belongs to the field of preparation of pesticide, medicine and dye intermediates, 2, 6-dichloro-4-aminophenol is obtained by adopting paranitroaniline as a raw material through the steps of chlorination, diazonium hydrolysis, hydrogenation and the like, methanol is adopted as a solvent for chlorination, filtrate can be repeatedly used, and the use of a large amount of acid water is reduced; toluene is selected as a solvent in diazotization, diazonium liquid is directly layered after being hydrolyzed, an organic layer is separated out, water vapor distillation is not needed, and the distillation risk and energy consumption are reduced; toluene is selected as a hydrogenation solvent, and an organic layer separated after the diazonium liquid is hydrolyzed is directly hydrogenated, so that the process flow is simplified.
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Paragraph 0023; 0031-0032; 0035-0036; 0039-0040

(2021/06/12)

Identification of Potent and Selective Inhibitors of Fat Mass Obesity-Associated Protein Using a Fragment-Merging Approach
Fat mass obesity-associated protein (FTO) is a DNA/RNA demethylase involved in the epigenetic regulation of various genes and is considered a therapeutic target for obesity, cancer, and neurological disorders. Here, we aimed to design novel FTO-selective inhibitors by merging fragments of previously reported FTO inhibitors. Among the synthesized analogues, compound 11b, which merges key fragments of Hz (3) and MA (4), inhibited FTO selectively over alkylation repair homologue 5 (ALKBH5), another DNA/RNA demethylase. Treatment of acute monocytic leukemia NOMO-1 cells with a prodrug of 11b decreased the viability of acute monocytic leukemia cells, increased the level of the FTO substrate N6-methyladenosine in mRNA, and induced upregulation of MYC and downregulation of RARA, which are FTO target genes. Thus, Hz (3)/MA (4) hybrid analogues represent an entry into a new class of FTO-selective inhibitors.
Elboray, Elghareeb E.,Fujiwara, Yoshie,Itoh, Yukihiro,Kitao, Yuki,Kotoku, Masayuki,Mellini, Paolo,Oba, Makoto,Obika, Satoshi,Prakash, Muthuraj,Roy, Rohini,Singh, Ritesh,Suzuki, Takayoshi,Takada, Yuri,Takahashi, Yukari,Terao, Mitsuhiro,Wang, Dan Ohtan,Yamaguchi, Takao,Yamamoto, Chika,Yamashita, Yasunobu
supporting information
p. 15810 - 15824
(2021/11/18)

General and selective synthesis of primary amines using Ni-based homogeneous catalysts
The development of base metal catalysts for industrially relevant amination and hydrogenation reactions by applying abundant and atom economical reagents continues to be important for the cost-effective and sustainable synthesis of amines which represent highly essential chemicals. In particular, the synthesis of primary amines is of central importance because these compounds serve as key precursors and central intermediates to produce value-added fine and bulk chemicals as well as pharmaceuticals, agrochemicals and materials. Here we report a Ni-triphos complex as the first Ni-based homogeneous catalyst for both reductive amination of carbonyl compounds with ammonia and hydrogenation of nitroarenes to prepare all kinds of primary amines. Remarkably, this Ni-complex enabled the synthesis of functionalized and structurally diverse benzylic, heterocyclic and aliphatic linear and branched primary amines as well as aromatic primary amines starting from inexpensive and easily accessible carbonyl compounds (aldehydes and ketones) and nitroarenes using ammonia and molecular hydrogen. This Ni-catalyzed reductive amination methodology has been applied for the amination of more complex pharmaceuticals and steroid derivatives. Detailed DFT computations have been performed for the Ni-triphos based reductive amination reaction, and they revealed that the overall reaction has an inner-sphere mechanism with H2metathesis as the rate-determining step.
Beller, Matthias,Chandrashekhar, Vishwas G.,Jagadeesh, Rajenahally V.,Jiao, Haijun,Murugesan, Kathiravan,Wei, Zhihong
p. 4332 - 4339
(2020/05/18)

