98276-82-5

Upstream product

• 4229-44-1 N-methylhydroxyamine hydrochloride 
• 350-46-9 4-Fluoronitrobenzene 
• 126614-92-4 N-Methyl-N-(4-nitrophenyl)-O-pivaloylhydroxylamine 
• 88867-70-3 C₁₁H₁₄N₂O₄ 

Downstream Products

• 6085-92-3 N-methyl-2-chloro-4-nitroaniline 

Relevant academic research and scientific papers

Cascade Approach to Highly Functionalized Biaryls by a Nucleophilic Aromatic Substitution with Arylhydroxylamines

A transition-metal free synthesis of highly functionalized 2-hydroxy-2′-amino-1,1′-biaryls from N-arylhydroxylamines has been developed. This operationally simple and readily scalable approach relies on a cascade of reactions that initially generates transient N,O-diarylhydroxylamines, via direct O-arylation, which then undergo rapid [3,3]-sigmatropic rearrangement and subsequent rearomatization to form NOBIN-type products. These structurally diverse functionalized biaryls are obtained under mild conditions in good to excellent isolated yields.

Competitive Base-Induced α-Elimination and Methanolysis of N-Aryl-O-pivaloylhydroxylamines

The N-aryl-O-pivaloylhydroxylamines 1a-c are quite stable in MeOH under neutral conditions, but under mildly basic conditions (0.05 M Et2NH or Et3N) they undergo rapid decomposition (t1/2 = ca. 3-5 h at 25 deg C) by two competitive processes: apparent α-elimination to generate the nitrenes 2a-c and pivalic acid and basic ester methanolysis to generate the hydroxylamines 3a-c and methyl pivalate.The nitrenes decompose into the corresponding anilines 5 and azobenzenes 7, while the hydroxylamines undergo nitrene-mediated oxidation into the corresponding azoxybenzenes 6.The mechanism of this latter process was probed by addition of excess hydroxylamine, and a mechanism for the oxidation consistent with available data (Scheme II) is proposed.It was also found that the nitrosobenzenes 8 undergo nucleophilic attack by conjugate bases 4a-c of the title compounds to produce one of the two possible isomeric nonsymmetrical azoxybenzenes.