Direct Amination of 1-Substituted 3,5-Dinitrobenzenes by 1,1,1-Trimethylhydrazinium Iodide

Direct Amination of 1-Substituted 3,5-Dinitrobenzenes by 1,1,1-Trimethylhydrazinium Iodide

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, OCH2CF3, OCH2CF2CF2H, OPh) that the amination occurs regioselect...

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Veröffentlicht in:Journal of organic chemistry 2003-03, Vol.68 (6), p.2498-2501
Hauptverfasser: Rozhkov, Vladimir V, Shevelev, Svyatoslav A, Chervin, Ivan I, Mitchell, Alexander R, Schmidt, Robert D
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container_end_page 2501
container_issue 6
container_start_page 2498
container_title Journal of organic chemistry
container_volume 68
creator Rozhkov, Vladimir V
Shevelev, Svyatoslav A
Chervin, Ivan I
Mitchell, Alexander R
Schmidt, Robert D
description 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, OCH2CF3, OCH2CF2CF2H, OPh) that the amination occurs regioselectively (ratio of ortho/para-isomers is ∼9:1) and with high yield. For X = SPh or SCH2Ph, the reaction proceeded with a low yield (less than 20%), with a ratio of ortho/para-isomers ≈ 1:1. For X = PhSO2 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.
doi_str_mv 10.1021/jo005774c
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A proposed mechanism for this reaction is discussed.</abstract><cop>United States</cop><pub>American Chemical Society</pub><pmid>12636426</pmid><doi>10.1021/jo005774c</doi><tpages>4</tpages></addata></record>
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title Direct Amination of 1-Substituted 3,5-Dinitrobenzenes by 1,1,1-Trimethylhydrazinium Iodide
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