23579-36-4

Upstream product

• 79322-28-4 4-methyl-5-phenyl-2,5-diaza-1-oxapentadiene 
• 90701-78-3 1-acetyl-4-methyl-5-phenyl-2,5-diaza-1-oxapentadiene 
• 10341-75-0 (E)-1-phenylethanone oxime 
• 90701-79-4 1,4-dimethyl-5-phenyl-2,5-diaza-1-oxapentadiene 
• 7677-24-9 trimethylsilyl cyanide 
• 85027-95-8 acetophenone oxime mesylate 

Downstream Products

• 40697-35-6 2-phenylhydrazono-propionitrile 

Relevant academic research and scientific papers

The Thermolysis of Polyazapentadienes. Part 3. Cyclisation of C-Methyl-1,2,5-triazapentadienes and Related Compounds: The Role of an Intermediate Spirodienyl Radical

A series of C-methyl-1,2,5-triazapentadienes and 2,5-diaza-1-oxapentadienes are prepared from pyruvaldehyde phenylhydrazones and oxime anils respectively.The 4-methyl derivatives show E/Z isomerism about the 4,5-double bond.Pyrolysis of the 5-phenyl derivatives (1), (3), (5), (7), and (10) causes cyclisation to 2-methylquinoxaline, though 2-phenyliminopropanonitrile is obtained from the oxime ester (9).Pyrolysis of the 5-p-tolyl derivatives (2), (4), (6), (8), and (11) qives mixtures of 2,6- and 2,7-dimethylquinoxaline.There are formed predominantly by the rearrangement reaction which involves the spirodienyl radical (19), but also by direct cyclisation of the iminyl radicals (17) and (18).

Organoaluminum-Promoted Beckmann Rearrangement of Oxime Sulfonates

The Beckmann rearrangement of oxime sulfonates with simultaneous nucleophilic trapping of the intermediary iminocarbocation by organoaluminum reagents is described.This process provides a new and highly efficient route to imino thioethers, imino selenoethers, imino nitriles, and α-alkylated amines starting from oxime sulfonates by the use of dialkylaluminum thiolates, selenolates, diethylaluminum chloride-trimethylsilyl cyanide, and trialkylaluminum-diisobutylaluminum hydride systems, respectively.The present organoaluminum-promoted Beckmann rearrangement of oxime sulfonates has been successfully applied to the synthesis of naturally occuring alkaloids, pumiliotoxin C and solenopsin A and B, in stereoselective fashion.Moreover, α,α-dialkylation of amines can be realized by the successive treatment of oxime sulfonates with trialkylaluminum followed by allylic or propargylic Grignard reagents in synthetically useful yields.