100-65-2

Basic information

• Product Name: N-Phenylhydroxylamine
• Synonyms: N-Phenylhydroxylamine;Phenylhydroxylamine;N-HYDROXYANILINE;N-HYDROXYLANILINE;Hydroxyaminobenzene;NCI C-60093;N-Hydroxybenzenamine;N-Phenylhydroxyamine
• CAS NO: 100-65-2
• Molecular Formula: C₆H₇NO
• Molecular Weight: 109.12588
• EINECS: 202-875-6
• Mol File: 100-65-2.mol

Chemical Properties

• Melting Point: 80-84℃
• Boiling Point: 204.59°C (rough estimate)
• Flash Point: 120.2°C
• Appearance: tan powder or crystals
• Density: 1.1143 (rough estimate)
• Vapor Pressure: 0.085mmHg at 25°C
• Refractive Index: 1.5444 (estimate)
• Storage Temp.: ?20°C
• PKA: 9.00±0.70(Predicted)
• Water Solubility: 20g/L(5 oC)
• Stability: Unstable - deteriorates with storage. Incompatible with strong oxidizing agents.
• CAS DataBase Reference: N-Phenylhydroxylamine(CAS DataBase Reference)
• NIST Chemistry Reference: N-Phenylhydroxylamine(100-65-2)
• EPA Substance Registry System: N-Phenylhydroxylamine(100-65-2)

Safety Data

• Hazard Codes: T
• Statements: 25
• Safety Statements: 45
• RIDADR: UN 2811
• WGK Germany: 3
• RTECS: NC4900000
• HazardClass: 6.1
• PackingGroup: Ⅲ
• Hazardous Substances Data: 100-65-2(Hazardous Substances Data)

Usage

Uses

Used in Pharmaceutical Industry:
N-Phenylhydroxylamine is used as a starting material for the synthesis of 2-alkylindoles, which are important in the development of pharmaceutical compounds. It is synthesized by treating with aliphatic terminal alkynes using a gold catalyst via sequential 3,3-rearrangements and cyclodehydrations.
Used in Chemical Synthesis:
N-Phenylhydroxylamine is used as a starting material for the synthesis of isoxazolidines, which are valuable in the chemical industry. It is produced by reacting with aldehydes and α, β-unsaturated aldehydes via a three-component one-pot catalytic reaction.
Used in Organic Chemistry:
N-Phenylhydroxylamine is used as a starting material for the synthesis of tetrahydro-1,2-oxazines, which are significant in organic chemistry. It is obtained by treating with an aldehyde and cyclopropane via a homo 3+2 dipolar cycloaddition reaction.
Additionally, N-Phenylhydroxylamine is used in the manufacture of cupferron, which is an important chemical compound with various applications.

Preparation

To a dispersion of 180 gm (2.75 gm-atom) of zinc dust in 500 ml of 50% aqueous ethanol, with vigorous stirring, is added 130 ml (156 gm, 1.27 mole) of nitrobenzene. The reaction is initiated by the dropwise addition of an aqueous ammonium chloride solution and can thereafter be maintained at a controllable rate by the cautious addition of the remaining ammonium chloride solution. The reaction temperature rises during this reduction step. Once reflux has subsided, the basic zinc salts are filtered off using a sintered glass funnel. The light green filtrate is cooled in an ice-salt mixture to precipitate the product. The yield is 100 gm (72.2%), m.p. 81°C. The reduction of 2-methyl-2-nitropropane is carried out in a similar manner at 10-20°C to afford a 68% yield of N-t-butylhydroxylamine (m.p. 60-62°C).

Air & Water Reactions

Soluble in hot water.

Reactivity Profile

N-Phenylhydroxylamine neutralizes acids in exothermic reactions to form salts plus water. May be incompatible with isocyanates, halogenated organics, peroxides, phenols (acidic), epoxides, anhydrides, and acid halides. Flammable gaseous hydrogen may be generated in combination with strong reducing agents, such as hydrides.

Fire Hazard

Flash point data for N-Phenylhydroxylamine are not available but N-Phenylhydroxylamine is probably nonflammable.

Safety Profile

Poison by ingestion and subcutaneous routes. Human systemic effects by skin contact: primary irritation. Preparative hazard. Mutation data reported. When heated to decomposition it emits toxic fumes of NOx.

Purification Methods

Impure base deteriorates rapidly. Crystallise it from H2O, *C6H6 or *C6H6/pet ether (40-60o). The picrate has m 186o (from EtOH), and the benzenesulfonate salt has m 70o (dec )(EtOH/*C6H6). [Beilstein 15 H 2, 15 I 3, 15, II 4, 15 III 5. 15 IV 4.]

