Nitroarylamines via the Vicarious Nucleophilic Substitution of Hydrogen:  Amination, Alkylamination, and Arylamination of Nitroarenes with Sulfenamides

Abstract

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Synthesis of polycyclic fused heterocycles based on 4,6-dinitro-1-phenyl-1H-indazole

“…The precipitate that formed was filtered off and recrystallized from EtOH. Compound 9b was obtained in a yield of 0.25 g (73% (10). A solution of diamine 6 (0.3 g) in a mixture of SOCl 2 (5 mL) and pyridine (5 mL) was refluxed for 1 h. Then the reaction mixture was cooled and poured onto ice (50 g).…”

Vicarious nucleophilic amination of nitroquinolines by 1,1,1‐trimethylhydrazinium iodide

“…The first fraction afforded 0.10 g (26%) of 8-amino-5-nitroquinoline (2b'), orange needles with mp 195-197 °C (lit. [11] 195-197 °C, lit. [14,18] …”

“…These effective amination reagents are hydroxylamine [3], 1,1,1-trimethylhydrazinium iodide (TMHI) [4][5][6], 4-amino- [7,8] or 4-alkylamino-1,2,4-triazoles [9] and sulfenamides [10,11].…”

“…Hasegawa et al, [3] reported the amination of 5-nitro-, 6-nitro-, 7-nitroand 8-nitroquinoline using hydroxylamine in potassium hydroxide as an aminating agent, obtaining a novel product, furazanoquinoline, besides the known amino derivatives substituted in ortho and/or para positions to the nitro group [3]. M kosza and Bia ecki [11] nitro-(17%) and 6-amino-5-nitrosoquinoline (29%) and with 6-nitroquinoline, 5-amino-6-nitroquinoline (98%) [11].…”

Direct Nucleophilic Addition versus a Single‐Electron Transfer Pathway of σH Adduct Formation in Vicarious Nucleophilic Substitution of Hydrogen

“…can undergo this reaction, without limitations, provided they are sufficiently stable and active nucleophiles. Besides carbanions, anions of alkyl hydroperoxides [5Ϫ8] -tert-butyl and cumyl in particular -and a plethora of aminating agents such as derivatives of hydrazine, [9,10] hydroxylamine [11,12] and sulfenamide [13,14] undergo the VNS, introducing OH and NH 2 or NHR substituents, respectively, into nitroaromatic rings.…”