104-91-6

Usage

Chemical Properties

black solid

Uses

Dyes.

Hazard

Dangerous fire and explosion risk, reacts violently with acids and alkalies, may explode spontaneously, intraplant transport must be in tightly covered steel barrels.

Safety Profile

Poison by parented and intraperitoneal routes. Mutation data reported. An irritant and sensitizer. Many nitroso compounds are carcinogens. A very dangerous fire and explosion hazard. When exposed to heat or flame, it burns explosively. Contamination by acid or alkali may cause ignition . Can heat spontaneously and cause fire. When heated to decomposition it emits toxic fumes of NOx. See also NITROSO COMPOUNDS.

Purification Methods

4-Nitrosophenol forms yellow crystals from xylene, *C6H6 (m ~144o) or Et2O (m 128-129o, dec). [Beilstein 7 H 622, 7 II 574, 7 III 3367.]

InChI:InChI=1/C6H5NO2/c8-6-4-2-1-3-5(6)7-9/h1-4,8H

Upstream product

• 5382-54-7 4-(4-nitroso-phenyl)-morpholine 
• 7696-65-3 (4-nitroso-phenyl)-p-tolyl-amine 
• 123-30-8 4-amino-phenol 
• 100-66-3 methoxybenzene 
• 108-95-2 phenol 
• 3420-97-1 1-ethoxy-4-nitrosobenzene 
• 100-65-2 N-Phenylhydroxylamine 
• 7732-18-5 water 
• 106-51-4 p-benzoquinone 
• 7664-93-9 sulfuric acid 
• 39159-56-3 N-benzyl-4-nitroso-aniline 
• 100316-72-1 4-nitroso-N,N-di-n-propylaniline 
• 120-22-9 N,N-diethyl-4-nitrosoaniline 
• 1186-52-3 tetradeuterioacetic acid 

Downstream Products

• 82485-84-5 6-amino-5-chloro-1,3-dimethoxybenzene 
• 99860-89-6 chloro-acetic acid-(2,6-dichloro-4-propoxy-anilide) 
• 99973-15-6 [1,4]benzoquinone-(furan-2-carbonylhydrazone)-oxime 
• 2054-19-5 (4-hydroxy-phenylimino)-phenyl-acetonitrile 
• 98547-89-8 S-(5-amino-2-hydroxy-phenyl)-isothiourea 
• 23576-79-6 4-(isopropylamino)phenol 
• 635-78-9 resorufin 
• 13852-15-8 2,8-dihydroxy-10-(4-hydroxy-phenyl)-3,7-ditridecyl-10H-phenoxazine-1,4,6,9-tetraone 
• 2164-97-8 2,8-dihydroxy-10-(4-hydroxy-phenyl)-10H-phenoxazine-1,4,6,9-tetraone 
• 28237-04-9 p-N-Fluorazoxyphenol 
• 55872-89-4 1-(4-nitrosophenylamino)pyrrole 
• 164517-88-8 3,8-Bis-[(E)-4-hydroxy-phenylimino]-2,3,7,8-tetrahydro-1H,6H-pyrido[2,3-g]quinoline-4,5,9,10-tetraone 
• 156-10-5 p-nitrosodiphenylamine 
• 106-48-9 4-chloro-phenol 

Relevant academic research and scientific papers

Enthalpies of combustion of 2-iodosobenzoic acid and 4-nitrosophenol: The dissociation enthalpy of the I-O bond

The standard (po = 0.1 MPa) molar enthalpies of combustion in oxygen, at T = 298.15 K, for crystalline 2-iodosobenzoic acid, (OI)C6H4COOH, and 4-nitrosophenol, (ON)C6H4OH, were measured by rotating-bomb calorimetry and static-bomb calorimetry, respectively. These values were used to derive the standard molar enthalpies of formation of the crystalline compounds. ΔfHom(cr)/(kJ · mol-1) 2-iodosobenzoic acid 2-(OI)C6H4COOH -336.9 ± 2.5 4-nitrosophenol 4-(ON)C6H4OH -70.2 ± 2.1 An indirect method was used for assessing the dissociation enthalpy of the (I-O) bond in the iodoso derivative, Dom(I-O)/(kJ · mol-1) = (264.5 ± 8.1), which is the first value reported for an iodine-oxygen bond in an organic molecule.

