659-49-4

Basic information

• Product Name: 4-nitrosoaniline
• Synonyms: 4-nitrosoaniline;4-Nitrosobenzenamine
• CAS NO: 659-49-4
• Molecular Formula: C₆H₆N₂O
• Molecular Weight: 122.12464
• EINECS: 211-535-6
• Mol File: 659-49-4.mol
• Article Data: 11

Chemical Properties

• Melting Point: 173.5°C
• Boiling Point: 227.52°C (rough estimate)
• Flash Point: 117.9°C
• Appearance: /
• Density: 1.2236 (rough estimate)
• Vapor Pressure: 0.00646mmHg at 25°C
• Refractive Index: 1.4738 (estimate)
• CAS DataBase Reference: 4-nitrosoaniline(CAS DataBase Reference)
• NIST Chemistry Reference: 4-nitrosoaniline(659-49-4)
• EPA Substance Registry System: 4-nitrosoaniline(659-49-4)

Safety Data

• Hazard Codes: Xn
• Statements: 20/21/22
• Safety Statements: 25-28
• Hazardous Substances Data: 659-49-4(Hazardous Substances Data)

Usage

General Description

4-Nitrosoaniline is a chemical compound with the molecular formula C6H6N2O2. It is a pale yellow solid that is not very soluble in water. 4-Nitrosoaniline is used as a reagent in organic synthesis and as a precursor to dyes and pigments. It is also used in the production of pharmaceuticals and as an intermediate in the manufacturing of rubber and plastics. It is considered to be a weak mutagen and is classified as a possible human carcinogen. Exposure to 4-Nitrosoaniline can lead to irritation of the skin, eyes, and respiratory system, and it should be handled with caution.

InChI:InChI=1/C6H6N2O/c7-5-1-3-6(8-9)4-2-5/h1-4H,7H2

Synthetic route

nitrobenzene (98-95-3) → 4-nitrosoaniline (659-49-4) + 4-nitro-aniline (100-01-6)

Conditions	Yield
With pyrene; tetramethyl ammoniumhydroxide; benzamide; potassium carbonate In dimethyl sulfoxide at 90℃; for 2.08333 - 2.16667h; Conversion of starting material;	A 94% B 6%
With potassium hydroxide; pyrene; potassium carbonate; urea In dimethyl sulfoxide at 90℃; for 2.08333 - 2.16667h; Conversion of starting material;	A 87% B 12%
With urea, monopotassium salt; urea In dimethyl sulfoxide at 90℃; for 2h;	A 56% B 5.5%

nitrobenzene (98-95-3) → 4-nitrosoaniline (659-49-4)

Conditions	Yield
With urea, monosodium salt; dimethyl sulfoxide; urea at 90℃; for 4h; Reagent/catalyst; Temperature;	89.5%
With urea, monosodium salt; urea In dimethyl sulfoxide at 90℃; for 2h; Reagent/catalyst;	82%
With urea, monosodium salt In dimethyl sulfoxide at 90℃; for 2h; Temperature; Reagent/catalyst;
With potassium carbonate; urea; potassium hydroxide In dimethyl sulfoxide at 90℃; for 5h;

nitrobenzene (98-95-3) → 4-nitrosoaniline (659-49-4) + N,N-bis(p-nitrophenyl)amine (1821-27-8) + 4-nitro-aniline (100-01-6)

Conditions	Yield
With potassium hydroxide; pyrene; benzamide; potassium carbonate In dimethyl sulfoxide at 70℃; for 2.08333 - 2.16667h; Product distribution / selectivity;	A 75% B 9% C 12%
With sodium hydroxide; pyrene; benzamide; potassium carbonate In dimethyl sulfoxide at 90℃; for 2.08333 - 2.16667h;	A 62% B 5% C 14%

1,4-phenylenediamine (106-50-3) → 4-nitrosoaniline (659-49-4)

Conditions	Yield
With urea hydrogen peroxide adduct; carbonic acid dimethyl ester at 20℃; for 2h;	65%

p-benzoquinone dioxime (105-11-3, 6133-83-1, 6421-98-3) → 4-nitrosoaniline (659-49-4) + 4-nitro-aniline (100-01-6)

Conditions	Yield
With PPA at 135 - 140℃; for 0.5h;	A 27% B 40%

p-nitrosophenol (104-91-6) + ammonium acetate (631-61-8) → 4-nitrosoaniline (659-49-4)

Conditions	Yield
With iron(III) chloride

p-nitrosophenol (104-91-6) → 4-nitrosoaniline (659-49-4)

