99-59-2

Basic information

• Product Name: 2-Amino-4-nitro anisidine
• Synonyms: 1-Amino-2-methoxy-5-nitrobenzene;1-Methoxy-2-amino-4-nitrobenzene;2-methoxy-5-nitro-anilin;2-Methoxy-5-nitrobenzamine;2-methoxy-5-nitro-benzenamin;2-Methoxy-5-nitrobenzenamine;2-methoxy-5-nitro-Benzenamine;3-Amino-4-methoxynitrobenzene
• CAS NO: 99-59-2
• Molecular Formula: C₇H₈N₂O₃
• Molecular Weight: 168.15
• EINECS: 202-770-5
• Product Categories: Intermediates of Dyes and Pigments;Amines;Building Blocks;C7;Chemical Synthesis;Nitrogen Compounds;Organic Building Blocks
• Mol File: 99-59-2.mol

Chemical Properties

• Melting Point: 117-119 °C(lit.)
• Boiling Point: 337.07°C (rough estimate)
• Flash Point: 119℃
• Appearance: orange to brown powder
• Density: 1.2068
• Vapor Pressure: 0.04Pa
• Refractive Index: 1.6010 (estimate)
• Solubility: 382mg/L in organic solvents at 20 ℃
• PKA: 2.42±0.10(Predicted)
• Water Solubility: Slightly soluble.
• Stability: Stable, but may be moisture sensitive. Incompatible with water, acids, strong oxidizing agents, acid chlorides, acid anhydrides,
• BRN: 879620
• CAS DataBase Reference: 2-Amino-4-nitro anisidine(CAS DataBase Reference)
• NIST Chemistry Reference: 2-Amino-4-nitro anisidine(99-59-2)
• EPA Substance Registry System: 2-Amino-4-nitro anisidine(99-59-2)

Safety Data

• Hazard Codes: Xi,Xn
• Statements: 36/37/38-20/21/22
• Safety Statements: 26-36-45-36/37
• WGK Germany: 2
• RTECS: BZ7175000
• TSCA: Yes
• Hazardous Substances Data: 99-59-2(Hazardous Substances Data)

Usage

Uses

Used in Dye Synthesis:
2-Amino-4-nitro anisidine is used as a key intermediate in the synthesis of 5-(9-acridinylamino)-p-anisidines, which are a class of organic dyes with potential applications in various industries.
Used in Textile Industry:
In the textile industry, 2-Amino-4-nitro anisidine is used as a precursor in the synthesis of disazo disperse dyes containing nitro and methoxy groups. These dyes are specifically used for the dyeing of polyester fibers, providing vibrant colors and improved dyeing performance.
Used in Pharmaceutical Industry:
Although not explicitly mentioned in the provided materials, 2-Amino-4-nitro anisidine can also be used as a building block in the synthesis of various pharmaceutical compounds, such as antibiotics, anti-inflammatory drugs, and other therapeutic agents. Its versatile chemical structure allows for further functionalization and modification to develop new drugs with improved properties.

Air & Water Reactions

Insoluble in water.

Reactivity Profile

2-Amino-4-nitro anisidine is incompatible with strong oxidizing agents, acids, acid chlorides, acid anhydrides and chloroformates .

Fire Hazard

Flash point data for 2-Amino-4-nitro anisidine are not available. 2-Amino-4-nitro anisidine is probably combustible.

Flammability and Explosibility

Nonflammable

Safety Profile

Suspected carcinogen with experimental carcinogenic and tumorigenic data. Moderately toxic by ingestion. Mutation data reported. When heated to decomposition it emits toxic fumes of NOx. See also NITRO COMPOUNDS OF AROMATIC HYDROCARBONS.

Potential Exposure

5-Nitro-o-anisidine is a chemical intermediate in the production of C.I. Pigment red 23, which is used as a colorant for commodities, such as printing inks, interior latex paints; lacquers, rubber, plastics, floor coverings; paper coating; and textiles. It is also used with other C.I. coupling components to produce various hues of red, brown, yellow, and violet on cotton, silk, acetate and nylon.

Waste Disposal

Incineration (982℃, 2.0 seconds minimum) with scrubbing for nitrogen oxides abatement.