Environment-friendly 2, 6-dichloro-4-nitroaniline preparation method
The invention discloses an environment-friendly 2, 6-dichloro-4-nitroaniline preparation method, and belongs to the field of environmental protection. The environment-friendly 2, 6-dichloro-4-nitroaniline preparation method comprises the following steps: step 1, adding o-dichlorobenzene, namely a component shown as a formula (I), into a nitric acid and sulfuric acid solution for reaction to obtainm-nitro-1, 2-dichlorobenzene, namely a component shown as a formula (II); step 2, adding the m-nitro-1, 2-dichlorobenzene obtained in the step 1 into an ammonia water solution for reaction to obtain2-chloro-4-nitroaniline, namely a component shown as a formula (III); step 3, dropwise adding hydrochloric acid and a hydrogen peroxide solution into the 2-chloro-4-nitroaniline obtained in the step 2. According to the new preparation method, the generation of polychlorophenol during the 2, 6-dichloro-4-nitroaniline preparation process is effectively reduced, the environmental protection meets therequirements of OECO-Textile 100, and a dye obtained after the actual production of the preparation method directly meets the requirements of OECO-Textile 100.
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(2020/08/27)

Identification of novel scaffold using ligand and structure based approach targeting shikimate kinase
Tuberculosis (TB) remains a major global health problem. It causes ill-health among millions of people each year and rank as the second leading cause of death from an infectious disease worldwide, after the human immunodeficiency virus (HIV). Shikimate kinase is one of the major enzymes targeted for TB. Most approaches to overcome TB were based on synthesis and screening of a known compounds to obtain a few representatives with desired potency. In this study, we have applied a virtual screening approach which combines ligand- and structure-based approaches to screen a large library of compounds as a starting point for the identification of new scaffolds for the development of shikimate kinase inhibitors. The combined approach has identified 2 new scaffolds as potential inhibitors of shikimate kinase. To prove the approach, few of the molecules and their derivatives, a total of 17 compounds, were synthesized. The compounds were tested for biological activity and shows moderate activity against shikimate kinase. The shikimate kinase enzyme inhibition study reveals that the compounds showed inhibition (IC50) at concentrations of 50 μg/mL (Compounds 21, 22, 24, 25, 26, 27, 30, 32, 34) and 25 μg/mL (14, 19, 23, 31, 33).
Rahul Reddy,Krishnasamy, Sivakumar Kullampalayam,Kathiravan
(2020/08/05)

Cyclic synthesis method of nitroaniline chloride
The invention discloses a cyclic synthesis method of nitroaniline chloride. The cyclic synthesis method comprises the following steps: (1) mixing nitroaniline and sulfuric acid, and preheating to a chlorination reaction temperature; (2) respectively inputting the solution obtained in the step (1) and chlorine into a reactor to carry out a chlorination reaction, cooling the material obtained in thereaction to obtain a supersaturated solution, and crystallizing to separate out a supersaturated product namely nitroaniline chloride; and (3) carrying out solid-liquid separation on the material cooled in the step (2), carrying out flash evaporation on the obtained saturated nitroaniline chloride/sulfuric acid solution, recycling hydrogen chloride, and circulating hydrogen chloride to the step (1) to replace sulfuric acid for dissolving nitroaniline, thereby realizing cyclic synthesis of nitroaniline chloride. Product super-saturation precipitation and saturated solution circulation are realized, the proportion of raw materials in a reaction system is reduced, the reaction is promoted to enter a uniform liquid phase system, meanwhile, mother liquor can be recycled, and the purposes of high efficiency, controllability and comprehensive utilization of resources are achieved.
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Paragraph 0032; 0033; 0038; 0039

(2020/10/05)

2,6-dichloro-4-nitroaniline low-temperature synthesis method
The invention discloses a low-temperature synthesis method of 2,6-dichloro-4-nitroaniline. The method comprises the following steps sequentially: (1) by taking 20-35% diluted hydrochloric acid or a filtrate obtained in the following step (2) as a solvent I, firstly adding p-nitroaniline into the solvent I, then, introducing chlorine gas for chlorination reaction, naturally standing a reaction solution at room temperature after the reaction ends, and filtrating so as to obtain 2,6-dichloro-4-nitroaniline and hydrochloric acid mother liquor; (2) by taking the hydrochloric acid mother liquor as a solvent II, adding the solvent II into a three-mouthed flask, then, adding p-nitroaniline, dropwise adding hydrogen peroxide, carrying out stirring reaction while carrying out heat preservation after dropwise adding is completed, naturally standing at room temperature after the reaction ends so as to precipitate solid, and filtrating, thereby obtaining 2,6-dichloro-4-nitroaniline and the filtrate. 2,6-dichloro-4-nitroaniline synthesized by adopting the method disclosed by the invention has advantages of low cost, high atomic economical efficiency, no wastewater discharge, environment friendliness, high efficiency and the like.
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Paragraph 0038; 0039; 0091

