99-09-2

Basic information

• Product Name: 3-Nitroaniline
• Synonyms: 3-nitro-benzenamin;3-Nitrobenzenamine;3-nitro-Benzenamine;3-Nitrobenzeneamine;3-Nitrophenylamine;3-Nitro-phenylamine;Amarthol Fast Orange R Base;amartholfastorangerbase
• CAS NO: 99-09-2
• Molecular Formula: C₆H₆N₂O₂
• Molecular Weight: 138.12
• EINECS: 202-729-1
• Product Categories: Intermediates of Dyes and Pigments;Anilines, Aromatic Amines and Nitro Compounds;Organics;Functional Materials;Organic Nonlinear Optical Materials;C2 to C6;Alpha Sort;Analytical Standards;AromaticsChemical Class;AromaticsVolatiles/ Semivolatiles;Chemical Class;N;NA - NIAnalytical Standards;Nitro Compounds;N-OAlphabetic;C2 to C6Photonic and Optical Materials;Amines;Nitrogen Compounds;NLO Chromophores and Intermediates;Non-Linear Optical (NLO) Materials;NA - NI;NLO Chromophores and Intermediates;Non-Linear Optical (NLO) Materials;Photonic and Optical Materials;Building Blocks;C6;Chemical Synthesis;Materials Science;Nitrogen Compounds;Organic and Printed Electronics;Organic Building Blocks;Dyestuff Intermediates
• Mol File: 99-09-2.mol
• Article Data: 164

Chemical Properties

• Melting Point: 111-114 °C(lit.)
• Boiling Point: 306 °C
• Flash Point: 196 °C
• Appearance: Yellow to ochre-yellow to orange/Crystals, Crystalline Powder and/or Chunks
• Density: 0,901 g/cm3
• Vapor Pressure: 1 mm Hg ( 119 °C)
• Refractive Index: 1.6396 (estimate)
• Storage Temp.: Store below +30°C.
• Solubility: 1.25g/l
• PKA: 2.466(at 25℃)
• Water Solubility: 1.25 g/L
• Merck: 14,6581
• BRN: 636962
• CAS DataBase Reference: 3-Nitroaniline(CAS DataBase Reference)
• NIST Chemistry Reference: 3-Nitroaniline(99-09-2)
• EPA Substance Registry System: 3-Nitroaniline(99-09-2)

Safety Data

• Hazard Codes: T
• Statements: 23/24/25-33-52/53
• Safety Statements: 28-36/37-45-61-28A
• RIDADR: UN 1661 6.1/PG 2
• WGK Germany: 2
• RTECS: BY6825000
• F: 8
• TSCA: Yes
• HazardClass: 6.1
• PackingGroup: II
• Hazardous Substances Data: 99-09-2(Hazardous Substances Data)

Usage

Chemical Properties

3-Nitroaniline is a ochre-yellow to orange crystalline powder, crystallizes as yellow needles from water. It is moderately soluble in organic solvents and sparingly soluble in water (0.11 %).

Physical properties

Yellow, rhombic crystals or powder. Finely dispersered particles form explosive mixtures. Combustible.

Uses

Different sources of media describe the Uses of 99-09-2 differently. You can refer to the following data:
1. Dyestuff intermediate. Acetylation of 3-nitroaniline followed by reduction gives 3-aminoacetanilide. Diazotization, followed by reduction of the diazosulfonate with ammonium bisulfite and subsequent hydrolysis, gives (3-nitrophenyl) hydrazine; an intermediate in the production of pyrazolone azo coupling components. 3-Nitroaniline is used as a diazo component (Fast Orange R Base) in azo dyes (e.g., C.I. Disperse Yellow 5 and C.I. Acid Orange 18).
2. 3-Nitroaniline is commonly used as a raw material for dyes. It is also used as a chemical intermediate for azo coupling component 17 and the dyes disperse yellow 5 and acid blue 29. The chemical is changed to other substances (dyestuffs and m-nitrophenol) during the dyeing process.

Preparation

M-nitroaniline partial reduction.

Synthesis Reference(s)

The Journal of Organic Chemistry, 45, p. 4992, 1980 DOI: 10.1021/jo01312a039Tetrahedron Letters, 30, p. 251, 1989 DOI: 10.1016/S0040-4039(00)95173-6Chemical and Pharmaceutical Bulletin, 34, p. 2013, 1986 DOI: 10.1248/cpb.34.2013

General Description

Yellow needles or yellow powder.