InChI:InChI=1/C7H8N2O3/c1-12-7-3-2-5(9(10)11)4-6(7)8/h2-4H,8H2,1H3

Upstream product

• 119-27-7 2,4-dinitroanisole 
• 93-26-5 2-methoxyacetanilide 
• 59263-62-6 2-methoxy-5-nitro-benzamide 
• 33721-54-9 N-(2-methoxy-5-nitrophenyl)acetamide 
• 90-04-0 2-methoxy-phenylamine 
• 288-32-4 1H-imidazole 
• 455-93-6 2-fluoro-1-methoxy-4-nitrobenzene 
• 136833-44-8 2-nitro-4-amino-5-methoxybenzoic acid 
• 121-44-8 triethylamine 
• 186581-53-3 diazomethane 
• 99-57-0 2-hydroxy-5-nitroaniline 
• 7732-18-5 water 
• 7647-01-0 hydrogenchloride 
• 13027-36-6 N-hydroxy-2-methoxy-5-nitroaniline 

Downstream Products

• 66095-84-9 N,N-bis-(2-hydroxy-ethyl)-2-methoxy-5-nitro-aniline 
• 33721-54-9 N-(2-methoxy-5-nitrophenyl)acetamide 
• 128500-58-3 N-(2-methoxy-5-nitrophenyl)-3-oxo-3-phenylpropanamide 
• 13142-91-1 N-(2-methoxy-5-nitrophenyl)-N'-phenyl-urea 
• 120309-35-5 N-(2-methoxy-5-nitrophenyl)-propionamide 
• 330469-45-9 isobutyric acid-(2-methoxy-5-nitro-anilide) 
• 63379-21-5 (2-methoxy-5-nitro-phenyl)-carbamic acid methyl ester 
• 301172-87-2 toluene-4-sulfonic acid-(2-methoxy-5-nitro-anilide) 
• 17012-47-4 8-methoxy-5-nitroquinoline 
• 32895-23-1 N¹-(2-Methoxy-5-nitrophenyl)-N⁴-acetyl-sulfanylamid 
• 59741-17-2 2-methoxy-5-nitrophenyl isocyanate 
• 71793-51-6 2-methoxy-5-nitrophenyl isothiocyanate 
• 100-17-4 para-methoxynitrobenzene 

Relevant articles and documents

A Common, Facile and Eco-Friendly Method for the Reduction of Nitroarenes, Selective Reduction of Poly-Nitroarenes and Deoxygenation of N-Oxide Containing Heteroarenes Using Elemental Sulfur

A transition metal-free, environment-friendly and practical protocol was developed either for the reduction of nitroarenes or for the deoxygenation of N-oxide containing heteroarenes. The reaction proceeded with the use of a non-toxic and cheap feedstock as elemental sulfur in aqueous methanol under relatively mild conditions. Green chemistry credentials were widely favorable compared to traditional and industrial protocols with good E-factors and a low production of waste. The strategy allowed the efficient reduction of a large variety of substituted-nitroarenes including various o-nitroanilines as well as selective reduction of various poly-nitroarenes in excellent yields with a broad substrate scope. The protocol was successfully extended to the deoxygenation of some N-oxide containing heteroarenes, like benzofuroxans, phenazine N,N'-dioxides, pyridine N-oxides, 2H-indazole N1-oxides, quinoxaline N1,N4-dioxides and benzo[d]imidazole N1,N3-dioxides. A gram-scale example for the synthesis of luminol, in green conditions, was reported. A solid mechanism of reaction was proposed from experimental evidences.

Photocatalytic C-H Amination of Aromatics Overcoming Redox Potential Limitations

We report the photocatalytic C-H amination of aromatics overcoming redox potential limitations. Radical cations of aromatic compounds are generated photocatalytically using Ru(phen)3(PF6)2, which has a reduction potential at a high oxidation state (Ered(RuIII/RuII) = +1.37 V vs SCE) lower than the oxidation potentials of aromatic substrates (Eox = +1.65 to +2.27 V vs SCE). The radical cations are trapped with pyridine to give N-arylpyridinium ions, which were converted to aromatic amines.

Pyrroloquinoline quinone synthetic method

The invention discloses a synthetic method of pyrroloquinoline quinone. The synthetic method comprises the following steps: carrying out alkali treatment on 2-methoxy-5-nitroaniline hydrochloride as a raw material, so as to obtain a compound 1; carrying out formylation on the compound 1 under a catalysis condition of an ionic liquid, so as to obtain a compound 2; adopting sodium borohydride to reduce the compound 2 to obtain a compound 3; carrying out diazotization on the compound 3, and then enabling action between the diazotized compound 3 and HBF4 to obtain a compound 4; enabling reaction of the compound 4 and 2-methylethyl acetoacetate to obtain a compound 5; treating the compound 5 with formic acid to obtain a compound 6; carrying out amid catalysis and exchange with the ionic liquid on the compound 6 to obtain a compound 7; enabling reaction of the compound 7 and 2-oxodimethyl glutaconate to obtain a compound 8; feeding hydrogen chloride to the compound 8 under the action of Cu(OAc)2*2H2O to obtain a compound 9; carrying out basic hydrolysis on the compound 9 to obtain a compound 10. The synthetic method disclosed by the invention is cheap and accessible in raw materials, stable, high in reaction yield, quick in reaction, and easy for product separation, and is environment-friendly as the catalyst can be recycled.

