55076-24-9

Upstream product

• 104-88-1 4-chlorobenzaldehyde 
• 698-16-8 benzohydroximoyl chloride 
• 139259-96-4 N-(acetyloxy)-N-(((4-chlorophenyl)methyl)oxy)benzamide 

Downstream Products

• 74-11-3 para-chlorobenzoic acid 
• 1126-46-1 Methyl 4-chlorobenzoate 

Relevant academic research and scientific papers

Thermal decomposition of N-acyloxy-N-alkoxyamides a new HERON reaction

The HERON reaction has been observed in the thermal decompositions of N-acyloxy-N-alkoxyamides 1b, members of the class of anomeric amides. The N,N-bisoxo-substitution results in reduced amide resonance and this, combined with an nO-σ*NOAcyl anomeric destabilization of the N-OAcyl bond, results in their intramolecular rearrangement to anhydrides 42 and alkoxynitrenes 43 in competition with homolysis of the N-OAcyl bond to alkoxyamidyls 51. The primary HERON product alkoxynitrenes are scavenged by oxygen, giving a nitrate ester, in competition with a rearrangement to nitriles and dimerization to hyponitrites, leading, under the conditions, to alcohols and aldehydes. Persistent alkoxyamidyls most likely form a 1,3-diradical in a solvent-cage reaction, which cyclizes to 3,5-disubstituted-(5H)-1,4,2-dioxazoles 47. Substituent effects support this competition reaction. CSIRO 2010.

Base-induced cycloreversion of nitrile oxide cycloadducts: Conversion of imines into secondary and tertiary amides and aromatic aldehydes into acids without a conventional oxidising agent

A series of substituted Δ2-1,2,4-oxadiazolines (4,5-dihydro-1,2,4-oxadiazoles) 12 have been prepared by 1,3-dipolar cycloaddition of nitrile oxides to imines and are found, upon treatment with KOBut, to undergo cycloreversion to give nitriles and amide anions. These can be protonated to give secondary amides or treated in situ with alkyl halides to give tertiary amides in moderate to good overall yield, although the reaction is restricted to examples with an aromatic substituent at the 5-position. The 1,4,2-dioxazoles 15, formed by cycloaddition of benzonitrile oxide to aromatic aldehydes, similarly undergo cycloreversion allowing direct conversion either into substituted benzoic acids or their methyl esters. Copyright 1996 by the Royal Society of Chemistry.