623-10-9

Usage

Uses

Used in Pharmaceutical and Agrochemical Industries:
N-(p-Tolyl)hydroxylamine is utilized as an intermediate in the synthesis of various pharmaceuticals and agrochemicals, contributing to the development of new drugs and pesticides.
Used in Antioxidant and Inhibitor Production:
N-(p-Tolyl)hydroxylamine serves as a key ingredient in the production of antioxidants and inhibitors, which are essential for preventing oxidation in various industrial applications and controlling chemical reactions.
Used in Rubber and Plastics Industry:
N-(p-Tolyl)hydroxylamine is employed in the rubber and plastics industry to enhance the properties of these materials, such as durability and resistance to degradation.

InChI:InChI=1/C7H9NO/c1-6-2-4-7(8-9)5-3-6/h2-5,8-9H,1H3

Upstream product

• 99-99-0 1-methyl-4-nitrobenzene 
• 106-49-0 p-toluidine 
• 623-11-0 1-methyl-4-nitrosobenzene 
• 100-63-0 phenylhydrazine 
• 70-18-8 GLUTATHIONE 
• 27451-21-4 N-hydroxy-N-(p-tolyl)acetamide 
• 79566-24-8 N-(3-Benzyl-4-phenyl-2-p-tolyl-isoxazolidin-5-yl)-N-p-tolyl-hydroxylamine 
• 78661-62-8 (Z)-2-phthalimido-1-p-tolyl-diazen-1-oxid 
• 1503-92-0 N-p-tolylbenzohydroxamic acid 
• 29556-29-4 N-p-Tolyl-p-chlorobenzohydroxamic acid 
• 13664-48-7 N-p-methylbenzoyl-N-p-methylphenylhydroxylamine 
• 60-29-7 diethyl ether 
• 64-19-7 acetic acid 
• 71-43-2 benzene 

Downstream Products

• 100957-77-5 N,N'-dihydroxy-N,N'-di-p-tolyl-methanediyldiamine 
• 102313-38-2 1-(N-hydroxy-p-toluidinomethyl)-piperidine 
• 955-98-6 di-p-tolyl-diazene (E)-N-oxide 
• 955-98-6 4,4'-Dimethyl-azoxybenzol 
• 99237-41-9 glyoxal-bis-(N-p-tolyl oxime ) 
• 911849-24-6 piperonal-(N-p-tolyl oxime ) 
• 955-98-6 1,2-bis(4-methylphenyl)diazene oxide 
• 92245-76-6 4-(2-methyl-5-nitro-benzyl)-aniline 
• 29418-24-4 (2,4-dimethyl-phenyl)-p-tolyl-diazene 
• 501-60-0 1,2-di(p-tolyl)diazene 
• 588-04-5 3,3'-dimethylazobenzene 
• 5913-01-9 N-hydroxy-N'-phenyl-N-p-tolyl-formamidine 
• 41565-47-3 3-(4-bromo-phenyl)-1-p-tolyl-triazen-1-ol 
• 41565-45-1 (3-nitro-benzenediazo)-p-tolylhydroxylamide 

Relevant academic research and scientific papers

Generating System-Level Responses from a Network of Simple Synthetic Replicators

The creation of reaction networks capable of exhibiting responses that are properties of entire systems represents a significant challenge for the chemical sciences. The system-level behavior of a reaction network is linked intrinsically to its topology and the functional connections between its nodes. A simple network of chemical reactions constructed from four reagents, in which each reagent reacts with exactly two others, can exhibit up-regulation of two products even when only a single chemical reaction is addressed catalytically. We implement a system with this topology using two maleimides and two nitrones of different sizes - either short or long and each bearing complementary recognition sites - that react pairwise through 1,3-dipolar cycloaddition reactions to create a network of four length-segregated replicating templates. Comprehensive 1H NMR spectroscopy experiments unravel the network topology, confirming that, in isolation, three out of four templates self-replicate, with the shortest template exhibiting the highest efficiency. The strongest template effects within the network are the mutually cross-catalytic relationships between the two templates of intermediate size. The network topology is such that the addition of different preformed templates as instructions to a mixture of all starting materials elicits system-level behavior. Instruction with a single template up-regulates the formation of two templates in a predictable manner. These results demonstrate that the rules governing system-level behavior can be unraveled through the application of wholly synthetic networks with well-defined chemistries and interactions.

