31335-69-0

Upstream product

• 64-18-6 formic acid 
• 100-65-2 N-Phenylhydroxylamine 
• 50-00-0 formaldehyd 
• 586-96-9 Nitrosobenzene 
• 100-61-8 N-methylaniline 
• 865-47-4 potassium tert-butylate 
• 2706-75-4 sodium glyoxylate 
• 5913-00-8 N-hydroxy-N,N'-diphenyl-formamidine 
• 7732-18-5 water 
• 62-53-3 aniline 
• 563-96-2 2,2-dihydroxyacetic acid 
• 98-95-3 nitrobenzene 
• 430-75-1 glyoxylate 
• 298-12-4 Glyoxilic acid 

Downstream Products

• 58246-76-7 indole-1-carboxaldehyde 
• 100-65-2 N-Phenylhydroxylamine 
• 80820-92-4 N-(4-Nitrophenyl)carbamoyloxy-N-phenylformamid 
• 80820-91-3 N-Cyclohexylcarbamoyloxy-N-phenylformamid 
• 64-18-6 formic acid 
• 123-30-8 4-amino-phenol 
• 103-71-9 phenyl isocyanate 
• 936476-34-5 Zn(C(CH₃)2SCH(C₃HN₂(CH₃)2)2)(HCON(C₆H₅)O) 
• 586-96-9 Nitrosobenzene 

Relevant academic research and scientific papers

Evidence for proton transfer from carbon to chloride ion in solution

Unambiguous evidence for proton transfer from carbon to chloride ion in solution has been obtained for the first time, in the formation of hydroxamic acids from aldehydes and nitrosobenzenes in acetonitrile.

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.

Reaction of 2-nitroso-2-methyl propane with formaldehyde, glyoxylate and glyoxylic acid

2-nitroso-2-methyl propane reacts with formaldehyde, glyoxylate, glyoxylic, pyruvic and phenylglyoxylic acid giving the corresponding N-t-butyl hydroxamic acids. These reactions involve formation of the dipolar addition intermediates and 2-nitroso-2-methyl propane acts as a nucleophile in the reaction step in which these intermediates are formed.

Reaction of Substituted Nitrosobenzenes with Formaldehyde

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

Transketolase Catalyzed Synthesis of N-Aryl Hydroxamic Acids

Hydroxamic acids are metal-chelating compounds that show important biological activity including anti-tumor effects. We have recently engineered the transketolase from Geobacillus stearothermopilus (TKgst) to convert benzaldehyde as a non-natur

Intermediate analogue inhibitors of mandelate racemase: N-Hydroxyformanilide and cupferron

Mandelate racemase (MR) catalyzes the 1,1-proton transfer that interconverts the enantiomers of mandelate. The transition state/intermediate analogues N-hydroxyformanilide (Ki = 2.79 ± 0.19 μM) and cupferron (Ki = 2.67 ± 0.09 μM) are

Intriguing salt effects in the formation of hydroxamic acids from aldehydes and nitroso compounds

Addition of inorganic chlorides and perchlorates into the reaction mixture in water leads to a significant increase of the rate constants observed for the formation of N-phenyl hydroxamic acids from nitrosobenzene and formaldehyde or acetaldehyde. The rate enhancements (relative to the reaction rate constant in pure water) vary from the 7.4-fold increase observed on addition of 2.0 mol dm-3 Mg(ClO4)2 into the reaction mixture to the 230.0-fold increase in the case of 2.0 mol dm-3 of MgCl2 added. Linear correlation between log kobs for the formation of the N-phenylformohydroxamic acid from nitrosobenzene and formaldehyde and the concentration of the anion of the salt added has been observed for MgCl2, CaCl2, LiCl, Mg(ClO4)2 and NaClO4, but different correlations were obtained for NaCl, HCl and HClO4. The observations are discussed in terms of ion pairing between the unstable cation reaction intermediates and the anion of the salt. The results obtained suggest that stabilization of the unstable cationic reaction intermediate by the formation of an ion pair with the salt anion is of key importance for the formation of hydroxamate from aldehydes and nitrosobenzenes in more concentrated inert salt water solutions.

Salt effects and kinetic isotope effects interconnected. Evidence for the involvement of chloride ion in the C-H bond breaking in aqueous solution?

An unusual change of the primary kinetic isotope effect in the formation of hydroxamic acid from nitrosobenzene and formaldehyde in mixed solvents on addition of very small quantities of salts and at higher salt concentration in water was observed and interpreted in terms of ion pairing and hydrogen bonding phenomena in the reaction.

Formation of Hydroxamic Acids Promoted by Metal Ions. Interaction of Nitroso Group with Coordinated Carbonyl Group

Hydroxamic acids are formed in the interaction of nitroso group of substituted nitrosobenzenes with carbonyl group of glyoxylate coordinated on iron(III) ion.