Direct amination of 1-substituted 3,5-dinitrobenzenes by 1,1,1-trimethylhydrazinium iodide

Vladimir V Rozhkov; Svyatoslav A Shevelev; Ivan I Chervin; Alexander R Mitchell; Robert D Schmidt

doi:10.1021/jo005774c

Direct amination of 1-substituted 3,5-dinitrobenzenes by 1,1,1-trimethylhydrazinium iodide

J Org Chem. 2003 Mar 21;68(6):2498-501. doi: 10.1021/jo005774c.

Authors

Vladimir V Rozhkov¹, Svyatoslav A Shevelev, Ivan I Chervin, Alexander R Mitchell, Robert D Schmidt

Affiliation

¹ N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, Leninski prosp., 47, 117913, Moscow, Russia.

PMID: 12636426
DOI: 10.1021/jo005774c

Abstract

The amination of 1-X-3,5-dinitrobenzenes via the vicarious nucleophilic substitution of hydrogen (VNS) with 1,1,1-trimethylhydrazinium iodide (TMHI) in the presence of t-BuOK or NaOMe in DMSO was studied. It was observed (when X = OMe, OCH(2)CF(3), OCH(2)CF(2)CF(2)H, OPh) that the amination occurs regioselectively (ratio of ortho/para-isomers is approximately 9:1) and with high yield. For X = SPh or SCH(2)Ph, the reaction proceeded with a low yield (less than 20%), with a ratio of ortho/para-isomers approximately 1:1. For X = PhSO(2) and 2 equiv of TMHI, a double amination occurs and 2,4-diamino-3,5-dinitro-1-phenylsulfonylbenzene predominates in the mixture of isomers. Under the same conditions, 1,3,5-trinitrobenzene undergoes a double amination to yield 2,4-diamino-1,3,5-trinitrobenzene. A proposed mechanism for this reaction is discussed.