1
C(CF3)3), 121.0 (q, JC–F = 292.7 Hz, CF3), 130.0 (CH-4,5),
Measurement of the partition coefficients
130.1 (CH-3,6), 133.9 (C-1,2); 19F-NMR (CD2Cl2): d ꢀ72.71.
A 7 mL vial was used to partition 0.010–0.030 mmol of 2a–g in
a well established biphasic system,6 which was prepared by
mixing 2.000 mL perfluoromethyl-cyclohexane and 2.000 mL
toluene. The vial was sealed and vigorously mixed for several
minutes. After standing at 25.0 1C for 24 hours, samples
(0.500 mL) were taken from both phases, which were analyzed
by GC using 1,4-dioxane in xylene as the internal standard. All
partition experiments were done in triplicate.
GC-MS (EI): m/z 574 (M+). IR (KBr): 1302 (s), 1258 (vs),
1143 (s), 1016 (s), 972 (s), 730 (s) cmꢀ1
.
m-Bis((nonafluoro-tert-butoxy)methyl)benzene (2c)
Yield: 1.83 g (42%) white solid, mp: 44.7–45.9 1C. Purity:
>99%. 1H NMR (CD2Cl2): d 5.09 (4H, s, PhCH2O),
7.36–7.40 (3H, m, PhCH), 7.43–7.46 (1H, m, PhCH);
4
13C NMR (CD2Cl2): d 71.8 (m, JC–F = 2 Hz, PhCH2O),
NMR measurements
80.8 (m, 2JC–F = 30 Hz, C(CF3)3), 121.3 (q, 1JC–F = 293.5 Hz,
CF3), 127.6 (CH-4,6), 128.8 (CH-5), 129.8 (CH-2), 136.4
(C-1,3); 19F NMR (CD2Cl2): d ꢀ72.54. GC-MS (EI): m/z
574 (M+). IR (KBr): 1300 (s), 1269 (vs), 1253 (vs), 1148 (s),
The temperature and concentration dependence 1H-NMR
experiments of 2g in c-C6F11CF3 were expressed using an
external deuterium source of D2O (1H d = 4.79) for concen-
tration dependence and CD2Cl2 for the low temperature study.
1018 (s), 972 (s), 730 (s) cmꢀ1
.
p-Bis((nonafluoro-tert-butoxy)methyl)benzene (2d)
Acknowledgements
Yield: 1.79 g (41%) white solid, mp: 93.2–95.8 1C. Purity:
>99%. 1H NMR (CD2Cl2): d 5.07 (4H, s, PhCH2O), 7.41
We are grateful for the continuous support and help of the
Technical Officers of the Department of Biology and Chemistry
of City University of Hong Kong. We would like to thank
Ka Chung Tong for his assistance in some of the synthetic
work. This work was funded by the City University of Hong
Kong, project number 7002604 (2010).
4
(4H, s, CH); 13C NMR (CD2Cl2): d 71.7 (m, JC–F = 2 Hz,
PhCH2O), 80.6 (m, 2JC–F = 30 Hz, C(CF3)3), 121.1 (q, 1JC–F
=
292.4 Hz, CF3), 128.8 (CH-2,3,5,6), 136.2 (C-1,4); 19F NMR
(CD2Cl2): d ꢀ72.66. GC-MS (EI): m/z 574 (M+). IR (KBr):
1304 (s), 1269 (vs), 1243 (vs), 1145 (s), 1017 (s), 972 (s),
730 (s) cmꢀ1
.
Notes and references
1,3,5-Tris((nonafluoro-tert-butoxy)methyl)benzene (2e)
1 B. Cornils, W. A. Herrmann, I. T. Horvath, W. Leitner, S. Mecking,
´
H. Olivier-Bourbigou and D. Vogt, Multiphase Homogeneous
Catalysis, Wiley-VCH, Weinheim, 2005.
2 C. Reichardt, Solvents and Solvent Effects in Organic Chemistry,
VCH, Weinheim, 2nd edn, 1990.
Yield: 2.73 g (59%) white solid, mp: 46.8–49.4 1C. Purity:
>99%. 1H NMR (CD2Cl2): d 5.01 (6H, s, PhCH2O), 7.37
4
(3H, s, CH); 13C NMR (CD2Cl2): d 71.3 (m, JC–F = 2 Hz,
=
3 I. T. Horva
4 I. T. Horvath and J. Ra
5 J. A. Gladysz, D. P. Curran and I. T. Horva
Fluorous Chemistry, Wiley/VCH, Weinheim, 2004.
6 J. A. Gladysz, C. Emnet and J. Rabai, Partition Coefficients
Involving Fluorous Solvents, in Handbook of Fluorous Chemistry,
ed. J. A. Gladysz, D. P. Curran and I. T. Horvath, Wiley-VCH,
Weinheim, 2004, ch. 6.
´
´
th, Green Chem., 2008, 10, 1028.
bai, Science, 1994, 266, 72.
th, Handbook of
PhCH2O), 80.6 (m, 2JC–F = 30 Hz, C(CF3)3), 121.1 (q, 1JC–F
´
293.6 Hz, CF3), 127.4 (CH-2,4,6), 136.9 (C-1,3,5);
19F NMR (CD2Cl2): d ꢀ72.75. GC-MS (EI): m/z 822 (M+).
