38974-06-0

Upstream product

• 70853-94-0 N-(2,4-dimethylphenyl)hydroxylamine 
• 95-68-1 2,4-Xylidine 
• 89-87-2 2,4-dimethylnitrobenzene 
• 99-99-0 1-methyl-4-nitrobenzene 
• 108-38-3 m-xylene 

Downstream Products

• 99766-50-4 bis-(2,4-dimethyl-phenyl)-diazene-N-oxide 
• 1616382-56-9 5-((2,4-dimethylphenyl)diazenyl)isophthalic acid 
• 1616382-55-8 dimethyl 5-((2,4-dimethylphenyl)diazenyl)isophthalate 

Relevant academic research and scientific papers

Azobenzene-functionalized metal-organic polyhedra for the optically responsive capture and release of guest molecules

Stimuli-responsive metal-organic polyhedra (srMOPs) functionalized with azobenzene showed UV-irradiation-induced isomerization from the insoluble trans-srMOP to the soluble cis-srMOP, whereas irradiation with blue light reversed this process. Guest molecules were trapped and released upon cis-to-trans and trans-to-cis isomerization of the srMOPs, respectively. This study provides a new direction in the ever-diversifying field of MOPs, while laying the groundwork for a new class of optically responsive materials. Lock in the guests, later set them free: Stimuli-responsive metal-organic polyhedra (srMOPs) functionalized with azobenzene showed UV-light-induced isomerization from insoluble srMOPs substituted with trans-azobenzene to soluble srMOPs with cis-azobenzene units; irradiation with blue light reversed this process (see picture). Guest molecules were trapped upon cis-to-trans and released upon trans-to-cis isomerization of the azobenzene units.

Tungsten- and molybdenum-based coordination polymer-catalyzed N-oxidation of primary aromatic amines with aqueous hydrogen peroxide

Recyclable tungsten- and molybdenum-based coordination polymers efficiently catalyzed the oxidation of primary aromatic amines to the corresponding nitroso derivatives with 30% aqueous hydrogen peroxide in high yields at room temperature.

Nitrosation of anisole, stability constants of complexes of the nitrosonium ion with aromatic nitroso compounds, and NMR studies of restricted rotation in the complexes

Anisole can be nitrosated in good yield under the acidic and anaerobic conditions previously reported for methylbenzenes. The product, 4-nitrosoanisole, is slowly converted into 4-nitrosophenol in acetic-sulfuric acid mixtures. The decrease in the rate constant for this reaction with increasing concentration of nitrosonium ion leads to an estimate of the stability constant of the complex between 4-nitrosoanisole and nitrosonium ion. Stability constants for the similar complexes formed by 4-nitrosotoluene and 1,3-dimethyl-4-nitrosobenzene with nitrosonium ion in trifluoroacetic acid have been determined by UV spectroscopy. Restricted rotation about the bond between nitrogen and aromatic carbon is evident from the 1H NMR spectra of the complexes; activation parameters for the rotation are reported and compared with similar data in the literature for restricted rotation in uncomplexed aromatic nitroso compounds.

Kinetics and mechanism of nitrosation of toluene, o-xylene, and m-xylene in trifluoroacetic acid, or in acetic-sulfuric acid mixtures, under nitric oxide

The title reactions give good yields with m-xylene, and modest yields with toluene and o-xylene which are successfully directly nitrosated for the first time. The advantages of purging with nitric oxide are demonstrated and discussed. The kinetics have been successfully interpreted in terms of a mechanism in which both the aromatic substrate and the nitrosoaromatics form, reversibly, complexes with nitrosonium ion. The nitrosoaromatics are unstable under the acid conditions and the method is successful only because of the protective complexation with the nitrosonium ion.

Nitrosation of m-xylene, anisole, 4-nitrophenyl phenyl ether and toluene in trifluoroacetic acid or in acetic-sulfuric acid mixtures under nitric oxide

Nitrosation in trifluoroacetic acid or in acetic-sulfuric acid mixtures is regioselective and accompanying non-selective nitrous acid catalysed nitration can be avoided by purging with nitric oxide.

Oxidation of Primary Aromatic Amines, Catalyzed by Tungsten Compounds

Treatment of o-nitroanilines and o-aminobenzoic acids with 30 percent hydrogen peroxide in the presence of Na2WO4 and H3PO4 results in selective formation of corresponding nitroso derivatives.In other cases, the products are azoxy compounds.Oxidation of anilines containing alkyl or alkoxy groups in the ortho and para positions with hydrogen peroxide in the presence of Na2WO4 and tetrabutylammonium bromide quantitatively yields corresponding nitrosobenzenes.The H2O2-Na2WO4-H3PO4 system in the presence of tetrabutylammonium bromide is proposed for preparation of nitroso derivatives from anilines containing electron-acceptor meta and para substituents.

Direct Nitrosation of Aromatic Hydrocarbons and Ethers with the Electrophilic Nitrosonium Cation

Various polymethylbenzenes and anisoles are selectively nitrosated with the electrophilic nitrosonium salt NO(1+)BF4(1-) in good conversions and yields under mild conditions in which the conventional procedure (based on nitrile neutralization with strong acid) is ineffective.The reactivity patterns in acetonitrile deduced from the various time/conversions in Tables 2 and 3 indicate that aromatic nitrosation is distinctly different from those previously established for electrophilic aromatic nitration.The contrasting behavior of NO(1+) in aromatic nitrosation is ascribed to a rate-limiting deprotonation of the reversibly formed Wheland intermediate, which in the case of aromatic nitration with NO2(1+) occurs with no deuterium kinetic isotope effect.Aromatic nitroso derivatives (unlike the nitro counterpart) are excellent electron donors that are subject to a reversible one-electron oxidation at positive potentials significantly less than that of the parent polymethylbenzene or anisole.As a result, the series of nitrosobenzenes are also much better Broensted bases than the corresponding nitro derivatives, and this marked distinction, therefore, accounts for the large differentiation in the deprotonation rates of their respective conjugate acids (i.e.Wheland intermediates).