Altering the regioselectivity of a nitroreductase in the synthesis of arylhydroxylamines by structure-based engineering

Nitroreductases have great potential for the highly efficient reduction of aryl nitro compounds to arylhydroxylamines. However, regioselective reduction of the desired nitro group in polynitroarenes is still a challenge. Here, we describe the structure-based engineering of Escherichia coli nitroreductase NfsB to alter its regioselectivity, in order to achieve reduction of a target nitro group. When 2,4-dinitrotoluene was used as the substrate, the wild-type enzyme regioselectively reduced the 4-NO2 group, but the T41L/N71S/F124W mutant primarily reduced the 2-NO2 group, without loss of activity. The crystal structure of T41L/N71S/F124W and docking experiments indicated that the regioselectivity change (from 4-NO2 to 2-NO2) might result from the increased hydrophobicity of residues 41 and 124 (proximal to FMN) and conformational changes in residues 70 and 124. The regioselectivity of nitroreductase NfsB from E. coli toward 2,4-dinitrotoluene was shifted from the 4-NO2 group to the 2-NO2 group without loss of activity, by introducing three mutations: T41L, N71S, and F124W. This study provides an example of a tailored enzyme for regioselective synthesis of the target arylhydroxylamines.

Selective partial hydrogenation of dinitrobenzenes to nitroanilines catalyzed by Ru/C

Ru/C was found to be a highly effective catalyst for the selective partial hydrogenation of a range of dinitrobenzenes to their corresponding nitroanilines with excellent selectivity under mild conditions. Furthermore, the effect from other substitute groups of dinitrobenzenes on partial hydrogenation was also explored in this study. Copyright

Effect of the electronic structure of the radical anions of 4-substituted 1,2-and 1,3-dinitrobenzenes on the regioselectivity of reduction of the nitro groups

Theoretical and experimental regularities of the regioselectivity of the reduction of one of the two nitro groups in unsymmetrical dinitrobenzenes were studied. It was found that the regioselectivity of the formation of isomeric nitroanilines depends on the structure of the substrate and the nature of the reducing agent. The reduction regioselectivity model was verified, according to which radical anion protonation is the major reaction direction. Pleiades Publishing, Inc. 2006.

New nitronate σ complexes and the mechanism of nucleophilic aromatic photosubstitution para to a nitro group

Photolysis of 4-nitroanisole with aliphatic amines gives mainly N-substituted 4-nitroanilines. Reactions of this type have been widely attributed to a geminate radical mechanism. We questioned this interpretation and have searched for and found by NMR spectroscopy a new class of stable nitronate adducts generated under the reaction conditions. The adducts imply that photosubstitution by amines para to the nitro group occurs by meta σ complex formation followed by an unprecedented sigmatropic rearrangement.

Guanidinium nitrate: A novel reagent for aryl nitrations

Nitration of various aromatic compounds utilising guanidinium nitrate in 85% sulfuric acid as a nitrating agent has been studied.

Nitration of o-Aminophenol, o-Anisidine, and o-Benzenediazonium Oxide in Sulfuric Acid

Entering into a reaction in the protonated form, o-aminophenol is nitrated in 80% sulfuric acid at the para and ortho positions to the hydroxy group to afford a mixture of 4-nitro- and 6-nitro-2-aminophenol and is nitrated and sulfonated in concentrated sulfuric acid, whereas o-anisidine is nitrated at the para positions in both cases, converting into 4-nitro-2-aminoanisole. After diazotization of o-aminophenol and subsequent nitration of o-benzenediazonium oxide, a mixture of the same derivatives as in diazotization of the nitration products of o-aminophenol is formed, but the 6-nitro isomer prevails.

Concerning the baker's yeast (Saccharomyces cerevisiae) mediated reduction of nitroarenes and other N-O containing functional groups

Nitro- and nitrosoarenes can be reduced using baker's yeast (Saccharomyces cerevisiae) under two distinct sets of conditions, one of which is in fact a well established non-enzymic process. In order to clarify reports in the literature a comparison of the two methods has been made.