Abstract
Benzotrifluoride (BTF, trifluoromethylbenzene, α,α,α-trifluorotoluene, C6H5CF3) and related compounds are introduced as new solvents for traditional organic synthesis and for fluorous synthesis. BTF is more environmentally friendly than many other organic solvents and is available in large quantities. BTF is relatively inert and is suitable for use as a solvent for a wide range of chemistry including ionic, transition-metal catalyzed and thermal reactions. It is especially useful for radical reactions, where it may replace benzene as the current solvent of choice for many common transformations. BTF and related solvents are also crucial components of fluorous synthesis since they can dissolve both standard organic molecules and highly fluorinated molecules. This chapter provides an overview of the reactivity and toxicological properties of BTF and analogs and then summarizes their recent uses as reaction solvents in both traditional organic and new fluorous synthesis.
Access this chapter
Tax calculation will be finalised at checkout
Purchases are for personal use only
Preview
Unable to display preview. Download preview PDF.
References
Ogawa A, Curran DP (1997) J Org Chem 62:450
Barbour AK, Belf LF, Buxton MW (1963) In: Stacey M, Tatlow JC, Edwards AG (eds) Advances in Fluorine Chemistry, vol 3. Butterworths, London, p 81
Brown JH, Suchling CW, Wholley WB (1949) J Chem Soc, Supp Issue S 95
Lademann R et al, US 3,966,832 (1978)
Robota S,US 3,859,372 (1975)
Baxamusa J, Robota S, US 4,183,873 (1980)
Sendlak LP,US 4,129,602 (1978)
Sendlak LP,US4,130,594(1978)
Ramanadin A, Seigneurin S, US 4,462,937 (1984)
Schlosser M, Katsoulos G, Takagishi S (1990) Synlett 747
Lefave GM (1949) J Am Chem Soc 71:4148
Simon JH, McArthur RE (1947) Ind Eng Chem 39:366
Hudlicky M (1976) Chemistry of Organic Fluoride Compounds. Ellis Harwood, p 274
Henne AL, Newman MS (1938) J Am Chem Soc 60:1697
Ramchandani RK, Wakharkar RD, Sudalai A (1996) Tetrahedron Lett 37:4063
Nagy G, Tramontana D (1995) Am Paint Coatings J 37
Hare CH ( 1997) Paint and Coatings Industry, XII, 10:202
Hare CH (1998) Modern Paint Coatings, 1:30
Registry of Toxic Effects of Chemical Substances (RTECS) compiled by the National Institute for Occupational Safety and Health of the U S Department of Health and Human Services, 1998, http://www.tomescps.com (accessed January 1999)
Hazardous Substance Data Bank (HSDB) compiled by the National Library of Medicine, 1998, http://www.tomescps.com (accessed January 1999)
(1996) Sax’s Dangerous Properties of Industrial Materials, 9th edn. Van Nostrand Reinhold, New York
Knaak JB, Smith LW, Fitzpatrick RD, Olson JR, Newton PE (1998) Inhalation Toxicology 10:65
SIDS Initial Assessment Report, OECD, 1996->99% to air
Manahan SE (1992) Toxicological Chemistry. Ann Arbor, MI, 138
National Research Council (1995) Prudent Practices in the Laboratory Handling and Disposal of Chemicals. National Academy Press, Washington DC
Yaws CL (1994) Handbook of Vapor Pressure, vol 2. Gulf, Houston, p 269
Perrin DD, Armarego WLF, Perrin DR ( 1980) Purification of Laboratory Chemicals, 2nd edn. Pergamon Press, New York
EC values are an empirical parameter of solvent polarity which are derived by measurement of the long-wave UV/ Visible absorption band of the negative solvachromatic Pyridinium-N-phenoxide betaine dyes in the solvent being studied. Higher values are an indication of greater solvent polarity. The above values were taken from the text by Reichardt C (1990) Solvents and Solvent Effects in Organic Chemistry, 2nd edn. VCH Publishing, Weinheim, p 365
Gómez AM, López JC, Fraser-Reid B (1993) Synlett 10:943
Kistyakowsky GB, Tichenor RL (1942) J Am Chem Soc 64:2302
Tarbell DS, Kincaid JF (1940) J Am Chem Soc 62:728
Diels O, Alder K (1928) Liebigs Ann Chem 460:98
Curran DP, Hale GR, Geib SJ, Balog A, Cass QB, Degani ALG, Hernandes MZ, Freitas LCG (1997) Tetrahedron:Asymmetry 8:3955
Giese B (1983) Angew Chem Int Ed Engl 22:753
Hanessian S, Léger R, Alpegioni M (1992) Carbohyd Res 228:145
Curran DP, Liu H, Josien H, Ko SB ( 1996) Tetrahedron 52:11385
Giese B, Kretzschmar G (1983) Chem Ber 116:3267. See also ref. 37
Kikukawa K, Umekawa H, Wada F, Matsuda T (1988) Chem Lett 881
Labadie JW, Stille JK (1983) J Am Chem Soc 105:6129
Henne AL, Newman MS ( 1938) J Am Chem Soc 60:1697
Ramchandani RK, Wakharkar RD, Sudalai A (1996) Tetrahedron Lett 37:4063
Kulka M (1954) J Am Chem Soc 76:5469
Sakurai H, Hosomi A, Hayashi J (1984) Org Synth 62:86
Fleming I, Dunogués J, Smithers R (1989) Org React 37:57
Mukaiyama T, Banno K, Narasaka K (1974) J Am Chem Soc 96:7503
Poll T, Sobczak A, Hartmann H, Helmchen G (1985) Tetrahedron Lett 26:3905
Drury WJ III, Ferraris D, Cox C, Young B, Lectka T (1998) J Am Chem Soc 120:11006.
