N-nitrosohydroxylamines I. Acetolysis and acid-catalyzed hydrolysis of N,O-dibenzyl-N-nitrosohydroxylamines. Reaction with potassium t-butoxide

✍ Scribed by Kunio Kano; Jean-Pierre Anselme

• Publisher: Elsevier Science
• Year: 1992
• Tongue: French
• Weight: 1004 KB
• Volume: 48
• Category: Article
• ISSN: 0040-4020
• DOI: 10.1016/s0040-4020(01)89037-2

✦ Synopsis

The major products of the hydrolysis of N,O-dibenzyl-N-nitrosohydroxylamines (3) are the denitrosated parent hydroxylamines (6); under mom forcing conditions, products of the further hydrolysis of 6 are obtained. Acetolysis in acetic acid gives the benzyl acetates derived from both N-and 0-substituents. With potassium tert-butoxide, the major path is abstraction of an 0-benzyl hydrogen followed by fragmentation to the aldehyde and the benzyldiazotate ion. Possible mechanisms for the formation of the products are discussed. 10076 K. KANO and J.-P. &WLME Results and Discussion A. Hydr0lG.s in concenbwd H_vtihlotic Acid The hydrolysis of N-@methylbenzyl)-0-benzyl-N-nitrosohydroxylamine (3a) in cont. hydrochloric acid carried out at 70-90 "gave the denitrosated product N-(p-methylbenzyl)-0-benzylhydroxylamine (6a) as the major product, in addition to p-methylbenzyl chloride (7a), benzyl chloride (7b), N-(p-methylbenzyl)hydroxylamine @a) and p-tolualdehyde (5n) (Scheme 2 and Table I); neither the alcohol (4a) nor benzaldehyde (5b) expected on the basis of the PMGH&Hz \ N-NO PhCH20' gMeC6H&H20H + PhCHO Pa