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Rearrangement reactions of aziridinylbenzaldoximes
Author(s) -
Johnson James E.,
Nwoko Delphine,
Hotema Martha,
Sanchez Natalia,
Alderman Reidun,
Lynch Vincent
Publication year - 1996
Publication title -
journal of heterocyclic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.321
H-Index - 59
eISSN - 1943-5193
pISSN - 0022-152X
DOI - 10.1002/jhet.5570330606
Subject(s) - chemistry , medicinal chemistry , stereochemistry , computational chemistry
Abstract Reactions of 2,2‐dimethylaziridine with benzohydroximoyl chlorides [ArC(Cl)NOH] give aziridinylbenzaldoximes 1 . It has been found that the aziridine ring in these compounds undergoes ring opening in hydrogen chloride‐dioxane solution to give (Z)‐ N ‐hydroxy‐ N ′‐(2‐chloro‐2‐methylpropyl)benzenecarboximidamides [ArC(NHCH 2 CR 1 R 2 Cl)NOH, 4 ]. Treatment of 1 with hydrochloric acid followed by neutralization with aqueous sodium hydroxide gave 6,6‐dimethyl‐3‐aryl‐1,2,4‐oxadiazines 2. Reaction of 4 with sodium hydride in dioxane gave 5‐isopropyl‐3‐aryl‐4,5‐dihydro‐1,2,4‐oxadiazoles 5. Reaction of the 4,5‐dihydro‐1,2,4‐oxadiazoles 5 with N ‐chlorosuccinimide gave the heteroaromatic 1,2,4‐oxadiazoles 6 . It is suggested that reactions of 4 with sodium hydride in dioxane solution involve the conjugate base of 4 which undergoes a 1,2‐hydride shift that is concerted with loss of chloride ion. In aqueous sodium hydroxide solution it is suggested that the conjugate base of 4 undergoes ionization of the chlorine atom followed by nucleophilic attack by the oximate anion.