InChI:InChI=1/C6H7NO/c8-7-6-4-2-1-3-5-6/h1-5,7-8H

Upstream product

• 186581-53-3 diazomethane 
• 60-29-7 diethyl ether 
• 586-96-9 Nitrosobenzene 
• 13532-81-5 glyoxime-N_.N'-diphenyl ether 
• 100-63-0 phenylhydrazine 
• 32954-65-7 N,O-diacetylphenylhydroxylamine 
• 3376-40-7 N-benzyl-N-phenylhydroxylamine 
• 98-95-3 nitrobenzene 
• 557-20-0 diethylzinc 
• 122-66-7 diphenyl hydrazine 
• 539-44-6 N-4-methylphenylhydrazine 
• 110-89-4 piperidine 
• 201024-81-9 C,N-diphenylnitrone 
• 27991-08-8 N-acetoacetylphenylhydroxyloamine 

Downstream Products

• 35225-46-8 N,N'-dihydroxy-N,N'-diphenyl-methanediyldiamine 
• 62-53-3 aniline 
• 105105-34-8 1-(N-hydroxy-anilinomethyl)-piperidine 
• 99981-89-2 4-(N-hydroxy-anilinomethyl)-morpholine 
• 495-48-7 Azoxybenzene 
• 20972-43-4 trans-azoxybenzene 
• 5615-81-6 3-(phenylamino)pyrrolidine-2,5-dione 
• 26454-88-6 1,4-diphenyl-2-(phenylamino) but-2-ene-1,4-dione 
• 35998-80-2 (Z)-N-phenyl-1-(1H-pyrrol-2-yl)methanimine oxide 
• 35998-79-9 furfural-(N-phenyl oxime ) 
• 37140-94-6 N-hydroxy-N-phenyl-nicotinamide 
• 7630-14-0 N-furoylphenylhydroxylamine 
• 29556-13-6 N-phenyl-2-thenohydroxamic acid 
• 84186-34-5 α-(3-indolyl) N-phenyl nitrone 

Relevant articles and documents

Metal Ion-Catalyzed Reduction of Substituted Nitrosobenzenes by 1-Benzyl-3,5-bis(1-pyrrolidinylcarbonyl)-1,4-dihydropyridine in Acetonitrile

Metal ion catalyzed reduction of substituted nitrosobenzenes by 1-benzyl-3,5-bis(1-pyrrolidinylcarbonyl)-1,4-dihydropyridine (BPDH) in acetonitrile has been studied for seven bivalent metal ions.The reduction of N-methylacridinium salt (MA) has also been examined.In the former cases, it was found that the metal ions catalyze the reduction by forming a 1 : 1 complex with BPDH according to a Michaelis-Menten type saturation kinetics which allowed to derive the association constants, KM, for the complexation and the second-order rate constants, k2, for the reduction.A linear relationship was found between log k2 and the ionization potentials of metal ions with a positive slope.A linear Hammett relationship was also observed between log k2 and the Hammett ? constants with a positive p value for three metal ions.These results suggest that a bivalent metal ion is sandwiched between the BPDH and the substrate and acts as a Lewis acid to stabilize the incipient N-oxide anion of the substrate which is formed by hydride transfer in the transition state.In the cases of MA, all metal ions inhibited the reduction.Repulsion between the positive charges of the metal ion-BPDH complex and the substrate salt appears to be prevailing.

ACID CATALYZED REDUCTION OF NITROSOBENZENE BY 3,5-DIPYRROLIDINOCARBAMOYL-N-BENZYL-1,4-DIHYDROPYRIDINE AS A NADH ANALOG

Acid catalyzed reduction of substituted nitrosobenzenes to the hydroxylamines by 3,5-dipyrrolidinocarbamoyl-N-benzyl-1,4-dihydropyridine has been studied in anhydrous acetonitrile.

Rapid and convenient conversion of nitroarenes to anilines under microwave conditions using nonprecious metals in mildly acidic medium

Nitroarenes are reduced to the corresponding aniline derivatives using iron or zinc under mild conditions under microwave heating conditions. Mild acidity is provided by ammonium chloride in an aqueous methanol medium. The conditions are tolerant to other functional groups, with the exception of bromoalkyl derivatives, which yield complex reaction mixtures; otherwise, yields are generally quite high (80–99%).

Green synthesized silver nanoparticles decorated on reduced graphene oxide for enhanced electrochemical sensing of nitrobenzene in waste water samples

In the present work, an electrochemical sensor for nitrobenzene (NB) has been developed based on a green synthesized silver nanoparticles (AgNPs) decorated reduced graphene oxide (RGO) modified glassy carbon electrode (GCE). The AgNPs were synthesized using Justicia glauca leaf extract as a reducing and stabilizing agent. A RGO-AgNPs composite modified electrode was prepared by a simple electrochemical reduction of AgNPs dispersed GO solution. FESEM of RGO-AgNPs composite confirms that AgNPs are firmly attached on the RGO sheets and the average size of AgNPs is found to be 40 ± 5 nm. The modified electrode shows good efficiency with lower overpotential for electrocatalytic reduction of NB than that of other modified electrodes (AgNPs and RGO). The DPV response confirms that the reduction peak current of NB is linear over the concentrations from 0.5 to 900 μM. The sensitivity of the sensors is found to be 0.836 μA μM-1 cm-2 with the detection limit of 0.261 μM for NB. In addition, the RGO-AgNPs composite modified electrode shows good selectivity in the presence of potentially interfering similar compounds and good practicality in the waste water samples. This journal is