Conditions	Yield
With iron(III) chloride; ammonium chloride

p-benzoquinone oxime (637-62-7) → 4-nitrosoaniline (659-49-4)

Conditions	Yield
With ammonium acetate; ammonium carbonate; ammonium chloride

4-azidoaniline (14860-64-1) → 4-nitrosoaniline (659-49-4) + 4-nitro-aniline (100-01-6)

Conditions	Yield
With oxygen In toluene at -196.1℃; Product distribution; Quantum yield; Mechanism; Irradiation; other solvents;

APMA → 4-nitrosoaniline (659-49-4)

Conditions	Yield
With sulfuric acid; sodium nitrite

p-nitrosophenol (104-91-6) + ammonium carbonate → 4-nitrosoaniline (659-49-4)

Conditions	Yield
With iron(III) chloride

p-benzoquinone oxime (637-62-7) + ammonium chloride + ammonium acetate (631-61-8) + ammonium carbonate → 4-nitrosoaniline (659-49-4)

hydrogenchloride (7647-01-0) + 1-(4-amino-phenyl)-3-phenyl-triazen-1-ol (861367-05-7) → 4-nitrosoaniline (659-49-4) + benzene (71-43-2) + nitrogen

4-nitrosoaniline (659-49-4) + benzaldehyde (100-52-7) + acetophenone (98-86-2) → C21H18N2O2

Conditions	Yield
With Rice-husk-supported FeCl3 nano-particles In ethanol at 20℃; for 14h; Mannich Aminomethylation; Green chemistry;	92%

diazomethane (186581-53-3, 908094-01-9) + 4-nitrosoaniline (659-49-4) → glyoxal-bis-[N-(4-amino-phenyl)-oxime ]

Conditions	Yield
With diethyl ether

Ketene (463-51-4) + 4-nitrosoaniline (659-49-4) → 4-(N-acetylamino)-1-nitrosobezene (67661-55-6)

Conditions	Yield
With acetic acid; toluene

ethanol (64-17-5) + 4-nitrosoaniline (659-49-4) + phenylhydrazine hydrochloride (59-88-1) → 1-(4-amino-phenyl)-3-phenyl-triazen-1-ol (861367-05-7) + 1,4-phenylenediamine (106-50-3)

4-nitrosoaniline (659-49-4) + 3-(ethylamino)phenol (621-31-8) → 5-ethyl-3-amino-7-hydroxy-phenazinium; chloride

Conditions	Yield
With ethanol; sodium acetate Loesen das Reaktionsprodukts in angesaeuertem Wasser und mit Kochsalz fallen;
With sodium acetate; acetic acid Loesen das Reaktionsprodukts in angesaeuertem Wasser und mit Kochsalz fallen;

4-nitrosoaniline (659-49-4) + 2,7-bis(phenylamino)naphthalene (261509-98-2) → 9-amino-2-anilino-7-phenyl-benzo[a]phenazinium; chloride-hydrochloride

Conditions	Yield
With hydrogenchloride; ethanol

4-nitrosoaniline (659-49-4) + aniline hydrochloride (142-04-1) → 3,7-diamino-5-phenyl-phenazinium; hydroxide (568-71-8)

Conditions	Yield
With water

4-nitrosoaniline (659-49-4) + phenylhydrazine hydrochloride (59-88-1) → 1-(4-amino-phenyl)-3-phenyl-triazen-1-ol (861367-05-7) + 1,4-phenylenediamine (106-50-3)

Conditions	Yield
With ethanol

4-nitrosoaniline (659-49-4) → 4-azidoaniline (14860-64-1)

Conditions	Yield
With hydrogen azide

4-nitrosoaniline (659-49-4) → 4-nitroso-aniline; sodium-compound

Conditions	Yield
With sodium hydroxide; diethyl ether; ethanol

4-nitrosoaniline (659-49-4) → 4-nitro-aniline (100-01-6)

Conditions	Yield
With potassium permanganate

4-nitrosoaniline (659-49-4) → 1,4-phenylenediamine (106-50-3)

Conditions	Yield
With diethyl ether; phenylhydrazine
With palladium on activated charcoal; ethanol; hydrazine hydrate
With 5%-palladium/activated carbon; hydrogen In ethanol at 80℃; under 15001.5 - 22502.3 Torr;
With 3.8% Pd/C; hydrogen In ethanol at 80℃; under 15001.5 Torr; Autoclave;	8.55 g

4-nitrosoaniline (659-49-4) + salicylaldehyde (90-02-8) → 2-[(4-Nitroso-phenylimino)-methyl]-phenol

Conditions	Yield
at 100℃;

