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O. Cohen et al. / Tetrahedron 66 (2010) 3579–3582
3.5.1. 1,4-Bis(trifluoromethyl)benzene (4f). Compound 4f was pre-
pared from 3f (376 mg,1.5 mmol) as described above in 65% yield. It
was also prepared from 6 (430 mg, 1.5 mmol) and 6 mole-equiv of
BrF3 as described above in 30% yield.
Acknowledgements
This work was supported by the USA-Israel Binational Science
Foundation (BSF), Jerusalem, Israel.
3.5.2. 7-Methyl-7-trifluoromethylpentadecane (9a). Compound 9a
was prepared from 8a (496 mg, 1.5 mmol) as described above in
References and notes
80% yield as colorless oil. 1H NMR
d
1.52–1.35 (4H, m), 1.27 (20H, br
s), 1.04 (3H, s), 0.92–0.85 ppm (6H, m); 13C NMR
130.6 (q,
J¼284 Hz), 43.4 (q, J¼23 Hz), 34.5, 32.6, 32.4, 31.1, 30.8, 30.2, 30.0,
1. Prakash, G. K. S.; Krishnamurti, R.; Olah, G. A. J. Am. Chem. Soc. 1989, 111, 393.
2. Langlois, B. R.; Billard, T. Synth. 2003, 185.
3. (a) Ait-Mohand, S.; Takechi, N.; Medebielle, M.; Dolbier, W. R., Jr. Org. Lett. 2001,
26, 4271; (b) Shono, T.; Kise, N.; Oka, H. Tetrahedron Lett. 1991, 32, 6567.
4. Umemoto, T.; Ishihara, S. J. Fluorine Chem. 1998, 92, 181.
5. Wang, C.-L. J. Org. React. 1985, 34, 319.
6. For earlier works with BrF3 see: Michalak, R. S.; Wilson, S. R.; Martin, J. C. J. Am.
Chem. Soc. 1984, 106, 7529; Soelch, R. R.; Mauer, G. W.; Lemal, D. M. J. Org. Chem.
1985, 50, 5845.
7. Rozen, S.; Lerman, O. J. Org. Chem. 1993, 58, 239.
8. (a) Rozen, S.; Mishani, E.; Bar-Haim, A. J. Org. Chem. 1994, 59, 2918; (b) Cohen,
O.; Rozen, S. Tetrahedron 2008, 64, 5362.
9. Hagooly, Y.; Cohen, O.; Rozen, S. Tetrahedron Lett. 2009, 50, 392.
10. Ben-David, I.; Rechavi, D.; Mishani, E.; Rozen, S. J. Fluorine Chem. 1999, 97, 75.
11. (a) Rozen, S.; Ben-David, I. J. Fluorine Chem. 1996, 76, 145; (b) Cohen, O.; Sasson,
R.; Rozen, S. J. Fluorine Chem. 2006, 127, 433.
12. Sasson, R.; Hagooly, A.; Rozen, S. Org. Lett. 2003, 5, 769.
13. Rozen, S. Acc. Chem. Res. 2005, 38, 803.
14. Sasson, R.; Hagooly, A.; Rozen, S. Org. Lett. 2003, 5, 769.
15. In certain cases radical reactions with BrF3 could be useful as in the pyruvic acid
derivatives which were turned into compounds possessing a terminal CF3
group with one carbon less than the starting material: Sasson, R.; Rozen, S.
Tetrahedron 2005, 60, 1083.
16. Kuroboshi, M.; Hiyama, T. Chem. Lett. 1992, 5, 827.
17. Savarin, C.; Srogl, J.; Liebeskind, S. L. Org. Lett. 2000, 2, 3229.
18. This material is commercially available.
19. For a preliminary communication see: Rozen, S.; Mishani, E. J. Chem. Soc., Chem.
Commun. 1994, 2081.
20. Rozen, S.; Rechavi, D.; Hagooly, A. J. Fluorine Chem. 2001, 111, 161.
21. Rozov, L. A.; Huang, C. G.; Halpern, D. F.; Vernice, G. G.; Ramig, K. Tetrahedron:
Asymmetry 1997, 8, 3023.
22. Wolniewicz, A.; Dmowski, W. J. Fluorine Chem. 2001, 109, 95.
23. Boguslavskaya, L. S.; Kartashov, A. V.; Chuvatkin, N. N. Zh. Org. Khim. (Eng.
Transln.) 1989, 25, 1835.
