Skip to main content

Electrochemical Fluorination for Preparing Aryl Fluorides

  • Reference work entry
  • First Online:
Fluorination

Part of the book series: Synthetic Organofluorine Chemistry ((SYOC))

Introduction

Aryl fluorides including fluorinated heteroaromatic compounds are of much importance since they exhibit unique and pronounced biological activities. In fact, a number of partially fluorinated aryl compounds are currently used as pharmaceuticals and agrochemicals. Electrochemical partial fluorination of aromatic compounds has received much attention. Electrochemical fluorination of aryl compounds very often provides difluoro products as well as monofluoro products since monofluoro products have similar or a little lower oxidation potentials compared with starting aryl compounds. Furthermore, electrochemical fluorination of aryl compounds sometimes provides nonaromatic multifluorinated products. Therefore, electrochemical fluorination of aryl compounds is usually not so selective, and the yield is generally moderate to low [591,592,593,4]. However, electrochemical partial fluorination can be carried out under safe conditions without any hazardous reagents. This is a big...

This is a preview of subscription content, log in via an institution to check access.

Access this chapter

Chapter
USD 29.95
Price excludes VAT (USA)
  • Available as PDF
  • Read on any device
  • Instant download
  • Own it forever
eBook
USD 379.99
Price excludes VAT (USA)
  • Available as EPUB and PDF
  • Read on any device
  • Instant download
  • Own it forever
Hardcover Book
USD 599.99
Price excludes VAT (USA)
  • Durable hardcover edition
  • Dispatched in 3 to 5 business days
  • Free shipping worldwide - see info

Tax calculation will be finalised at checkout

Purchases are for personal use only

Institutional subscriptions

References

  1. Ronzhkov IN (1983) Anodic fluorination. In: Baizer MM, Lund H (eds) Organic Electrochemistry, 2nd edn. Dekker, New York.

    Google Scholar 

  2. Childs WV, Christensen L, Klink FW, Kolpin CF (1990) Anodic fluorination. In: Lund H, Baizer M. M (eds) Organic Electrochemistry, 3rd edn. Dekker, New York.

    Google Scholar 

  3. Fuchigami T (2000) Electrochemical partial fluorination. In: Lund H, Hammerich O (eds) Organic Electrochemistry, 4th edn. Dekker, New York, Chapter 25.

    Google Scholar 

  4. Fuchigami T, Inagi S (2016) Fluorination. In: Hammerich O, Speiser B (eds) Organic Electrochemistry, 5th edn. CRC Press, Chapter 20.

    Google Scholar 

  5. Knunyants IL., Rozhkov IN., Bukhtiarov AV., Goldin MM., Kudryavtseu RV New Method for introducing fluorine into the aromatic ring Izv Akad Nauk SSSR, Ser Khim (1970) 1207–1208.

    Google Scholar 

  6. Rozhkov IN (1976) Radical-cation mechanism of the anodic fluorination of organic compounds. Russ Chem Rev 45: 615–629.

    Google Scholar 

  7. Rozhkov IN, Gambaryan NP, Galpern EG (1976) The application of the Dewar-Zimmerman rules to the reactions between aromatic radical cations and fluoride ion. Tetrahedron Lett 17 : 4819–4822.

    Google Scholar 

  8. Ludman CL, McCarron EM, O’Malley RF (1972) The electrolytic fluorination of anthracene derivatives. J Electrochem Soc 119 : 874–876.

    CAS  Google Scholar 

  9. Meurs JHH., Sopher DW, Eilenberg W (1989) Oxidative Fluorination of Arenes. Angew Chem Int Ed 28: 927–928.

    Google Scholar 

  10. Laurent EG, Tardivel R, Benotmane H, Bensadat A (1990) Fluorofonctionnalisation de 1-alkylindènes stéréosélectivité comparée: fluoroacétamidation électrochimique et bromofluoration = Fluorofunctionalization of 1-alkylindenes, comparative stereoselectivity: electrochemical fluoroacetamidation and bromofluorination Bull Soc Chim Fr 127: 468–475.

    Google Scholar 

  11. Carpenter JF, Ekes LH, King PF, Mariani HA, Mirza Zadeh M, O’Malley RF, Roman VJ (1983) Electrochemical Fluorination of Anthracene Derivatives. II. J Electrochem Soc 130: 2170–2172.

    CAS  Google Scholar 

  12. O’Malley RF, Mariani HA, Buhler DR, Jerina DM (1981) Anodic fluorination of benz[a]anthracene. J Org Chem 46: 2816–2818.

    Google Scholar 

  13. Momota K, Morita M, Matsuda Y (1993) Electrochemical fluorination of benzene in acetonitrile solutions. Electrochim Acta 38, 619–624.

    CAS  Google Scholar 

  14. Momota K, Morita M, Matsuda Y (1993) Electrochemical fluorination of aromatic compounds in liquid R4NF·mHF-Part I. Basic properties of R4NF·mFand the fluorination of benzene, fluorobenzene and 1,4-difluorobenzene. Electrochim. Acta 38: 1123–1130.

    CAS  Google Scholar 

  15. Momota K, Kato K, Morita M, Matsuda Y (1994) Electrochemical fluorination of aromatic compounds in liquid R4NF·mHF-Part II. Fluorination of di- and tri-fluorobenzenes. Electrochim Acta 39: 41–49.

    CAS  Google Scholar 

  16. Momota K, Horio H, Kato K, Morita M, Matsuda Y (1995) Electrochemical fluorination of aromatic compounds in liquid R4NF·mHF-Part IV. fluorination of chlorobenzene. Electrochim Acta 40: 233–240.