4-nitrosoaniline (659-49-4) + benzoyl chloride (98-88-4) → [1,4]benzoquinone-mono-(O-benzoyl oxime ) (26880-35-3)

Conditions	Yield
With sodium hydroxide

4-nitrosoaniline (659-49-4) + benzoyl chloride (98-88-4) → [1,4]benzoquinone-benzoylimine-(O-benzoyl oxime ) (29654-44-2)

Conditions	Yield
With sodium hydroxide

4-nitrosoaniline (659-49-4) + hydrazine carboxamide (4426-72-6, 51433-48-8) → 3-(4-amino-phenyl)-3-hydroxy-triazene-1-carboxylic acid amide

4-nitrosoaniline (659-49-4) + aniline hydrochloride (142-04-1) + aniline (62-53-3) → azophenin (4435-12-5)

Conditions	Yield
at 80 - 100℃;

4-nitrosoaniline (659-49-4) + aniline (62-53-3) → azophenin (4435-12-5)

Conditions	Yield
With aniline hydrochloride at 80 - 100℃;

diethyl ether (60-29-7) + 4-nitrosoaniline (659-49-4) + phenylhydrazine (100-63-0) → 1,4-phenylenediamine (106-50-3)

4-nitrosoaniline (659-49-4) + benzoyl chloride (98-88-4) + diluted NaOH/KOH → [1,4]benzoquinone-benzoylimine-(O-benzoyl oxime ) (29654-44-2)

Upstream product

• 7647-01-0 hydrogenchloride 
• 861367-05-7 1-(4-amino-phenyl)-3-phenyl-triazen-1-ol 
• 98-95-3 nitrobenzene 
• 100-01-6 4-nitro-aniline 
• 106-50-3 1,4-phenylenediamine 
• 637-62-7 p-benzoquinone oxime 
• 631-61-8 ammonium acetate 
• 104-91-6 p-nitrosophenol 
• 105-11-3 p-benzoquinone dioxime 
• 14860-64-1 4-azidoaniline 

Downstream Products

• 106-50-3 1,4-phenylenediamine 
• 101-54-2 N-phenylphenylene-1,4-diamine 
• 100-01-6 4-nitro-aniline 
• 637-62-7 p-benzoquinone oxime 
• 7664-41-7 ammonia 
• 105-11-3 p-benzoquinone dioxime 
• 29654-44-2 [1,4]benzoquinone-benzoylimine-(O-benzoyl oxime ) 
• 4435-12-5 azophenin 
• 26880-35-3 [1,4]benzoquinone-mono-(O-benzoyl oxime ) 
• 14860-64-1 4-azidoaniline 
• 861367-05-7 1-(4-amino-phenyl)-3-phenyl-triazen-1-ol 
• 568-71-8 3,7-diamino-5-phenyl-phenazinium; hydroxide 
• 67661-55-6 4-(N-acetylamino)-1-nitrosobezene 

Relevant articles and documents

Tungstate-supported silica-coated magnetite nanoparticles: a novel magnetically recoverable nanocatalyst for green synthesis of nitroso arenes

Tungstate ion was heterogenized on the silica-coated magnetite nanoparticles and applied for the selective oxidation of anilines to nitroso arenes—with hydrogen peroxide/urea as oxidant in dimethyl carbonate as solvent—in moderate–good yields (40–96%). The catalyst was characterized using different techniques including Fourier-transform infrared spectroscopy, X-ray powder diffraction, vibrating sample magnetometry, scanning electron microscopy, energy dispersive X-ray and inductively coupled plasma atomic emission spectroscopy (ICP-AES). The catalyst was easily recovered using an external magnet and reused for six times.

An efficient preparation of 4-nitrosoaniline from the reaction of nitrobenzene with alkali metal ureates

This paper describes the synthesis of alkali metal salts of urea (ureates) and their application to the direct preparation of 4-nitrosoaniline from nitrobenzene via nucleophilic aromatic substitution of hydrogen. Sodium and potassium ureates were readily prepared from the reaction of urea with sodium hydride, metal methoxides, and metal hydroxides. The effect of ureates as nucleophiles on the conversion of nitrobenzene to 4-nitrosoaniline was investigated and compared with that of a urea-metal hydroxide mixture. It was found that the ureates were superior for producing 4-nitrosoaniline owing to their higher thermal stability of the ureate. The ureate obtained from the treatment of urea with sodium hydride gave the highest yield for the preparation of 4-nitrosoaniline. The ureates generated from the reaction of urea with metal hydroxide also gave high yields of 4-nitrosoaniline. Catalytic hydrogenation of 4-nitrosoaniline afforded polymer-grade 1,4-benzenediamine in quantitative yield.