화학공학소재연구정보센터
Journal of Industrial and Engineering Chemistry, Vol.31, 26-38, November, 2015
Ionic liquids based fluorination of organic compounds using electrochemical method
E-mail:,
Ionic liquids due to their advantageous properties gain importance in many fields. This study aims to overview the use of ionic liquids in the selective partial fluorination of organic compounds through electrochemical method. In addition to ionic liquid based fluorination, the earlier approaches of fluorination through an electrochemical process have also been highlighted. The factors such as electrode materials (Pt, Ni, and C), types of solvents (CH3CN, DMC, THF, DME, Sulfone, etc.) and type of electrolytes (Et3N·3HF, Et3NF·3HF, py·HF, etc.) which affect the electrochemical fluorination of organic compounds have been reviewed. For electrode preparation, the carbon, platinum and nickel were considered suitable materials to be used as an electrode. In CH3CN media, Et3N·3HF and Et4NF·3HF showed better efficiency during fluorination of organic compounds. Solvent play an important role in electrochemical fluorination of organic compounds, with the change of solvent the percentage yield is highly affected. Py-HF is a convenient solvent-supporting electrolyte medium with a reasonably good conductivity. The electrolyte containing solvents have some side effects on electrochemical fluorination of organic compounds as observed in cyclic voltammetric analysis. Therefore electrochemical fluorination to organic compounds without the use of solvent gained more importance. The ionic liquids have been reported for its dual properties, as solvent as well as a fluorinating agent for organic compounds in electrochemical processes. It has been concluded that solvents free electrochemical fluorination of organic compounds gives good results as compare to solvent based. Ionic liquids due to more oxidative stability were noted to have considerable effect on the yield and selectivity of organic compound fluorination.
  1. Filler R, Kobayashi Y (Eds.), Biomedicinal Aspects of Fluorine Chemistry, Kodansha & Elsevier Biomedical, Tokyo, 1982.
  2. Welch JT, Tetrahedron, 43, 3123 (1987)
  3. Welch JT, Eswarakrishnan S, Fluorine in Bioorganic Chemistry, Wiley, New York, 1991.
  4. Yoshioka H, Nakayama C, Matsuo NJ, Synth. Org. Chem. Jpn., 42, 809 (1984)
  5. Johno M, Itoh K, Lee J, Ouchi Y, Takezoe H, Fukuda A, Kitazume T, Jpn. J. Appl. Phys., 29, L107 (1990)
  6. Rozhkov N, Russ. Chem. Rev., 45, 615 (1976)
  7. Rozhkov IN, Baizer MM, Lund H (Eds.), Organic Electrochemistry, 2nd ed., Marcel Dekker, New York, 1983 (Chapter 24).
  8. Holitzer E, Sartori P, Chem. Ing. Tech., 58, 19 (1986)
  9. Sartori P, Bull. Electrochem., 6(4), 471 (1990)
  10. Childs WV, Chtistensen L, Klink FW, Koplin CF, in: Baizer MM, Lund H (Eds.), Organic Electrochemistry, 3rd ed., Marcel Dekker, New York, 1991 (Chapter 24).
  11. Landini D, Maia A, Rampoldi A, J. Org. Chem., 54, 328 (1989)
  12. Fuchigami T, Higashiya S, Hou S, Dawood K, Rev. Heteroat. Chem., 19, 67 (1999)
  13. Fuchigami T, in: Mariano PS (Ed.), Advances in Electron-Transfer Chemistry, vol. 67, JAI Press, Greenwich, CT, 1999, p. 4.
  14. Fuchigami T, in: Hammerich O, Lund H (Eds.), Organic Electrochemistry, 4th ed., Dekker, New York, 2001, p. 1035.
  15. Torii S:, in: Ebel HF (Ed.), Electro Organic Synthesis - Methods and Applications; Part I: Oxidations; Monographs in Modern Chemistry, Kodansha, Tokyo, 1985.
  16. Simons JH, Trans. Electrochem. Soc., 95, 47 (1949)
  17. Nenitzescu D, Rev. Roum. Chim., 52(5), 453 (2007)
  18. Muhammad N, Man Z, Bustam MA, Mutalib MIA, Rafiq S, J. Ind. Eng. Chem., 19(1), 207 (2014)
  19. Ying A, Li Z, Ni Y, Xu S, Hou H, Hu H, J. Ind. Eng. Chem., 24, 127 (2015)
  20. Duchet L, Legeay JC, Carrie D, Paquin L, Vanden Eynde JJ, Bazureau JP, Tetrahedron, 66, 986 (2010)
  21. Singh RK, Gupta P, Sharma OP, Ray SS, J. Ind. Eng. Chem., 24, 14 (2015)
  22. Zanoni MVB, Rogers EI, Hardacre C, Compton RG, Anal. Chim. Acta, 659, 115 (2010)
  23. Wei Y, Keke C, Xiaofang Z, Yingying K, Xiujuan T, Xiaoxiang H, Ind. Eng. Chem., http://dx.doi.org/10.1016/j.jiec.2015.04.002. (2015)
  24. Fontanals N, Ronka S, Borrull F, Trochimczuk AW, Marce RM, Talanta, 80, 250 (2009)
  25. Seddon KR, J. Chem. Technol. Biotechnol., 68(4), 351 (1997)
  26. Sartori P, Ignat’ev N, J. Fluor. Chem., 87, 157 (1998)
  27. Alsmeyer YW, Childs WV, Flynn RM, Moor GG1, Smeltzer JC, in: Banks RE, Smart BE, Tatlow JC(Eds.), Organofluorine Chemistry, Plenum, p. 121 (Chapter 5).
