Selectfluor

Selectfluor
Names
IUPAC names
1-(chloromethyl)-4-fluoro-1,4-diazo
niabicyclo[2.2.2]octane ditetrafluoroborate
Other names
F-TEDA, N-Chloromethyl-N-fluorotriethylenediammonium bis(tetrafluoroborate)
Identifiers
140681-55-6 YesY
3D model (Jmol) Interactive image
ChemSpider 2007047 N
ECHA InfoCard 100.101.349
EC Number 414-380-4
PubChem 2724933
Properties
C7H14B2ClF9N2
Molar mass 354.26 g/mol
Appearance colourless solid
Melting point 234
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
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Infobox references

1-Chloromethyl-4-fluoro-1,4-diazoniabicyclo[2.2.2]octane bis(tetrafluoroborate) or Selectfluor, a trademark of Air Products and Chemicals, is a reagent in chemistry that is used as a fluorine donor. This compound is a derivative of the heterocycle DABCO . This colourless salt was first described in 1992[1] and has since been commercialized for use in organofluorine chemistry for electrophilic fluorination.

Preparation

Selectfluor is synthesized by the N-alkylation of diazabicyclo[2.2.2]octane (DABCO) with dichloromethane, followed by ion exchange with sodium tetrafluoroborate (replacing the chloride counterion for the tetrafluoroborate). Finally, this salt is treated with elemental fluorine and sodium tetrafluoroborate:[1]

Applications

The conventional source of "electrophilic fluorine", i.e. the equivalent to the superelectrophile F+, is gaseous fluorine, which requires specialised equipment for manipulation. Selectfluor reagent is a salt, the use of which requires only routine procedures. Like F2, the salt delivers the equivalent of F+. It is mainly used in the synthesis of organofluorine compounds:[2][3][4][5]

The ability of Selectfluor to transfer fluorine to alkyl radicals has recently been demonstrated.[6][7]

Specialized applications

Selectfluor reagent also serves as a strong oxidant, a property that is useful in other reactions in organic chemistry. Oxidation of alcohols and phenols. As applied to electrophilic iodination, Selectfluor reagent activates the I–I bond in I2 molecule.

References

  1. 1 2 Banks, R. Eric; Mohialdin-Khaffaf, Suad N.; Lal, G. Sankar; Sharif, Iqbal; Syvret, Robert G. (1992). "1-Alkyl-4-fluoro-1,4-diazoniabicyclo[2.2.2]octane salts: a novel family of electrophilic fluorinating agents". Journal of the Chemical Society Chemical Communications (8): 595. doi:10.1039/C39920000595.
  2. ↑ Banks, R. Eric; Besheesh, Mohamed K.; Mohialdin-Khaffaf, Suad N.; Sharif, Iqbal (1996). "N-Halogeno compounds. Part 18. 1-Alkyl-4-fluoro-1,4-diazoniabicyclo[2.2.2]octane salts: user-friendly site-selective electrophilic fluorinating agents of the N-fluoroammonium class". Journal of the Chemical Society Perkin 1: 2069–2076. doi:10.1039/P19960002069.
  3. ↑ Manral, Laxmi (2006). "Selectfluor (F-TEDA-BF4) C7H14B2ClF9N2". Synlett (5): 0807. doi:10.1055/s-2006-933124.
  4. ↑ Stojan Stavbera and Marko Zupana (2005). "Selectfluortm F-TEDA-BF4 As a Versatile Mediator or Catalyst in Organic Chemistry" (PDF). Acta Chim. Slov. 52: 13–26.
  5. ↑ Singh, R.P.; Shreeve, J. M. (2004). "Recent Highlights in Electrophilic Fluorination with 1-Chloromethyl-4-Fluoro-1,4-Diazoniabicyclo[2.2.2]Octane Bis(Tetrafluoroborate)". Acc. Chem. Res. 37 (1): 31–44. doi:10.1021/ar030043v. PMID 14730992.
  6. ↑ Rueda-Becerril, M.; Chatalova-Sazepin, C.; Leung, J. C. T.; Okbinoglu, T.; Kennepohl, P.; Paquin, J.-F.; Sammis, G. M. (2012). "Fluorine transfer to alkyl radicals". J. Am. Chem. Soc. 134 (9): 4026–4029. doi:10.1021/ja211679v.
  7. ↑ Paquin, J.-F.; Sammis, G.; Chatalova-Sazepin, C.; Hemelaere, R. (2015). "Recent advances in radical fluorination". Synthesis. 47 (17): 2554–2569. doi:10.1055/s-0034-1378824.

Other References

  1. Lal, G. S., J. Org. Chem. 1993, 58, 2791.
  2. Lal, G. S., Synth. Commun. 1995, 25 (5), 725.
  3. Banks, R. E.; Lawrence, N. J.; Popplewell, A. L., J. Chem. Soc., Chem. Commun. 1994, 343.
  4. Banks, R. E., J. Fluorine Chem. 1998, 87, 1.
  5. Zupan, M.; Iskra, J.; Stavber, S., J. Fluorine Chem., 1995, 70, 7.
  6. Matthews, D.P.; Miller, S. C.; Jarvi E. T.; Sabol, J. S.; McCarthy, J. R., Tettrahedron Lett. 1993, 34 (19), 3057.
  7. Brunaus, M.; Dell, C. P.; Owton, W. M., J. Fluorine Chem. 1994, 201.
  8. McClinton, M. A. ; Sik, V., J. Chem. Soc., Perkin Trans. I, 1992, 1891.
  9. Hodson, H. F.; Madge, D. J.; Slawin, A. N. Z.; Widdawson, D. A.; Williams, D. J., Tetrahedron, 1994, 50 (6), 1899.
  10. Stavber, S.; Zupan, M., J. Chem. Soc., Chem. Commun. 1994, 149.
  11. Stavber, S.; Sotler, J.; Zupan, M., Tettrahedron Lett. 1994, 35 (7), 1105.

Patents

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