Air & Water Reactions

Insoluble in water.

Reactivity Profile

Thermal stability of 3-Nitroaniline is reduced by various impurities. 3-Nitroaniline may be sensitive to prolonged exposure to light. 3-Nitroaniline may react explosively with ethylene oxide at 266° F. 3-Nitroaniline is incompatible with acids (nitric, sulfuric), acid chlorides, acid anhydrides, chloroformates and strong oxidizing agents. . Unstable when heated.

Hazard

Moderate fire risk. Toxic when absorbed by skin.

Fire Hazard

Flash point data for 3-Nitroaniline are not available; however, 3-Nitroaniline is probably combustible.

Synthesis

1,3-Dinitrobenzene is added towarmwater containing magnesium sulfate. An aqueous solution of sodium hydrogen sulfide (6molar equivalents) is added gradually to the vigorously stirred emulsion, and reduction is completed by heating to 90℃. The 3-nitroaniline produced solidifies on cooling and is separated by filtration.

Environmental fate

Biological. A bacterial culture isolated from the Oconee River in North Georgia degraded 3- nitroaniline to the intermediate 4-nitrocatechol (Paris and Wolfe, 1987). A Pseudomonas sp. strain P6, isolated from a Matapeake silt loam, did not grow on 3-nitroaniline as the sole source of carbon. However, in the presence of 4-nitroaniline, all of the applied 3-nitroaniline metabolized completely to carbon dioxide (Zeyer and Kearney, 1983). In the presence of suspended natural populations from unpolluted aquatic systems, the second-order microbial transformation rate constant determined in the laboratory was reported to be 4.6 ± 0.1 x 10-13 L/organism?h (Steen, 1991). In activated sludge inoculum, following a 20-d adaptation period, no degradation was observed (Pitter, 1976). Chemical/Physical. Reacts with acids forming water soluble salts.

Purification Methods

Purify it as for o-nitroaniline. Warning: it is absorbed through the skin. [Beilstein 12 IV 1589.]

InChI:InChI=1/C6H6N2O2/c9-8(10)7-6-4-2-1-3-5-6/h1-5,7H

Upstream product

• 99-65-0 meta-dinitrobenzene 
• 623-11-0 1-methyl-4-nitrosobenzene 
• 33322-43-9 3-nitro-benzoic acid bromoamide 
• 122-28-1 N-(3-nitrophenyl)acetanilide 
• 108-24-7 acetic anhydride 
• 542-15-4 anilinium nitrate 
• 99-61-6 3-nitro-benzaldehyde 
• 108-45-2 m-phenylenediamine 
• 103-29-7 1,1'-(1,2-ethanediyl)bisbenzene 
• 53821-16-2 (3-nitrophenyl)carbamic acid benzyl ester 
• 125519-67-7 (2-Methyl-propenyl)-(3-nitro-phenyl)-amine 
• 7647-01-0 hydrogenchloride 
• 3320-87-4 isocyanic acid (3-nitro-phenyl) ester 
• 71-43-2 benzene 

Downstream Products

• 24812-82-6 3-[N,N-Bis(2-hydroxyethyl)amino]nitrobenzene 
• 78662-36-9 thiophene-2-carbaldehyde-(3-nitro-phenylimine) 
• 121761-12-4 selenophene-2-carbaldehyde-(3-nitro-phenylimine) 
• 90736-46-2 3-[2]furyl-acrylaldehyde-(3-nitro-phenylimine) 
• 36647-25-3 N-(3-nitrophenyl)phthalimide 
• 19336-84-6 2-[(3-nitrophenyl)aminocarbonyl]benzoic acid 
• 2352-35-4 2,4,6-tris(3-nitroaniline)-1,3,5-triazine 
• 95733-79-2 N-m-Nitrophenylchelidamic acid 
• 53555-12-7 4-nitro-2-(3-nitro-phenyl)-isoindoline-1,3-dione 
• 6275-72-5 ethyl N-(m-nitrophenyl)carbamate 
• 10480-31-6 N-(2-chloro-benzylidene)-3-nitro-aniline 
• 13289-29-7 N-(2-nitrophenyl)-N'-(3-nitrophenyl)urea 
• 13252-27-2 1-(m-nitrophenyl)-3-(p-nitrophenyl)urea 
• 29103-51-3 N,N-dibenzyl-3-nitroaniline 