Decorating of ultra small and recyclable nanoscale zero-valent iron on NH2-SiO2 for enhanced high-performance removal of water pollutants

The synthesis of nanoscale zero-valent iron (NZVI) with dimensions ranging from 20 to 100 nm has received tremendous attention in the control of environmental pollutants. However, due to strong magnetic attraction and van der Waals forces of NZVI, creating well-dispersed and stable NZVI particles with subnanometre size while avoiding their aggregation and retaining surface activity is a challenge. Here, for the first time, a novel Fe0@NH2-SiO2 nanocomposite was prepared by making SiO2 amino-functionalization in a simple process of hydrolysis polymerization, grafting Fe3+ on NH2-SiO2 nanospheres, and reduction by sodium borohydrid. It was found that the surface of NH2-SiO2 nanospheres (around 200 nm) was uniformly decorated by plentiful of well-defined Fe0 nanoparticles with a diameter of 0 nanoparticles showed a remarkable reduction activity in the application for the removal of water pollutants, and could be recycled easily with the aid of NaBH4.

Green fabrication of 3-dimensional flower-shaped zinc glycerolate and ZnO microstructures for p-nitrophenol sensing

The solvent or reaction medium always plays a lead role in synthesis chemistry. Glycerol has been studied as a green solvent for different organic transformations and is also expected to give interesting control in material synthesis. In this study, we use aqueous glycerol to synthesize zinc glycerolate and the corresponding ZnO micro-flower structures with an intention to encourage the utilization of glycerol as a green reaction medium in material synthesis. A zinc ammonium complex is used as a source of zinc, which converts to zinc glycerolate in the presence of glycerol. Glycerol plays a dual role as a reactant to form zinc glycerolate and as a solvent to control the morphology. The unreacted glycerol is recovered after the reaction and reused further. The flower-structured zinc glycerolate and ZnO are then used for the first time to modify a glassy carbon electrode to make a binder-free non-enzymatic amperometric chemical sensor for p-nitrophenol that is a brutal environmental pollutant. The modified electrode is found to be an excellent alternative for the purpose with respect to sensitivity, selectivity and stability.

Investigation of photoelectrocatalytic activity of Cu2O nanoparticles for p-nitrophenol using rotating ring-disk electrode and application for electrocatalytic determination

A cuprous oxide (Cu2O) nanoparticles modified Pt rotating ring-disk electrode (RRDE) was successfully fabricated, and the electrocatalytic determination of p-nitrophenol (PNP) using this electrode was developed. Cu2O nanoparticles were obtained by reducing the copper-citrate complex with hydrazine hydrate (N2H4·H 2O) in a template-free process. The hydrodynamic differential pulse voltammetry (HDPV) technique was applied for in situ monitor the photoelectrochemical behavior of PNP under visible light using nano-Cu 2O modified Pt RRDE as working electrode. PNP undergoes photoelectrocatalytic degradation on nano-Cu2O modified disk to give electroactive p-hydroxylamino phenol species which is compulsive transported and can only be detected at ring electrode at around 0.05 V with oxidation signal. The effects of illumination time, applied bias potential, rotation rates and pH of the reaction medium have been discussed. Under optimized conditions for electrocatalytic determination, the anodic current is linear with PNP concentration in the range of 1.0 × 10-5 to 1.0 × 10 -3 M, with a detection limit of 1.0 × 10-7 M and good precision (RSD = 2.8%, n = 10). The detection limit could be improved to 1.0 × 10-8 M by given illumination time. The proposed nano-Cu2O modified RRDE can be potentially applied for electrochemical detection of p-nitrophenol. And it also indicated that modified RRDE technique is a promising way for photoelecrocatalytic degradation and mechanism analysis of organic pollutants.

Nitrosation kinetics of phenolic components of foods and beverages

The kinetics of the reactions between sodium nitrite and phenol or m-, o-, or p-cresol in potassium hydrogen phthalate buffers of pH 2.5-5.7 were determined by integration of the monitored absorbance of the C-nitroso reaction products. At pH > 3, the dominant reaction was C-nitrosation through a mechanism that appears to consist of a diffusion-controlled attack on the nitrosatable substrate by NO+/NO2H2+ ions followed by a slow proton transfer step; the latter step is supported by the observation of basic catalysis by the buffer which does not form alternative nitrosating agents as nitrosyl compounds. The catalytic coefficients of both anionic forms of the buffer have been determined. The observed order of substrate reactivities (o-cresol ≈ m-cresol > phenol ? p-cresol) is explained by the hyperconjugative effect of the methyl group in o- and m-cresol, and by its blocking the para position in p-cresol. Analysis of a plot of ΔH# against ΔS# shows that the reaction with p-cresol differs from those with o- and m-cresol as regards the formation and decomposition of the transition state. The genotoxicity of nitrosatable phenols is compared with their reactivity with NO+/NO2H2+.