Effect of substituents on the rate of oxidation of anilines with peroxomonosulfate monoanion (HOOSO3-) in aqueous acetonitrile: A mechanistic study

Mechanistic studies on the oxidation of 18 meta-, para-, and ortho-substituted anilines (Ans) by HOOSO3- in aqueous acetonitrile medium have been performed. The reaction can be characterized by the experimental rate equation, -d[HSO5-]/dt = k[An][HSO5-] The addition of p-toluenesulfonic acid (TsOH) retards the reaction. The increase in the reactivity of anilines as the medium is made more aqueous is interpreted. The reaction is enhanced by electron-donating groups on the amine in the series consistent with the rate-limiting nucleophilic attack of the amine on the persulfate oxygen. The proposed mechanism involves the conversion of phenylhydroxylamine to nitrosobenzene in a fast step. The ESR study reveals the absence of free radicals in the reaction. Various attempts have been made to analyze the experimental rate constants in terms of LFER plots. Improved correlations are obtained with σ- values and the σ- form of the Yukawa-Tsuno equation.

A study on the selective hydrogenation of nitroaromatics to N-arylhydroxylamines using a supported Pt nanoparticle catalyst

A supported Pt nanoparticle-based catalyst was used in the chemoselective hydrogenation of nitroarenes to N-arylhydroxylamines (N-AHA). Optimization of NB hydrogenation conditions showed that substantially higher N-PHA yields can be obtained at low temperature. Especially, the influence of an increased hydrogen pressure on selectivity is remarkable. Maximum yields increase from 55% N-PHA at 4 bar H2 to 80% at 23 bar H2 in ethanol. Further optimization led to the use of small amounts of amine additive, TMEDA, with 50 bar H2 raising the maximum yield to 97% N-PHA. The decreased N-PHA hydrogenation rate at high H2 pressure and the presence of TMEDA allow for selective transformation of a range of other nitroarenes containing electron-withdrawing and -donating (reducible) functional groups to their N-AHAs in excellent (more than 90%) yields.

Supported bimetallic catalyst Pt-Pb/SiO2for selective conversion of nitrobenzene to p-aminophenol in pressurized CO2/H2O system

Various supported Pt-Pb bimetallic catalysts were prepared and applied for the catalytic conversion of nitrobenzene to p-aminophenol in the environmentally benign pressurized CO2/H2O system. Among the bimetallic catalysts prepared, Pt-Pb/SiO2is the best and nitrobenzene could be converted to p-aminophenol with a selectivity as high as 82% when the reaction was carried out using this catalyst at 110 °C under 5 MPa CO2and 0.2 MPa H2.

The selective reduction of nitroarenes to N-arylhydroxylamines using Zn in a CO2/H2O system

Nitroarenes are reduced to the corresponding N-arylhydroxylamines with high selectivity using Zn dust in a CO2/H2O system under mild conditions. The yield of N-phenylhydroxylamine from nitrobenzene is 88% when the reaction is carried out at 25 °C for 1.5 hours with a Zn to nitrobenzene molar ratio equal to 3 under 0.1 MPa CO2. Other nitroarenes, which contain reducible functionality other than a nitro group, are also reduced to the corresponding N-arylhydroxylamines with yield from 88% to 99%. The process fully removes the need to use NH4Cl and is environmentally benign. The Royal Society of Chemistry 2009.

Model molecules with oxygenated groups catalyze the reduction of nitrobenzene: Insight into carbocatalysis

The role of different oxygen functional groups on a carbon catalyst was studied in the reduction of nitrobenzene by using a series of model molecules. The carbonyl and hydroxyl groups played important roles, which may be ascribed to their ability to activate hydrazine. In comparison, the ester, ether, and lactone groups seemed to be inactive, whereas the carboxylic group had a negative effect. The reaction occurred most likely through a direct route, during which nitrosobenzene may be converted directly into aniline. Modeling carbon: Thanks to model molecules, the carbon-catalyzed reduction of nitrobenzene is mimicked. The role of different oxygen functional groups on a carbon catalyst is studied, and the carbonyl and hydroxyl groups seem to be the most important moieties, which may be ascribed to their ability to activate hydrazine. The reaction occurs more likely through a direct route, during which nitrosobenzene may also be converted directly into aniline.

SELECTIVE HYDROGENATION OF NITROBENZENE IN APROTIC MEDIA

The kinetics of hydrogenation of nitrobenzene in aprotic media was studied, and a scheme of the mechanism and a kinetic equation, corresponding to it, for the initial reaction rate are proposed.High selectivity with respect to N-phenylhydroxylamine is apparently due to the aprotic nature and donor properties of the solvent and also to the functioning of the catalyst as a unique "hydrogen electrode."