Synthetic methods involving neighboring group interaction in o-substituted nitrobenzene derivatives

Hydroxynitrobenzodifuroxan and its salts

“…A common procedure for the preparation of benzofuroxans involves thermolysis of a benzene compound containing adjacent azido and nitro groups [4]. Thus, in our approach to the synthesis of hydroxynitrobenzodifuroxan (5-nitro [1,2,5]oxadiazolo [3,4-e] [2,1,3]benzoxadiazol-4-ol-3,8-dioxide) (1), we centered on the formation of a diazido-trinitrobenzene intermediate that also contains a hydrolysable group (such as the methoxy group in 3 in Scheme 1) [5].…”

“…In form B, these groups are para to each other. The transformation between forms A and B is an example of the Boulton-Katritzky rearrangement [4,8,9] and in this case an example of an adjacent nitro group and two furoxan rings. Previously reported examples include nitro group-furoxan [8] and furoxan-furazan combinations [9].…”

Kinetics of base‐catalyzed cyclization of 2,6‐dinitrophenylsulfanyl ethanenitrile and 2,4,6‐trinitrophenylsulfanyl ethanenitrile

“…The ring closure reaction of ortho-substituted nitroarenes, involving the condensation reaction between a nitro group and nucleophilic center at the ortho-standing substituent, can be considered a standard way for the preparation of various heterocyclic N-oxides (nitrones). [6] In our previous papers [1][2][3][4][5] we have dealt with structurereactivity relationships of 6-substituted methyl 2,4-dinitrophenylsulfanyl ethanoates. When a carbanion is linked with 2,4-dinitro-6-Z-trisubstituted benzene ring by a sulfur-bridge substituted benzothiazole-N-oxide is formed in such cases where Z is an alkyl group, [3] halogen, [3] or another nitro group.…”

Aspects of heterocyclisation reactions mediated by nucleophilic interaction of aromatic nitro groups with ortho heterocumulene side chains

“…Direct interaction of the nitro substituent with electron-rich and electron-poor side-chains in ortho-substituted nitroaromatic and nitroheteroaromatic compounds is a well documented [1][2][3] and fruitful source of novel heterocyclisation reactions. However, among such processes, heterocyclisations initiated by the nucleophilic interaction of aromatic/heteroaromatic nitro groups with ortho heterocumulene substituents are relatively rare.…”