    CAS  Google Scholar 

  17. Morita M, Momota K, Horio H, Kato K, Matsuda Y (1994) Electrochemical fluorination of bromobenzene in liquid Et4NF-mHF. Denki Kagaku 62, 1196–1201.

    CAS  Google Scholar 

  18. Meures JHH, Eilenberg W (1991) Oxidative fluorination in amine-HF mixtures. Tetrahedron 47: 705–714.

    Google Scholar 

  19. Momota K, Mukai K, Kato K, Morita M (1998) Electrochemical fluorination of aromatic compounds in liquid R4NF·mHF-Part VI. The fluorination of toluene, monofluoromethylbenzene and difluoromethylbenzene. Electrochim Acta 43: 2503–2514.

    CAS  Google Scholar 

  20. Momota K, Kato K, Morita M, Matsuda Y (1994) Electrochemical fluorination of aromatic compounds in liquid R4NF·mHF-Part III. Fluorination of trifluoromethylbenzenes. Electrochim Acta 39: 681–690.

    CAS  Google Scholar 

  21. Fukuhara T, Sawaguchi M, Yoneda N (2000) Anodic fluorination of phenols using Et3N-5HF electrolyte. Electrochem Commun 2: 259–261.

    CAS  Google Scholar 

  22. Sawaguchi M, Fukuhara T, Yoneda N (2001) Anodic oxidative fluorination of 2,6-di-tert-butylphenols. J Electroanal Chem 507: 66–70.

    CAS  Google Scholar 

  23. Fukuhara T, Akiyama Y, Yoneda N, Tada T, Hara S (2002) Effective synthesis of difluorocyclohexadienones by electrochemical oxidation of phenols. Terahedron Lett 43: 6583–6585.

    CAS  Google Scholar 

  24. Ballinger JR, Teare FW, Bowen BM, Garnett ES (1985) Electrochemical monofluorination of pyridine: synthesis of 2-fluoropyridine at a platinum anode. Electrochim Acta 30: 1075–1077.

    CAS  Google Scholar 

  25. Konno A, Shimojo M, Fuchigami T (1988) Electrochemical partial fluorination of organic compounds Part 26. Anodic monofluorination of ethyl isonicotinate. J Fluorine Chem 87: 137–140.

    Google Scholar 

  26. Makino K, Yoshioka H. (1988) Selective fluorination of ethyl 1-methylpyrazole-4-carboxylates with poly(hydrogen fluoride)-amine complex under electrolytic anodic oxidation. J Fluorine Chem 39: 435–440.

    CAS  Google Scholar 

  27. Tajima T, Ishii H, Fuchigami T (2001) Electrolytic partial fluorination of organic compounds. Part 48: Anodic fluorination of 2-cyano-1-methylpyrrole. Tetrahedron Lett 42: 4857–4860.

    CAS  Google Scholar 

  28. Saeki K, Tomomitsu M, Kawazoe Y, Momota K, Kimoto H (1996) Fluorinated benzo[h]quinolines and benzo[f]quinolines. Chem Pharm Bull 44, 2254–2258.

    CAS  Google Scholar 

  29. Sono M, Toyoda N, Shizuri Y, Tori M (1994) Functionalisation including fluorination of caffeine, guanosine tetraacetate, and uridine triacetate using electrochemical oxidation. Tetrahedron Lett 35: 9237–9238.

    CAS  Google Scholar 

  30. Sono M, Toyoda N, Shimizu K, Noda E, Shizuri Y, Tori M (1996) Functionalization including fluorination of nitrogen-containing compounds using electrochemical oxidation. Chem Pharm Bull 44: 1141–1145.

    CAS  Google Scholar 

  31. Riyadh SM, Fuchigami T (2002) Electrolytic partial fluorination of organic compounds. 64. Anodic mono- and difluorination of thiazolyl sulfides. J Org Chem 67: 9379–9383.

    CAS  PubMed  Google Scholar 

  32. Andres DF, Dietrich U, Laurent EG, Marquet BS (1997) Anodic fluorination of vinyl sulfides-synthesis of α-fluoro-β-thio-α,β-unsaturated carbonyl compounds. Tetrahedron 53: 647–658.

    CAS  Google Scholar 

  33. Hou Y, Higashiya S, Fuchigami T (1999) Electrolytic partial fluorination of organic compounds. 32. Regioselective anodic mono- and difluorination of flavones. J Org Chem 64: 3346–3349.

    CAS  PubMed  Google Scholar 

  34. Yin B, Wang L, Inagi S, Fuchigami T (2010) Electrosynthesis of fluorinated indole derivatives, Tetrahedron, 66: 6820–6825.

    CAS  Google Scholar 

Download references

Author information

Authors and Affiliations

Authors

Corresponding author

Correspondence to Toshio Fuchigami .

Editor information

Editors and Affiliations

Rights and permissions

Reprints and permissions

Copyright information

© 2020 Springer Nature Singapore Pte Ltd.

About this entry

Check for updates. Verify currency and authenticity via CrossMark

Cite this entry

Fuchigami, T., Inagi, S. (2020). Electrochemical Fluorination for Preparing Aryl Fluorides. In: Hu, J., Umemoto, T. (eds) Fluorination. Synthetic Organofluorine Chemistry. Springer, Singapore. https://doi.org/10.1007/978-981-10-3896-9_25

Download citation

Publish with us

Policies and ethics