(2017/04/04)

A chlorine direct chlorination and at the same time the hydrogen peroxide oxidizing chloride preparation of 2,6-dichloro-4-nitroaniline method
The invention relates to a method for preparing 2,6-dichloro-4-nitroaniline through direct chlorination of chlorine gas and oxidative chlorination of hydrogen peroxide. The method comprises the following steps: (1) adding paranitroaniline into hydrochloric acid at the concentration of 5-35wt%, heating to 40-80 DEG C, stirring for uniformly mixing, slowly inflating the chlorine gas within 0.5-5h, slowly adding hydrogen peroxide dropwise, and after adding the chlorine gas and the hydrogen peroxide, continuing to preserve heat and react for 0.3-1.5h; (2) filtering a product obtained in the step (1), washing a filter cake to be neutral, and drying to obtain the 2,6-dichloro-4-nitroaniline. By regulating a dosage ratio of the chlorine gas to the hydrogen peroxide, the concentration of the hydrochloric acid in a reaction system can be kept unchanged, the reaction process is steady and easily controlled, and the product is high in yield and purity.
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Paragraph 0037-0039

(2017/02/02)

Clean technology for continuously synthesizing 2,6-dichloro-p-nitroaniline
A clean technology for continuously synthesizing 2,6-dichloro-p-nitroaniline adopts multistage serially connected reaction kettles and comprises the following steps: continuously adding 2,4-dinitroaniline, hydrochloric acid and chlorine to a first stage reaction kettle, carrying out a chlorination reaction under stirring, allowing parts of a material in a previous reaction kettle to enter a self reaction kettle through a pump and to circulate, allowing parts of the material in the previous reaction kettle to enter a next reaction kettle, continuously carrying out the chlorination reaction, allowing tail gas generated in the previous reaction kettle to enter the next reaction kettle, continuously carrying out the chlorination reaction, allowing parts of a material in a final stage reaction kettle to enter the self reaction kettle through a pump and to circulate, continuously discharging and filtering parts of the final obtained material after a detection result shows the reaction is completed to obtain a filter cake which is a 2,6-dichloro-p-nitroaniline product, allowing a mother liquor obtained after filtration to enter a mother liquor recovery tank, blowing air to the mother liquor in the mother liquor recovery tank, reusing hydrogen chloride tail gas obtained after blowing, pumping the blown mother liquor with certain acidity into a mother liquor storage tank, and recycling the mother liquor in the mother liquor storage tank to substitute hydrochloric acid.
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Paragraph 0042; 0043; 0044; 0045; 0046

(2016/12/16)

Steric-Hindrance-Induced Regio- and Chemoselective Oxidation of Aromatic Amines
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
p. 7876 - 7883
(2015/09/01)

Sodium lauryl sulfate-catalyzed oxidative chlorination of aromatic compounds
Chlorination of commercially important aromatic compounds using sodium chloride as chlorine source and sodium periodate as oxidant in acidic medium catalyzed by sodium lauryl sulfate (SLS) led to the chloro-substituted aromatics in good yields and purity. Addition of sodium lauryl sulfate led to increased chlorination rate, better yield, excellent purity, and better quality of end product. The advantages of the present method are greater yield, excellent purity, and shorter reaction time at room temperature. Also dichlorinated product can be obtained by increasing the amount of sodium chloride and sodium periodate at slightly higher temperature (40C).
Mahajan, Tanu,Kumar, Lalit,Dwivedi, K.,Agarwal, D. D.
p. 3655 - 3663,9
(2020/08/31)

The use of sodium chlorate/hydrochloric acid mixtures as a novel and selective chlorination agent
Sodium chlorate/hydrochloric acid mixtures were used to chlorinate activated arenes and the α-position of ketones. This chlorination method was used to produce selectively mono-, di-, and trichlorinated compounds by controlling the molarity of sodium chlorate. This reagent proved to be much more efficient and easier to handle than chlorine gas.
Moon, Byung Seok,Choi, Han Young,Koh, Hun Yeong,Chi, Dae Yoon
experimental part
p. 472 - 476
(2011/12/04)

