M.E. Hirschberg et al. / Journal of Fluorine Chemistry 137 (2012) 50–53
53
19F NMR (CD3CN, 27 8C)
d
, ppm: À58.1 (d, 2JF,F = 62 Hz, 2F, axial),
1.77 mmol). The unreacted educt (43%) and IF5 (7%) were removed
in vacuum before.
2
À42.4 (t, JF,F = 62 Hz, 1F, equatorial). 1H NMR (CD3CN, 27 8C)
d,
ppm: 8.03 (m, 2H), 7.76 (m, 1H), 7.68 (m, 2H).
C4F9IF2 in [BMPL][(C2F5)3PF3]: 19F NMR (CD3CN, 27 8C)
d, ppm:
The addition of benzyl alcohol to the solution of C6H5SF3/
[BMPL][(C2F5)3PF3] at 0 8C resulted in C6H5CH2F.
À82.0 (m, 2F, CF2), À82.1 (tt, JF,F = 10 Hz, JF,F = 2 Hz, 3F, CF3),
À119.1 (m, 2F, CF2), À126.7 (m, 2F, CF2), À174.7 (m, 2F, IF2).
2
C6H5CH2F: 19F NMR (CD3CN, 27 8C)
d
, ppm: À206.3 (t, JF,H = 48 Hz,
3.6. Syntheses of C4F9I(OCCF3)2 in [BMPL][(C2F5)3PF3]
1F). 1H NMR (CD3CN, 27 8C)
2JH,F = 48 Hz, 2H).
d, ppm: 7.43 (m, 5H), 5.39 (d,
C4F9I (1.33 g, 3.84 mmol) was added to cold (0 8C)
[BMPL][(C2F5)3PF3] (14.4 g, 24.5 mmol). Diluted fluorine (5 vol%
in nitrogen) was bubbled into the stirred two-phase system.
During the reaction, a solution was formed. After the addition of
1.5 equiv. of fluorine, the fluorination was stopped, the mixture
was degassed with nitrogen and (CF3CO)2O (1.61 g, 7.66 mmol)
was added. The pale yellow solution was stirred for 24 h at 20 8C,
and a white solid precipitated. The suspension was extracted with
CHCl3 (3 Â 5 mL). The CHCl3 phase was concentrated in vacuum
(2.0 hPa, 20 8C, 2 h). The residue was crystallised from a mixture of
CHCl3/n-hexane (5 mL/5 mL) at À60 8C and dried in vacuum (2 hPa,
20 8C, 1 h). The yield was 29% (0.63 g, 1.10 mmol).
After the addition of 2-phenyl-1,3-dithiane to the solution of
C6H5SF3/[BMPL][(C2F5)3PF3] at 0 8C the product C6H5CHF2 was
formed.
2
C6H5CHF2: 19F NMR (CD3CN, 27 8C)
d
, ppm: À111.0 (d, JF,H = 56 Hz,
2F). 1H NMR (CD3CN, 27 8C) , ppm: 7.50 (m, 5H), 6.62 (t, 2JH,F = 56 Hz,
d
1H).
3.4. Synthesis of 4-FC6H4IF2 in [BMPL][(C2F5)3PF3]
19F NMR (CD3CN, 27 8C)
d
, ppm: À61.7 (m, 2F, CF2), À73.6 (s,
4-FC6H4I (0.96 g, 4.32 mmol) was added to cold (À20 8C)
[BMPL][(C2F5)3PF3] (9.54 g, 16.20 mmol). A mixture of fluorine
in nitrogen (5 vol%) was bubbled into the stirred two-phase
system. During the reaction, a white solid precipitated. After
addition of 0.8 equiv. of fluorine, the fluorination was stopped, the
reaction mixture degassed with nitrogen and was extracted with
CHCl3 (2 Â 15 mL). The CHCl3 phase was concentrated in vacuum
(1.5 hPa, 20 8C, 1 h) and a mixture of CHCl3/n-hexane (3 mL/3 mL)
was added. A solution resulted which was cooled to À50 8C. A
white solid precipitated which was washed with n-hexane
(2 Â 5 mL) and dried in vacuum (1.5 hPa, 20 8C, 1 h). White solid
was obtained in 51% yield (0.46 g, 1.77 mmol).
1JC,F = 288 Hz, 6F, CF3), À80.9 (m, 3F, CF3), À115.5 (m, 2F, CF2),
À125.7 (m, 2F, CF2).
Acknowledgements
We thank Dr. Jane Hu¨bner (Bergische Universita¨t Wuppertal,
Germany) for analytical measurements and we acknowledge the
Solvay Company (Bad Wimpfen) for donation of a fluorine gas
cylinder.
References
19F NMR (CDCl3, 27 8C)
d
, ppm: À109.1 (m, 1F, 4-FC6H4), À175.2
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