  28. Gramstad T, Haszeldine RN, J. Chem. Soc., 173 (1956)
  29. Kubisa P, Prog. Polym. Sci, 34, 1333 (2009)
  30. Laurent E, Marquet B, Tardivel R, Tetrahedron, 45, 4431 (1989)
  31. Meurs JH, Eilenberg W, Tetrahedron, 47, 705 (1991)
  32. Doughty AG, Fleischmann M, Pletcher D, J. Electroanal. Chem., 51, 329 (1974)
  33. Simons JH, Fluorine Chemistry, vol. 1, Academic Press, New York, 1950p. 414.
  34. Gramstead T, Haszeldine RN, J. Chem. Soc., 173 (1956)
  35. Sartori P, J. Fluor. Chem., 103, 57 (2000)
  36. Burden JC, Tatlow JC, Adv. Fluor. Chem., 1, 129 (1960)
  37. Page M, C. R. Acad. Sci., 246C, 2094 (1967)
  38. Stein L, Neil JM, Alms GR, Inorg. Chem., 11, 2472 (1969)
  39. Semenii VY, Stepanov VVA, Ignat’ev NV, Furin GG, Yagupolskii LM, Zh. Obshch. Khim., 55, 2716 (1985)
  40. Laurent E, Marquet B, Tardivel R, J. Fluor. Chem., 49, 115 (1990)
  41. Bensadat A, Bodennec G, Laurent E, Tardivel R, J. Fluor. Chem., 20, 333 (1982)
  42. Benotmane H, Bensadat A, J. Sot. Alger. Chim., 73, 1 (1991)
  43. Fuchigami T, Konno A, Nakagawa K, Shimojo M, J. Org. Chem., 59, 5937 (1994)
  44. Hou Y, Fuchigami T, J. Electrochem. Soc., 1(47), 4567 (2000)
  45. Shaaban MR, Ishii H, Fuchigami T, J. Org. Chem., 65, 8685 (2000)
  46. Huba F, Yeager EB, Olah GA, Electrochim. Acta, 24, 489 (1979)
  47. Nikitin EV, 1gnatev YA, Romakhim AS, Parakin OV, Romanov GV, Kargin YM, Pudovik AN, Zh. Obshch. Khim., 52, 1024-1 (1982)
  48. Hasegawa M, Ishii H, Fuchigami T, Green Chem., 5, 512 (2003)
  49. Fuchigami T, Shimojo M, Konno A, Nakagawa K, J. Org. Chem., 55, 6074 (1990)
  50. Suryanarayanan V, Chellammal S, Noel M, J. Fluor. Chem., 93, 53 (1999)
  51. Brigaud T, Laurent E, Tetrahedron Lett., 31, 2287 (1990)
  52. Fuchigami T, Konno A, Shimojo M, J. Org. Chem., 60, 3459 (1995)
  53. Fuchigami T, Sunaga T, Ishii H, Atobe M, in: Proceedings of the100th ECS Meeting, Philadelphia, May, 2002 (abstract 1220).
  54. Konno T, Fuchigami J, AAPG Bull., 25, 690 (1995)
  55. Suda K, Hotoda K, Aoyagi M, Takanmi T, J. Chem. Soc.-Perkin Trans. 1, 11, 1327 (1995)
  56. Fuchigami T, Konno A, Nakagawa K, Shimoja M, J. Org. Chem., 59, 5937 (1994)
  57. Narizuka S, Fuchigami T, J. Org. Chem., 58, 4200 (1993)
  58. Narizuka S, Koshiyama H, Konno A, Fuchigami T, J. Fluor. Chem., 73, 121 (1995)
  59. Konno A, Fuchigami T, J. Appl. Electrochem., 25(2), 173 (1995)
  60. Sartori P, Ignat’ev N, Datsenko S, J. Fluor. Chem., 75, 157 (1995)
  61. Yin DW, Zarkowsky DS, Thomas DW, Zhao MM, Huffman MA, Org. Lett., 6(9), 1465 (2004)
  62. Rozhkov IN, Russ. Chem. Rev., 45, 615 (1976)
  63. Childs WV, Christensen L, Mink FW, Kolpin CF, in: Lund H, Baizer MM (Eds.), In Organic Electrochemistry, 3rd ed., Marcel Dekker, New York, 1991 (Chapter 26).