Relevant articles and documents

Support effect of Rh catalysts on the hydrogenation of m-dinitrobenzene

The effect of the support (ZrO2, Al2O3, and TiO2) of Rh (1 wt%) catalysts for the hydrogenation of m-dinitrobenzene (m-DNB) in liquid phase was studied. The catalysts were reduced at 300 °C and characterized by

Carbon supported gold and silver: Application in the gas phase hydrogenation of m-dinitrobenzene

Abstract We have studied the gas phase continuous hydrogenation of m-dinitrobenzene (m-DNB) over acid treated activated carbon (AC) supported Au and Ag prepared by deposition-precipitation. Temperature programmed reduction of a 1%wt. metal loading generat

Au/Ni/Ni(OH)2/C Nanocatalyst with High Catalytic Activity and Selectivity for m-dinitrobenzene Hydrogenation

The Au/Ni/Ni(OH)2/C bimetallic nanocatalysts with different Au loadings (Au/Ni/Ni(OH)2/C-1: 0.05 wt%Au; Au/Ni/Ni(OH)2/C-2: 0.46 wt%Au; Au/Ni/Ni(OH)2/C-3: 2.60 wt%Au) were prepared at room temperature. The characterization results proved the nanostructure of Au islands supported on the Ni/Ni(OH)2 nanoparticles (NPs) and synergy effect of Au-, Ni- and Ni(OH)2-related species in Au/Ni/Ni(OH)2/C. These are the main reasons why their catalytic performance and selectivity to m-nitroaniline in m-dinitrobenzene hydrogenation were much higher than those of monometallic catalysts (Au/C and Ni/Ni(OH)2/C). Because Au/Ni/Ni(OH)2/C-2 was with high dispersion of Au, Au(0)/Aun+ ratio≈1:1 on the surface, novel nanostructure, moderate capacity of activating and dissociating hydrogen, and synergistic effect, it had much better catalytic activity (conversion of m-dinitrobenzene-100%) and higher selectivity to m-nitroaniline (95.0%) in m-dinitrobenzene hydrogenation reaction compared to other two supported bimetallic catalysts (Au/Ni/Ni(OH)2/C-1 and Au/Ni/Ni(OH)2/C-3). Au/Ni/Ni(OH)2/C-2 also exhibited high stability. Graphic abstract: [Figure not available: see fulltext.]

Aluminum Metal-Organic Framework-Ligated Single-Site Nickel(II)-Hydride for Heterogeneous Chemoselective Catalysis

The development of chemoselective and heterogeneous earth-abundant metal catalysts is essential for environmentally friendly chemical synthesis. We report a highly efficient, chemoselective, and reusable single-site nickel(II) hydride catalyst based on robust and porous aluminum metal-organic frameworks (MOFs) (DUT-5) for hydrogenation of nitro and nitrile compounds to the corresponding amines and hydrogenolysis of aryl ethers under mild conditions. The nickel-hydride catalyst was prepared by the metalation of aluminum hydroxide secondary building units (SBUs) of DUT-5 having the formula of Al(μ2-OH)(bpdc) (bpdc = 4,4′-biphenyldicarboxylate) with NiBr2 followed by a reaction with NaEt3BH. DUT-5-NiH has a broad substrate scope with excellent functional group tolerance in the hydrogenation of aromatic and aliphatic nitro and nitrile compounds under 1 bar H2 and could be recycled and reused at least 10 times. By changing the reaction conditions of the hydrogenation of nitriles, symmetric or unsymmetric secondary amines were also afforded selectively. The experimental and computational studies suggested reversible nitrile coordination to nickel followed by 1,2-insertion of coordinated nitrile into the nickel-hydride bond occurring in the turnover-limiting step. In addition, DUT-5-NiH is also an active catalyst for chemoselective hydrogenolysis of carbon-oxygen bonds in aryl ethers to afford hydrocarbons under atmospheric hydrogen in the absence of any base, which is important for the generation of fuels from biomass. This work highlights the potential of MOF-based single-site earth-abundant metal catalysts for practical and eco-friendly production of chemical feedstocks and biofuels.