96018-75-6

Upstream product

• 50-00-0 formaldehyd 
• 932-78-5 1-chloro-3-nitrosobenzene 
• 298-12-4 Glyoxilic acid 
• 10468-17-4 N-(3-chlorophenyl)hydroxylamine 
• 2258-42-6 formyl acetic anhydride 

Relevant academic research and scientific papers

Formation of hydroxamic acids promoted by metal ions. Interaction of aldehyde carbonyl group with C-nitroso group in the presence of ferric ions

Formation of N-phenyl substituted hydroxamic acids in the reaction of formaldehyde with substituted nitrosobenzene is strongly catalysed by Fe3+ ions, which stabilize the transition state for the rate-controlling proton transfer from the carbon of nitrosocarbinolic cation intermediate leading to the product, hydroxamic acid.

Reactions of Carbonyl Group with Nitroso Compounds: Reaction of Formaldehyde with Substituted Nitrosobenzenes

Formaldehyde reacts with substituted nitrosobenzenes giving the corresponding N-phenylhydroxamic acids.A mechanism involving three sequential steps in this reaction is proposed.The first step is the nucleophilic attack of the nitroso group on the carbonyl group which leads to the formation of the unstable tetrahedral zwitterionic intermediate.This step followed by the proton transfer to the zwitterionic intermediate to form more stable nitrosocarbinolic cation intermediate, which in the subsequent step undergoes the rate-controlling elimination of proton from the C-atom of nitrosocarbinolic group, leading to the final product, hydroxamic acid.The first and the second step appear to be reversible.The experimental evidence obtained, which is the basis for such a description of the investigated reaction, includes: a) the order of reactivity of substituted nitrosobenzenes, as demonstrated by the plot of log kobs vs. ? Hammett parameters with slope of -1.74; b) the observation of a general-acid catalysis; c) the observation of the inverse solvent deuterium isotope effect of ca. 1.8 in the reaction; d) the observation of kinetic primary deuterium isotope effect of ca. 8 related to to the 'water' reactions of formaldehyde with substituted nitrosobenzenes; e) the observation of general-base catalysis in the reaction; f) the observation of the kinetic primary deuterium isotope effect of ca. 2.1 for the acetate-ion catalyzed reaction.

A facile synthesis of N-aryl-N-hydroxyformamides from N-arylhydroxylamines

Several N-arylhydroxylamines (2) have been formylated for the first time with acetic formic anhydride to yield N-hydroxyformanilides (3) in better yields than hitherto reported.

N-Arylhydroxamic Acids: Reaction of Nitroso Aromatics with α-Oxo Acids

A practical and high-yielding route to N-arylhydroxamic acids from nitroso aromatics and α-oxo acids 1a-d is desctibed.In aqueous and acetic acid containing media, the reactions exhibit second-order reaction kinetics overall.In the aqueous medium, the rate constant (kobsd) for N-phenylacetohydroxamic acid (8b) formation increased with increasing +>, though there were some side pathways involving azoxybenzene formation.In general, kobsd for the reaction in the acetic acid containing medium was about one-tenth of that in HCl at pH 0.6.On a preparative scale, acetic acid is better than HCl, in that both reactants showed sufficient solubilities in acetic acid for a high reaction velocity and no side reaction was detected.With this method, the proximate carcinogens, N-(4-biphenylyl)acetohydroxamic acid (12b) and N-(2-fluorenyl)acetohydroxamic acid (13b), could be easily prepared.Under both conditions, the order of kobsd for the reactions of nitrosobenzene (2) with α-oxo acids 1a-d was glyoxylic (1a) > pyruvic (1b) 2-oxobutyric (1c) > benzoylformic (1d) acid.For the reactions of substituted nitrosobenzenes 3-6 with pyruvic acid (1b), the order of kobsd was p-phenyl (6) > unsubstituted (2) > p-chloro (5) > m-chloro (4) >> o-chloro (3) nitrosobenzene.The negative Hammett reaction constant value obtained indicates that an electron-donating substituent is preferable for the reaction.The reaction mechanism and other factors affecting N-arylhydroxamic acid formation are also descussed.

Reaction of Substituted Nitrosobenzenes with Formaldehyde

Substituted nitrosobenzenes react with formaldehyde in an acid-catalysed reaction giving N-phenylhydroxamic acids.

Reaction of Nitroso Aromatics with Glyoxylic Acid. A New Path to Hydroxamic Acids

In aqueous solution substituted aromatic nitroso compounds react rapidly with glyoxylic acid to produce N-hydroxyformanilides and CO2.The reaction is nearly quantitative for all nitroso aromatics investigated and serves as a convenient synthetic route to