Nitrosation products from S-nitrosothiols via preliminary nitric oxide formation

High yields of N-nitroso-N-methylaniline were obtained from S-nitrosothiols (RSNO) and N-methylaniline in water at pH 7.4. Reactions were completely inhibited by the presence of EDTA and also when oxygen was removed from the solutions. Lower yields of 4-nitrosophenol were obtained from phenol under similar conditions and there was strong evidence of the rapid formation of a nitroso product (absorbance maximum at 390 nm) from uric acid which decomposed more slowly under the reaction conditions and could not be isolated. The results are consistent with prior nitric oxide formation, by the well-known Cu2+-catalysed (in which the active reagent is Cu+) decomposition of the S-nitrosothiol, subsequent oxidation of NO yielding NO2, which reacts further with NO to give N2O3, which then effects conventional electrophilic nitrosation in direct competition with its hydrolysis to nitrite. With phenol as the reactant, higher yields of 4-nitrosophenol were only possible when there was a very large excess of phenol over RSNO, probably due to the more effective relative competition of the hydrolysis reaction, given the lower reactivity in nitrosation of phenol compared with N-methylaniline. Nitrosation of uric acid is unknown, but we were able to observe the fairly rapid build-up of the same absorbance at 390 nm, from uric acid and nitrous acid only at around pH 4, which disappeared more slowly. The results suggest that uric acid behaves as do amides generally in that a nitroso compound is formed, which decomposes by an acid-catalysed route.

Nitrosation of phenolic compounds: Inhibition and enhancement

The nitrosation of phenol, m-, o-, and p-cresol, 2,3-, 3,5-, and 2,6- dimethylphenol, 3,5-di-tert-butylphenol, 2,4,6-trimethylphenol, o- chlorophenol, and o-bromophenol was studied. Kinetic monitoring of the reactions was accomplished by spectrophotometric analysis of the products at 345 nm. At pH > 3, the dominant reaction was C-nitrosation through a mechanism that appears to consist of an attack on the nitrosatable substrate by NO+/NO2H2+, followed by a slow proton transfer. The finding of an isokinetic relationship supports the idea that the same mechanisms operates throughout the series. The observed sequence of nitrosatable substrate reactivities is explained by (i) the preferred para-orientation of the hydroxyl group for the electrophilic attack of nitrosating agents, (ii) steric hindrance of alkyl substituents, which reduces or prevents attack by nitrosating agents, and (iii) the hyperconjugative effect of the methyl substituent, which causes electronic charge to flow into the aromatic nucleus, as well as the opposite electronic withdrawing effect induced by halogen substituents. The results show that potential nitrosation of widespread environmental species such as chlorophenols is negligible, but more attention should be paid to polyphenols with strongly nucleophilic carbon atoms.

N-Oxidation of arylamines to nitrosobenzenes using chloroperoxidase purified from Musa paradisiaca stem juice

N-Oxidation of arylamines to their corresponding nitrosobenzenes using a new chloroperoxidase purified from Musa paradisiaca stem juice has been examined. The enzymatic characteristics of the stem chloroperoxidase using 4-chloroaniline as substrate were determined. The Km values for 4-chloroaniline and H2O2 were 770 μM and 154 μM respectively, while the pH and temperature optima were 4.4 and 30°C respectively. The substrate specificities of the enzyme for the arylamines 3,4-dichloroamine, p-aminobenzoic acid, p-toluidine, p-anisidine, m-anisidine, p-aminophenol, o-aminophenol and m-aminophenol have been characterized. The feasibility of using concentrated M. paradisiaca stem juice for the specific conversion of 4-chloroaniline to 4-chloronitrosobenzene has been demonstrated. This enzyme can be used for the N-oxidation of other arylamines.

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.

Synthesis of Di(hetero)arylamines from Nitrosoarenes and Boronic Acids: A General, Mild, and Transition-Metal-Free Coupling

The synthesis of di(hetero)arylamines by a transition-metal-free cross-coupling between nitrosoarenes and boronic acids is reported. The procedure is experimentally simple, fast, mild, and scalable and has a wide functional group tolerance, including carbonyls, nitro, halogens, free OH and NH groups. It also permits the synthesis of sterically hindered compounds.