Synthesis of aromatic aminosulfonic acid nitroamides
Nitration of aromatic aminosulfonic acid primary amides to furnish the corresponding sulfononitroamides has been described for the first time. The conditions of nitration applied ensure chemoselective mononitration and prevent decomposition of the product. Synthesis of dabsyl nitroamide sodium salt, as a potential β-amyloid aggregation inhibitor is also reported. Georg Thieme Verlag Stuttgart.
Minksztym, Kazimierz
p. 1819 - 1822
(2008/02/12)

Molecular rearrangement. 36. Selective α-CH oxidation of alkylarenes by nitrogen dioxide on thermolysis with nitramines
Thermolysis of 2,4,6-trichloro-N-nitroaniline 1 and N-methyl-2,4-dinitro-N- nitroaniline 2 each with primaryl alkylbenzenes led to the formation of acylbenzenes. Similar reactions with secondary alkylbenzenes afforded a mixture of acetophenone and aliphatic aldehydes. Use of tert-butylbenzene in this reaction yielded formaldehyde and 2,3-diphenyl-2,3-dimethylbutane. The mechanisms of the studied reactions are discussed.
Badr, Mahmoud Z. A.
p. 6706 - 6710
(2007/10/03)

Environmentally benign chlorination and bromination of aromatic amines, hydrocarbons and naphthols
A simple and efficient procedure for chlorination and bromination of aromatic amines, hydrocarbons and naphthols by the action of aqueous hydrohalic acid and hydrogen peroxide is described. This environmentally clean and safe procedure involves in situ generation of the active halogen and its uncatalyzed reaction with the substrates in this study.
Vyas, Punita V.,Bhatt, Anjani K.,Ramachandraiah, Gadde,Bedekar, Ashutosh V.
p. 4085 - 4088
(2007/10/03)

Multinuclear Magnetic Resonance Spectroscopic and Semiempirical Molecular Orbital (AM1) Studies of Substituted Anisoles
13C, 15N, and 17O NMR spectra have been recorded for 4-nitroanisole (1), its 2-methyl-, 2-chloro-, 2-bromo-, 2-iodo-, 2,6-diamethyl-, 2,6-dichloro, 2,6-dibromo-, and 2,6-diiodo-derivatives 2-9, also nitrobenzene (1a), its 3-methyl-, 3-chloro-, 3-bromo-, and 3-iodo-derivatives 2a-5a and 3,5-dichloro- and 3,5-dibromo-derivatives 7a and 8a.Analysis of the chemical shifts of carbon bearing nitro group and nitro oxygens in these compounds suggests that presence of one substituent ortho- to the methoxyl group enhances its resonance interaction with the benzene ring whereas presence of two ortho-substituents inhibits this resonance.However, in no case the resonance is completely inhibited.The extent of enhancement or inhibition is almost independent of the nature of the ortho-substituent.This conclusion has also been arrived by analyzing the reported chemical shifts of the para-carbons in anisoles 1b-9b and the corresponding carbons in benzene derivatives 1c-9c.Though evidence could not be obtained for steric enhancement of resonance using methoxyl oxygen chemical shifts, analysis of these chemical shifts in di-ortho-substituted anisoles 6-9 and 6a furnishes evidence for steric inhibition of resonance.However, 15N chemical shifts are of no use in studying these phenomena.Semiempirical molecular orbital calculations using AM1 Hamiltonian suggest that the methoxyl group is coplanar with the benzene ring in anisole, 4-nitroanisole and 2-substituted-4-nitroanisoles but is perpendicular to the benzene ring in 2,6-disubstituted-4-nitroanisoles.Moreover, in 2-substituted-4-nitroanisoles the O-methyl group is anti to the 2-substituent.
Pandiarajan, Karuppiah,Kabilan, Senthamaraikannan,Sankar, Punnaivanam,Kolehmainen,Erkki,Nevalainen, Tapio,Kauppinen, Reijo
p. 2639 - 2646
(2007/10/02)

Magnetic susceptibilities of organic compounds: Part V - Influence of substituents on diamagnetic susceptibilities of disubstituted and trisubstituted benzenes
The magnetic susceptibilities of a number of triads of isomeric disubstituted benzenes have been determined, choosing the compounds in such a way that the substituents are present in the following combinations: (i) two electron-releasing substituents, (ii) a halogeno and an electron-releasing substituent, (iii) a halogeno and an electron-attracting substituent, and (iv) two halogeno substituents.The data show that for types (i), (ii) and (iv), the ortho isomers have the highest magnetic susceptibilities, the susceptibilities decreasing in the order: ortho > meta > para; for type (iii), the meta-isomers have the highest susceptibilities, the susceptibilities decreasing in the order: meta > para > ortho.The diamagnetic susceptibilities of some isomeric trisubstituted benzenes have also been determined and the data reveal that the susceptibility is the highest where the crowding of substituents is the highest (1,2,3-isomer) and lowest where the substituents are staggered and least crowded (1,3,5-isomer).Another observation made in the case of trisubstituted benzene is the applicability of a principle of additivity of their diamagnetic susceptibilities.
Baliah, V.,Jeyanthy, J. Judith Diana
p. 472 - 476
(2007/10/02)