Synthesis, crystal structure, theoretical study and application of 1-(4-methylphenyl)-3-(2- (trifluoromethyl)phenyl)triaz-1-ene 1-oxide in the extraction of Ni ions: Synthesis of a new triazene 1-oxide derivative, X-ray crystal structure and its theoretical studies

The crystal structure of 1-(4-methylphenyl)-3-(2-(trifluoromethyl)phenyl)triaz-1-ene 1-oxide (L) is monoclinic and has a space group of P21/c with a = 8.066(2) ?, b = 16.740(5) ?, c = 11.730(4) ?, β = 117.76(3)° and Z = 4. In this study, direct procedures were used to solve the crystalline structure of this complex and refine it by full-matrix least-squares to ultimate values of R1 = 0.0610 and wR2 = 0.1661 with 1474 reflections (I > 2σ(I)). The molecule is included in inter-hydrogen bonding with C5–H5 acting as donors and O atoms of N-oxide groups as acceptors (O1······H5) with a distance of 2.638 ?. These results were also confirmed by theoretical studies. The spectrophotometric titrations of the synthesized L with metal ions showed a substantially greater stability constant for its nickel ion complex with a mole ratio equal to 1. Consequently, the ligand was used for the selective extraction and spectrophotometric determining the Ni2+ ion in natural water. Under optimized conditions, the calibrating curve was linear over a nickel concentration range of 9.2 × 10?7–8.4 × 10?3 M. The detecting limit of this method was 6.0 × 10?7 M Ni2+. No considerable interference was found from at least 100 times concentrations of a number of possibly interfering ions.

Selective Mild Oxidation of Anilines into Nitroarenes by Catalytic Activation of Mesoporous Frameworks Linked with Gold-Loaded Mn3O4 Nanoparticles

This work reports the synthesis and catalytic application of mesoporous Au-loaded Mn3O4 nanoparticle assemblies (MNAs) with different Au contents, i. e., 0.2, 0.5 and 1 wt %, towards the selective oxidation of anilines into the corresponding nitroarenes. Among common oxidants, as well as several supported gold nanoparticle platforms, Au/Mn3O4 MNAs containing 0.5 wt % Au with an average particle size of 3–4 nm show the best catalytic performance in the presence of tert-butyl hydroperoxide (TBHP) as a mild oxidant. In all cases, the corresponding nitroarenes were isolated in high to excellent yields (85–97 %) and selectivity (>98 %) from acetonitrile or greener solvents, such as ethyl acetate, after simple flash chromatography purification. The 0.5 % Au/Mn3O4 catalyst can be isolated and reused four times without a significant loss of its activity and can be applied successfully to a lab-scale reaction of p-toluidine (1 mmol) leading to the p-nitrotulene in 83 % yield. The presence of AuNPs on the Mn3O4 surface enhances the catalytic activity for the formation of the desired nitroarene. A reasonable mechanism was proposed including the plausible formation of two intermediates, the corresponding N-aryl hydroxylamine and the nitrosoarene.

Polystyrene stabilized iridium nanoparticles catalyzed chemo- and regio-selective semi-hydrogenation of nitroarenes to N-arylhydroxylamines

Polystyrene stabilized Iridium (Ir@PS) nanoparticles (NPs) as a heterogeneous catalyst have been developed and characterized by IR, UV–Vis, SEM, TEM, EDX and XRD studies. The prepared Ir@PS catalyst showed excellent reactivity for chemo- and regio-selective controlled-hydrogenation of functionalized nitroarenes to corresponding N-arylhydroxylamine using hydrazine hydrate as reducing source and environmentally benign polyethylene glycol (PEG-400) as green solvent. The present methodology was applied for vast substrate scope and found to be compatible with wide range of reducible functional groups. The reaction performed at 85 °C or ambient temperature and completed within 5–80 minutes. The catalyst can easily be filtered out from reaction mixture and reusable.

Electrochemically Tuned Oxidative [4+2] Annulation and Dioxygenation of Olefins with Hydroxamic Acids

This work represents the first [4+2] annulation of hydroxamic acids with olefins for the synthesis of benzo[c][1,2]oxazines scaffold via anode-selective electrochemical oxidation. This protocol features mild conditions, is oxidant free, shows high regioselectivity and stereoselectivity, broad substrate scope of both alkenes and hydroxamic acids, and is compatible with terpenes, peptides, and steroids. Significantly, the dioxygenation of olefins employing hydroxamic acid is also successfully achieved by switching the anode material under the same reaction conditions. The study not only reveals a new reactivity of hydroxamic acids and its first application in electrosynthesis but also provides a successful example of anode material-tuned product selectivity.

