5553-70-8

Upstream product

• 23135-14-0 N,O-dibenzyl-N-nitrosohydroxylamine 
• 108-24-7 acetic anhydride 
• 4383-24-8 N,O-dibenzylhydroxylamine 
• 17146-21-3 O-(benzyl)benzaldoxime 
• 100-52-7 benzaldehyde 
• 10229-60-4 Z-benzaldehyde O-benzyloxime 
• 2687-43-6 O-benzylhydoxylamine hydrochloride 

Downstream Products

• 588-46-5 N-(phenylmethyl)acetamide 
• 7340-01-4 N-hydroxy-N-benzyl acetamide 
• 19051-17-3 (N-benzylacetylamino)acetate 

Relevant academic research and scientific papers

Base-promoted aromatic [3,3] sigmatropic rearrangement of N-acyl-O-arylhydroxylamine derivatives

The base-promoted aromatic [3,3] sigmatropic rearrangement of N-acyl-O-arylhydroxylamines giving α-(2-hydroxyphenyl)amides was successfully demonstrated. The substrates were prepared from N-substituted hydroxylamines by N-acylation followed by copper(I)-mediated O-arylation with boronic acids. Treatment of the substrates with lithium hexamethyldisilazide (LiHMDS) in THF at 0 °C to room temperature generated the corresponding amide enolates. The aromatic [3,3] rearrangement of the enolates provided the desired products in moderate to good yields. A crossover experiment produced only intramolecular products and clarified that the reaction proceeds via the aromatic [3,3] sigmatropic rearrangement, not a bond-cleavage–recombination process. Our method is a formal α-arylation of amides.

Reductive cleavage of N-O bonds in hydroxylamines and hydroxamic acid derivatives using samarium diiodide

An efficient process for the reductive cleavage of N-O bonds using samarium diiodide is detailed for a variety of structural types to define the scope and limitations of the method. The reduction is shown to be compatible with base sensitive substrates such as trifluoroacetamide derivatives, which cannot be reduced satisfactorily using aluminum amalgam or sodium amalgam. Direct quenching of the reduction mixture with acylating agents is demonstrated to provide high yields of protected amines in a one-pot process from the N-O derivatives.

N-NITROSOHYDROXYLAMINES III. REACTION OF N,O-DIBENZYL-N-NITROSOHYDROXYLAMINES WITH ACETIC ANHYDRIDE

The major path of the reaction of N,O-dibenzyl-N-nitrosohydroxylamines (3) with acetic anhydride appears to proceed by initial radical cleavage of the N-N bond with loss of nitric oxide.The formation of the main products (5) may be rationalized by subsequent transformation of the resulting hydroxylamino radicals.

THE UNUSAL REARRANGEMENT OF N-NITROSO-N,O-DIBENZYLHYDROXYLAMINES WITH ACETIC ANHYDRIDE

Treatment of N-nitroso-N,O-dibenzylhydroxylamine (2a) with acetic anhydride in benzene at reflux results in a remarkable rearrangement to 2-benzoyl-1-acetylbenzylhydrazine and it was established that it is the N-benzyl substituent of 2a that is transformed into the benzoyl group of the rearranged product (3a).