  64. Knunyants IL, Rozhkov IN, Bukhtiarov AV, Go’ldin MM, Kudryawtseu RV, Izv. Akad. Nauk. SSR Ser. Khim., 1207 (1970)
  65. Rozhkov IN, Bukhtiarov AV, Kuleshova ND, Knunyants IL, Dokl. Akad. Nauk. SSSR, 193, 1322 (1970)
  66. Fuchigami T, Rev. Heteroat. Chem., 10, 155 (1994)
  67. Fuchigami T, Sano M, J. Electroanal. Chem., 414(1), 81 (1996)
  68. Schmidt H, Schmidt HD, Chem. Tech., 5, 454 (1953)
  69. Schmidt H, Schmidt HD, J. Pract. Chem., 2, 105 (1955)
  70. Schmidt H, Meinert H, Angew. Chem.-Int. Edit., 72, 109 (1960)
  71. Knunyants IL, Rozhkov IN, Bukhtiarov AV, Goldin MM, Kudryavvtseu RV, Izv. Akad. Nauk. SSSR. Ser. Khim., 73, 65 (1970)
  72. Rozhkov IN, Bukhtiarov AV, Kuleshova ND, Knunyants IL, Dokl. Akad. Nauk. SSSR 193 (1970) 1322, CA. 74 (1971) 70-878.
  73. Knunyants IL, Rozhkov IN, Bukhtiarov AV, Izv. Akad. Nauk. SSSR. Ser. Chem., 478, 1369 (1971)
  74. Nikitin EV, 1gnatev YA, Romakhim AS, Parakin OV, Romanov GV, Kargin YM, Pudovik AN, Zh. Obshch. Khim., 52, 1207 (1982)
  75. Alvemhe G, Laurent A, Laurent E, Tardivel R, Ann. Chim. Fr., 9, 659 (1984)
  76. Fuchigami T, Narizuka S, Konno A, J. Org. Chem., 57, 3755 (1992)
  77. Konno A, Naito W, Fuchigami T, Tetrahedron Lett., 33, 7017 (1992)
  78. Narizuka S, Konno A, Matsuyama H, Fuchigami T, Denki Kagaku, 61, 868 (1993)
  79. Anderson JL, Ding J, Welton T, Armstrong DW, J. Am. Chem. Soc., 124, 142 (2002)
  80. Welton T, Chem. Rev., 99(8), 2071 (1999)
  81. Holbrey JD, Seddon KR, Clean Prod. Process., 1, 223 (1999)
  82. Ishii H, Fuchigami T, Electrochemistry, 70, 46 (2002)
  83. Wasserscheid P, Keim W, Angew. Chem.-Int. Edit., 39(21), 3772 (2000)
  84. Sheldon R, Chem. Commun., 2399 (2001)
  85. Hasegawa M, Ishii H, Fuchigami T, Tetrahedron Lett., 43, 1503 (2002)
  86. Momota K, Morita M, Matsuda Y, Electrochim. Acta, 38, 1123 (1993)
  87. Chen SQ, Hatakeyama T, Fukuhara T, Hara S, Yoneda N, Electrochim. Acta, 42(13-14), 1951 (1997)
  88. Hou Y, Higashiya S, Fuchigami T, J. Org. Chem., 62, 8773 (1997)
  89. Cerichelli G, Crestoni ME, Fornarini S, Gazz. Chim. Ital., 120, 749 (1990)
  90. Erian AW, Konno A, Fuchigami T, J. Org. Chem., 60, 7654 (1996)
  91. Tajima T, Ishii H, Fuchigami T, Electrochem. Commun., 3(8), 467 (2001)
  92. Hasegawa M, Fuchigami T, Electrochim. Acta, 49(20), 3367 (2004)
  93. Cao Y, Fuchigami T, Electrochim. Acta, 51(12), 2477 (2006)
  94. Cao Y, Fuchigami T, J. Electroanal. Chem., 587(1), 25 (2006)
  95. Cao Y, Suzuki K, Tajima T, Fuchigami T, Tetrahedron, 61, 6854 (2005)
  96. Zagipa B, Hidaka A, Cao Y, Fuchigami T, J. Fluor. Chem., 127, 552 (2006)
  97. Fuchigami T, J. Fluor. Chem., 128, 311 (2007)
  98. Tajima T, Ishii H, Fuchigami T, Electrochem. Commun., 4, 589 (2002)