´
IR (KBr): 1256 (vs), 1152 (s), 1026 (s), 973 (s), 727 (s) cmꢀ1
.
´
´
1-Bromo-2,4,6-tris((nonafluoro-tert-butoxy)methyl)benzene (2f)
Yield: 2.14 g (52%) white solid, mp: 47.2–48.3 1C. Purity:
7 J. P. Giesy and K. Kannan, Environ. Sci. Technol., 2001, 35, 1339.
8 D. J. Luebker, K. J. Hansen, N. M. Bass, J. L. Butenhoff and
A. M. Seacat, Toxicology, 2002, 176, 175.
9 Provisional Health Advisories for Perfluorooctanoic Acid (PFOA)
and Perfluorooctane Sulfonate (PFOS), US Environmental Protec-
tion Agency, January 8, 2009 (www.epa.gov).
10 A. Arakaki, Y. Ishii, T. Tokuhisa, S. Murata, K. Sato, T. Sonoi
and H. Tatsu, Appl. Microbiol. Biotechnol., 2010, 88, 1193.
´
11 I. T. Horvath, Changing Designer Issues in Fluorous Chemistry,
1st International Symposium of Fluorous Technologies, Bordeaux,
France, July 3–5, 2005, Abstract books, p. 1.
12 (a) N. Kudo, N. Bandi, E. Suzuki, M. Katakura and Y. Kawashima,
Chem.-Biol. Interact., 2000, 124, 119; (b) K. P. Das, B. E. Grey,
R. D. Zehr, C. R. Wood, J. L. Butenhoff, S.-C. Chang,
D. J. Ehresman, Y.-M. Tan and C. Lau, Toxicol. Sci., 2008, 105, 173.
1
>99%. H NMR (CD2Cl2): d 5.11 (2H, s, Ph-4-CH2O), 5.20
(4H, s, Ph-2,6-CH2O), 7.50 (2H, s, CH); 13C NMR (CD2Cl2):
4
2
d 70.8 (m, JC–F = 2 Hz, PhCH2O), 80.6 (m, JC–F = 30 Hz,
C(CF3)3), 121.0 (q, 1JC–F = 293.5 Hz, CF3), 122.2 (C-1), 127.7
(CH-3,5), 136.1 (C-2,6), 136.5 (C-4); 19F NMR (CD2Cl2):
d ꢀ72.68 (2,6-CH2OC(CF3)), ꢀ72.81 (CF3). GC-MS (EI):
m/z 900 (M+). IR (KBr): 1262 (vs), 1156 (s), 1027 (s), 973
(s), 729 (s) cmꢀ1
.
2,6-Bis((nonafluoro-tert-butoxy)methyl)pyridine (2g)
13 D. Szabo
J. Fluorine Chem., 2006, 127, 1496.
14 L. E. Kiss, I. Kovesdi and I. J. Ra
´
, J. Mohl, A.-M. Ba
´
lint, A. Bodor and J. Ra
´
bai,
Yield: 3.19 g (73%) white solid, mp: 69.2–70.6 1C. Purity:
>99%. 1H NMR (CD2Cl2): d 5.15 (4H, s, PyCH2O), 7.43
(2H, d, 3JH–H = 7.8 Hz, CH-3,5), 7.85 (1H, t, 3JH–H = 7.8 Hz,
´
bai, J. Fluorine Chem., 2001,
¨
108, 95.
15 Q. Chu, C. Henry and D. P. Curran, Org. Lett., 2008, 10, 2453.
16 (a) R. Ghorbani-Vaghei, M. Chegini, H. Veisi and M. Karimi-
Tabar, Tetrahedron Lett., 2004, 50, 1861; (b) A. Podgorsek,
S. Stavber, M. Zupan and J. Iskra, Tetrahedron, 2009, 65, 4429;
(c) R. Rajagopal, S. A. Siddiqui, T. Daniel, R. J. Lahoti and
K. V. Srinivasan, J. Mol. Catal. A: Chem., 2004, 210, 165;
(d) I. Lee, Y. You, S.-J. Lim and S. Y. Park, Chem. Lett., 2007,
4
CH-4); 13C NMR (CD2Cl2): d 72.2 (m, JC–F = 2 Hz,
PyCH2O), 80.6 (m, 2JC–F = 30 Hz, C(CF3)3), 121.0 (q, 1JC–F
=
293.1 Hz, CF3), 121.1 (CH-3,5), 138.7 (CH-4), 155.3 (C-2,6);
19F NMR (CD2Cl2): d ꢀ72.79. GC-MS (EI): m/z 575 (M+).
IR (KBr): 1302 (s), 1263 (vs), 1160 (s), 1026 (s), 971 (s),
729 (s) cmꢀ1
.
888; (e) N. J. Ronde, D. Totev, C. Muller, M. Lutz, A. L. Spek and
¨
c
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