Ishihara K, Hanaki N, Yamamoto H (1983) J Am Chem Soc 115:10695.
Höfle G, Steglich W, Vorbruggen H (1978) Angew Chem Int Ed Engl 17:569
Höfle G, Steglich W (1972) Synthesis 619.
Chandhary SK, Hernandez O (1979) Tetrahedron Lett 20:99.
Henkel JG, Spurlock LA (1973) J Am Chem Soc 95:8339
Sigiyama K, Hirao A, Nakahama S (1996) Macromol Chem Phys 197:3149
Strekowski L, Wydra RL, Harden DB, Honkan VA (1990) Heterocycles 31:1565
Kitagawa O, Izawa H, Sato K, Dobashi A, Taguchi T ( 1998) J Org Chem 63:2634
Mitsunobu O (1980) Synthesis 1
Azord-Hossain M (1997) Tetrahedron Lett 38:49
Stang PJ, Trepkow W (1980) Synthesis 983
Okuma K, Swern D (1978) Tetrahedron 34:1651
Dess DB, Martin JC (1983) J Org Chem 48:4155
Ireland RE, Liu L (1993) J Org Chem 58:2899
Dess DB, Martin JC (1991) J Am Chem Soc 113:7277
Reich HJ, Wollowitz S (1993) Org React 44:1
Reich HJ, Renga JM, Reich IL (1975) J Am Chem Soc 97:5434
Prasad M, Lu Y, Kim H-Y, Hu B, Repic O, Blacklock TJ, submitted for publication
Ek A, Witkop B (1954) J Am Chem Soc 76:5579
Fabbri D, Delogu G, De Lucchi O (1993) J Org Chem 58:1748
Josien H, Ko SB, Bom D, Curran DP (1998) Chem Eur J 4:67
Fu GC, Nguyen ST, Grubbs RH (1993) J Am Chem Soc 115:9856
Perasis NA, Bzowej EI (1990) J Am Chem Soc 112:6392
Labadie SS (1989) J Org Chem 54:2496
Trost BM, Van Vranken DL (1993) J Am Chem Soc 115:444
Chung YK, Lee BY, Jeong N, Hudecek M, Pauson PL (1993) Organometallics 12:220
Jacobsen EN, Zhang W, Muci AR, Ecker JR, Deng L (1991) J Am Chem Soc 113:7063
Starks CM, Liotta C ( 1978) Phase Transfer Catalysis, Principles and Techniques. Academic Press, New York, p 110
Liotta CL, Harris HP (1974) J Am Chem Soc 96:2250
Reynolds KA, O’Hagan D, Gani D, Robinson JA (1988) J Chem Soc Perkin Trans I 3195
Vedejs E, Meier GP, Snoble KAJ (1981) J Am Chem Soc 103:2823
Studer A, Hadida S, Ferrito R, Kim S-Y, Jeger P, Wipf P, Curran DP (1997) Science 275:823
Curran DP (1996) Chemtracts-Organic Chemistry 9:75
Horvath, IT (1998) Acc Chem Res 31:641
Cornils B (1997) Angew Chem Int Ed 36:2057
Curran DP, Hadida S, He M (1997) J Org Chem 62:6714
Kainz S, Luo ZY, Curran DP, Leitner W (1998) Synthesis 142
Curran DP (1998) Angew Chem Int Ed 37:117
Curran DP, Hadida S (1996) J Am Chem Soc 118:2531
Studer A, Curran DP (1997) Tetrahedron 53:6681
Linclau B, Singh AK, Curran DP (1999) J Org Chem, in press
Nishikido J, Nakajima H, Saeki T, Ishii A, Mikami K (1998) Synlett 1347
Author information
Authors and Affiliations
Editor information
Editors and Affiliations
Rights and permissions
Copyright information
© 1999 Springer-Verlag Berlin Heidelberg
About this chapter
Cite this chapter
Maul, J.J., Ostrowski, P.J., Ublacker, G.A., Linclau, B., Curran, D.P. (1999). Benzotrifluoride and Derivatives: Useful Solvents for Organic Synthesis and Fluorous Synthesis. In: Knochel, P. (eds) Modern Solvents in Organic Synthesis. Topics in Current Chemistry, vol 206. Springer, Berlin, Heidelberg. https://doi.org/10.1007/3-540-48664-X_4
Download citation
DOI: https://doi.org/10.1007/3-540-48664-X_4
Published:
Publisher Name: Springer, Berlin, Heidelberg
Print ISBN: 978-3-540-66213-6
Online ISBN: 978-3-540-48664-0
eBook Packages: Springer Book Archive