Halo- and Azidodediazoniation of Arenediazonium Tetrafluoroborates with Trimethylsilyl Halides and Trimethylsilyl Azide and Sandmeyer-Type Bromodediazoniation with Cu(I)Br in [BMIM][PF₆] Ionic Liquid^§

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Abstract

Reaction of [ArN₂][BF₄] salts immobilized in [BMIM][PF₆] ionic liquid (IL) with TMSX (X = I, Br) and TMSN₃ represents an efficient method for the preparation of iodo-, bromo-, and azido-derivatives via dediazoniation. The reactions can also be effected starting with ArNH₂ by in situ diazotization with [NO][BF₄] followed by reaction with TMSX or TMSN₃. Depending on the substituents on the benzenediazonium cation, competing fluorodediazoniation (ArF formation) and hydrodediazoniation (ArH formation) were observed. Dediazoniation with TMSN₃ and with TMSI generally gave the highest chemoselectivity toward ArN₃ and ArI formation. The IL was recycled and reused up to 5 times with no appreciable decrease in the conversions. Multinuclear NMR monitoring of the interaction of [ArN₂][BF₄]/TMSX, [BMIM][PF₆]/TMSX, and [BMIM][PF₆]/TMSX/[ArN₂][BF₄] indicated that TMSF is formed primarily via [ArN₂][BF₄]/TMSX, generating [ArN₂][X] in situ, which gives ArX on dediazoniation. Competing formation of ArF in Sandmeyer-type bromodediazoniation of [ArN₂][BF₄] with Cu(I)Br immobilized in the IL points to significant involvement of heterolytic dediazoniation.

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This article has been cited by 3 ACS Journal articles (3 most recent appear below).

• 

  Ethylammonium Nitrate (EAN)/Tf₂O and EAN/TFAA: Ionic Liquid Based Systems for Aromatic Nitration

  Gopalakrishnan Aridoss and Kenneth K. Laali
  The Journal of Organic Chemistry2011 76 (19), 8088-8094

  • Ethylammonium Nitrate (EAN)/Tf₂O and EAN/TFAA: Ionic Liquid Based Systems for Aromatic Nitration

    Gopalakrishnan Aridoss and Kenneth K. Laali
    The Journal of Organic Chemistry2011 76 (19), 8088-8094

    Acting as in situ sources of triflyl nitrate (TfONO2) and trifluoroacetyl nitrate (CF3COONO2), the EAN/Tf2O and EAN/TFAA systems, generated via metathesis in the readily available ethylammonium nitrate (EAN) ionic liquid as solvent, are powerful ...

    Abstract | Full Text HTML | Hi-Res PDF | PDF w/ Links
• 

  2,3-Disubstituted Indoles via Palladium-Catalyzed Reaction of 2-Alkynyltrifluoroacetanilides with Arenediazonium Tetrafluoroborates

  Sandro Cacchi, Giancarlo Fabrizi, Antonella Goggiamani, Alcide Perboni, Alessio Sferrazza and Paolo Stabile
  Organic Letters2010 12 (14), 3279-3281

  • 2,3-Disubstituted Indoles via Palladium-Catalyzed Reaction of 2-Alkynyltrifluoroacetanilides with Arenediazonium Tetrafluoroborates

    Sandro Cacchi, Giancarlo Fabrizi, Antonella Goggiamani, Alcide Perboni, Alessio Sferrazza and Paolo Stabile
    Organic Letters2010 12 (14), 3279-3281

    A novel palladium-catalyzed synthesis of free N−H 2,3-disubstituted indoles from arenediazonium tetrafluoroborates and 2-alkynyltrifluoroacetanilides is presented. The reaction tolerates a variety of useful substituents both in the starting alkyne and ...

    Abstract | Full Text HTML | Hi-Res PDF | PDF w/ Links
• 

  Biaryl Construction through Kumada Coupling with Diaryl Sulfates as One-by-One Electrophiles under Mild Conditions

  Bing-Tao Guan, Xing-Yu Lu, Yang Zheng, Da-Gang Yu, Tong Wu, Kun-Lin Li, Bi-Jie Li and Zhang-Jie Shi
  Organic Letters2010 12 (2), 396-399

  • Biaryl Construction through Kumada Coupling with Diaryl Sulfates as One-by-One Electrophiles under Mild Conditions

    Bing-Tao Guan, Xing-Yu Lu, Yang Zheng, Da-Gang Yu, Tong Wu, Kun-Lin Li, Bi-Jie Li and Zhang-Jie Shi
    Organic Letters2010 12 (2), 396-399

    Diaryl sulfates were successfully applied as one-by-one organo electrophiles in Kumada coupling to construct biaryls with the emission of harmless inorganic salts.

    Abstract | Full Text HTML | Hi-Res PDF | PDF w/ Links

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