24. Duddeck, H.; Spitzer, M.; Bolte, G. Liebigs Ann. Chem. 1985, 3, 545.
25. Rozen, S.; Gal, C. J. Org. Chem. 1987, 52, 4928.
d
24.2, 23.4, 20.1, 14.8, 14.7 ppm; 19F NMR
d
ꢁ75.1 ppm (s); HRMS (CI)
(m/z) calcd for C17H33F3¼293.2456 (MꢁH)þ, found 293.2455.
3.5.3. 1,1,1-Trifluoro-2,2-dimethyldodecane (9b). Compound 9b was
prepared from 8b (433 mg, 1.5 mmol) as described above in 70%
yield as colorless oil. 1H NMR
d 1.48–1.39 (2H, m), 1.27 (16H, br s),
1.07 (6H, q, J¼1 Hz), 0.88 ppm (3H, t, J¼7 Hz); 13C NMR
d 130.5 (q,
J¼283 Hz), 40.8 (q, J¼24 Hz), 36.4, 32.6, 31.0, 30.4, 30.3, 30.2, 30.0,
24.2, 23.4, 21.2, 14.8 ppm; 19F NMR
d
ꢁ78.9 ppm (s); HRMS (CI)
(m/z) calcd for C14H27F3¼251.1987 (MꢁH)þ, found 251.1981.
3.5.4. 1-Methyl-1-trifluoromethylcyclohexane (9c)22. Compound 9c
was prepared from 8c (2.02 g,10 mmol) as described above in 80% yield.
3.5.5. 1-Trifluoromethyladamantane (9d)24. Compound 9d was pre-
pared from 8d (313 mg, 1.3 mmol) as described above in 65% yield.
3.5.6. 7-Trifluoromethylpentadecane (9e). Compound 9e was pre-
pared from 8e (950 mg, 3 mmol) as described above in 45% yield as
colorless oil. 1H NMR
d
2.08–1.95 (1H, m), 1.65–152 (2H, m), 1.48–
1.24 (22H, m), 0.95–0.87 ppm (6H, m); 13C NMR
129.5 (q,
J¼280 Hz), 43.3 (q, J¼25 Hz), 32.6, 32.3, 30.4, 30.1, 30.0, 28.6, 27.6,
d
23.4, 23.3,14.8,14.7 ppm; 19F NMR
d
ꢁ70.6 ppm (d, J¼10 Hz); HRMS
(CI) (m/z) calcd for C16H31F3¼279.2300 (MꢁH)þ, found 279.2298.
26. Mlinaric-Majerski, K.; Veljkovic, J.; Kaselj, M.; Marchand, A. P. Eur. J. Org. Chem.
2004, 2923.
27. Alexandrov, A. M.; Sorochinskii, A. E.; Krasnoshchek, A. P. Zh. Org. Khim. (Eng.
Transln.) 1979, 15, 336.
28. Levesque, G.; Gressier, J. C.; Proust, M. Synth. 1981, 963.
29. Sasson, R.; Hagooly, A.; Rozen, S. J. Fluorine Chem. 2006, 127, 962.
30. Dagan, S.; Amirav, A. J. Am. Mass. Spectrom. 1995, 6, 120.
31. Amirav, A.; Gordin, A.; Tzanani, N. Rapid Commun. Mass Spectrom. 2001, 15, 811.
32. (a) Alon, T.; Amirav, A. Rapid Commun. Mass Spectrom. 2006, 20, 2579; (b)
Amirav, A.; Gordin, A.; Poliak, M.; Fialkov, A. B. J. Mass. Spectrom. 2008,
43, 141.
3.5.7. 1,1-Dicyclohexyl-2,2,2-trifluoroethane (9f). Compound 9f was
prepared from 8f (428 mg, 1.5 mmol) as described above in 40%
yield as colorless oil. dH 1.87–1.44 (13H, m), 1.39–1.00 ppm (10H,
m); dC 129.6 (q, J¼283 Hz), 54.7 (q, J¼22 Hz), 37.9, 33.1, 31.3, 27.8,
27.7, 26.9 ppm; dF ꢁ61.6 ppm (d, J¼12 Hz); HRMS (CI) (m/z) calcd
for C14H23F3¼247.1674 (MꢁH)þ, found 247.1670.
3.5.8. 2-Trifluoromethyladamantane (9g)27. Compound 9g was
prepared from 8g (962 mg, 4 mmol) as described above in 35% yield.
33. Lehmann, E.; Naumann, D.; Schmeisser, M. Z. Anorg. Allg. Chem. 1972, 388, 1.