15N Nuclear polarisation in rearrangement of 2,6-dichloro-N-nitroaniline and 2,6-dibromo-N-nitroaniline
The acid-catalysed rearrangements of 2,6-dichloro-N-nitroaniline and 2,6-dibromo-N-nitroaniline to give the corresponding 4-nitro derivatives have been followed by 1H and 15N nmr spectroscopy in deuteriochloroform at 30 deg C.When 15NO2-labelled nitramines are used, the 15N nmr signals for both the substrate and product show enhanced absorption during reaction.When one labelled nitramine and one unlabelled nitramine rearranged together, isotopic exchange occurs and 15N nmr signals are seen for both substrates and both products.For the initially unlabelled nitramine and its product, these signals are in emission.The change in the enhancement of the signals during reaction shows that the nuclear polarization arises from the rearrangement, not from a preliminary equilibrium.
Abu-Namous, Adel M. A.,Ridd, John H.,Sandall, John P. B.
p. 1124 - 1129
(2007/10/02)

Oxidative Cyclizations. VII. Cyclization of 2-Substituted Anilines with Alkaline Hypohalite
The Green-Rowe oxidation of 2-nitroanilines with alkaline hypohlorite, to yield benzofuroxans, is demonstrated by studies of the visible spectra of transient intermediates to proceed through N-chlorination and a singlet nitrene.Two variations on the route to the nitrene are possible.The cyclization step is represented as an internal capture of the nitrene by the ortho substituent, and on this basis the Green-Rowe oxidative cyclization is now extended to anilines whose ortho substituent is benzoyl or phenylazo.It is not however successful for ortho phenyl.Azo compounds were observed as byproducts in some of these reactions, and are shown to arise via N,N-dichloroanilines.
Dyall, Leonard K.
p. 2013 - 2026
(2007/10/02)

Water-insoluble azo dyestuffs which are derivatives of 1-aryl-3-trifluoromethyl-5-pyrazolones
Water-insoluble azo dyestuffs corresponding to the formula: STR1 in which X represents halogen, cyano, nitro, alkyl, polyfluoroalkyl, polyfluoroalkoxy, alkylsulphonyl, sulphonamido, or sulphonamido substituted by one or two alkyl groups; Y and Z are the same or different and represent hydrogen, halogen, cyano, nitro, alkyl, alkoxy, polyfluoroalkyl, polyfluoroalkoxy, alkylsulphonyl, sulphonamido or sulphonamidosubstituted by one or two alkyl groups; R represents hydrogen, halogen, cyano, nitro, alkyl, alkoxy, polyfluoroalkyl, polyfluoroalkoxy, alkylsulphonyl, sulphonamido, or sulphonamido substituted by one or two alkyl groups; m is equal to 0 or 1; and the nucleus A may be substituted by one or more chlorine atoms or alkyl, alkoxy or acylamino groups. These dyestuffs may be used for dyeing synthetic or artificial textile fibers, especially polyester fibers.
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(2008/06/13)

Succinimido azo dyestuffs
The invention relates to water-insoluble azo dyestuffs of the formula SPC1 In which A represents the residue of a diazo component of the azobenzene series, R1 a hydrogen atom or an alkyl group which may be substituted which may be substituted, R2 an alkyl group which may be substituted, R3 represents a divalent organic residue which together with the grouping EQU1 may form a 5- to 7-membered heterocycle, and X represents a hydrogen atom or an alkyl, alkoxy, aryloxy or arylmercapto group. The dyestuffs dye polyester fibre in orange, red or blue shades with good fastness: the use of such succinimido containing azo dyestuffs in imparting blue to red color to fibers or fabrics of wool, cellulose triacetate, polyamides and polyesters. The dyeings display excellent fastness to light, sublimation and abrasion on polyester fibers.
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(2008/06/13)