Polyfunctionalized biaryls accessed by a one-pot nucleophilic aromatic substitution and sigmatropic rearrangement reaction cascade under mild conditions

A practical synthetic method has been developed for polyfunctionalized biaryls based on a facile one-pot nucleophilic aromatic substitution (SNAr) reaction and [5,5]- or [3,3]-sigmatropic rearrangement reaction cascade. Under mild basic conditions, N-arylhydroxylamines reacted with o-activated fluoro (het)arenes to form N,O-diarylhydroxylamine intermediates which underwent spontaneously selective [5,5]-sigmatropic rearrangement reaction to produce diverse functionalized 4-amino-4′-hydroxy-1,1′-biaryls. A sequential SNAr reaction and [3,3]-sigmatropic rearrangement took place between N-arylhydroxylamines and 2-fluoropyridine derivatives or 4-fluorobenzonitrile to afford functionalized 2-amino-2′-hydroxy-1,1′-biaryls. As invaluable and unique building blocks, the resulting biaryls were applied in the straightforward synthesis of N2,O2-coronarene, carbazole, aza- and diaza carbazole derivatives.

Practical bromination of arylhydroxylamines with SOBr2 towards ortho-bromo-anilides

A facile approach for synthesizing ortho-bromoanilides from readily available aryhydroxylamines and thionyl bromide is demonstrated in this work. Mild reaction conditions and broad scope of substrates ranging from heterocyclic structures to pharmaceutics-potential motifs are used in the reactions of this paper. Efficient bromination of ortho C–H bonds of the aryhydroxylamines has been achieved. Ortho-bromoanilide products were obtained in good to excellent yields, and model scaled-up reactions of this synthetic approach are shown in this work.

Selective Reduction of Nitroarenes to Arylamines by the Cooperative Action of Methylhydrazine and a Tris(N-heterocyclic thioamidate) Cobalt(III) Complex

We report an efficient catalytic protocol that chemoselectively reduces nitroarenes to arylamines, by using methylhydrazine as a reducing agent in combination with the easily synthesized and robust catalyst tris(N-heterocyclic thioamidate) Co(III) complex [Co(κS,N-tfmp2S)3], tfmp2S = 4-(trifluoromethyl)-pyrimidine-2-thiolate. A series of arylamines and heterocyclic amines were formed in excellent yields and chemoselectivity. High conversion yields of nitroarenes into the corresponding amines were observed by using polar protic solvents, such as MeOH and iPrOH. Among several hydrogen donors that were examined, methylhydrazine demonstrated the best performance. Preliminary mechanistic investigations, supported by UV-vis and NMR spectroscopy, cyclic voltammetry, and high-resolution mass spectrometry, suggest a cooperative action of methylhydrazine and [Co(κS,N-tfmp2S)3] via a coordination activation pathway that leads to the formation of a reduced cobalt species, responsible for the catalytic transformation. In general, the corresponding N-arylhydroxylamines were identified as the sole intermediates. Nevertheless, the corresponding nitrosoarenes can also be formed as intermediates, which, however, are rapidly transformed into the desired arylamines in the presence of methylhydrazine through a noncatalytic path. On the basis of the observed high chemoselectivity and yields, and the fast and clean reaction processes, the present catalytic system [Co(κS,N-tfmp2S)3]/MeNHNH2 shows promise for the efficient synthesis of aromatic amines that could find various industrial applications.

Selective Photoinduced Reduction of Nitroarenes to N-Arylhydroxylamines

We report the selective photoinduced reduction of nitroarenes to N-arylhydroxylamines. The present methodology facilitates this transformation in the absence of catalyst or additives and uses only light and methylhydrazine. This noncatalytic photoinduced transformation proceeds with a broad scope, excellent functional-group tolerance, and high yields. The potential of this protocol reflects on the selective and straightforward conversion of two general antibiotics, azomycin and chloramphenicol, to the bioactive hydroxylamine species.

Tandem selective reduction of nitroarenes catalyzed by palladium nanoclusters

We report a catalytic tandem reduction of nitroarenes by sodium borohydride (NaBH4) in aqueous solution under ambient conditions, which can selectively produce five categories of nitrogen-containing compounds: anilines, N-aryl hydroxylamines, azoxy-, azo- and hydrazo-compounds. The catalyst is in situ-generated ultrasmall palladium nanoclusters (Pd NCs, diameter of 1.3 ± 0.3 nm) from the reduction of Pd(OAc)2 by NaBH4. These highly active Pd NCs are stabilized by surface-coordinated nitroarenes, which inhibit the further growth and aggregation of Pd NCs. By controlling the concentration of Pd(OAc)2 (0.1-0.5 mol% of nitroarene) and NaBH4, the water/ethanol solvent ratio and the tandem reaction sequence, each of the five categories of N-containing compounds can be obtained with excellent yields (up to 98%) in less than 30 min at room temperature. This tunable catalytic tandem reaction works efficiently with a broad range of nitroarene substrates and offers a green and sustainable method for the rapid and large-scale production of valuable N-containing chemicals.