V.M. Karpov et al. / Journal of Fluorine Chemistry 107 (2001) 53±57
57
mixture was poured on to ice, extracted with CHCl3 and
dried over MgSO4. The solvent was distilled off to give
1.32 g of the product, containing 20% (yield 19.4%) of
5, 39% (38.1%) of 6, 5% (3.4%) of 7, 18% (12.4%) of 8,
3% (2.3%) of 9 and compound 10 (<1%).
with 0.24 g of SO2ClF, and the spectrum was recorded
again. The 19F NMR spectra of the solutions of fluorene
5 in SbF5 and in the system SbF5±SO2ClF contained the
signals of cation 26 and did not contain the signals of the
precursor 5.
3. Pentafluorobenzene (0.65 g) was added at room tem-
perature to the solution of 1.15 g of indan 2 in 6.7 g of
SbF5 (1:1:8) in a nickel bomb. The mixture was held at
room temperature for 50 h, then heated at 1708C for
15 h and treated as in (2) to give 1.41 g of the product,
containing 13% (yield 12%) of 5, 32% (29.7%) of 6, 2%
(1.4%) of 9, 14% (12%) of 10 and 15% (13.5%) of 11.
4. In a similar manner, from 1.05 g of indan 2, 0.59 g of
pentafluorobenzene and 5.36 g of SbF5 (1:1:7) was
obtained 1.3 g of the product, containing 6% (yield
5.6%) of 5, 44% (41.2%) of 6, 5% (3.6%) of 9, 15%
(13.1%) of 10 and 11% (10%) of 11. Individual
compounds 5, 6, 9, 10 and compound 11 contaminated
with about 15% of 10 were isolated by preparative GLC
from the pooled products obtained in several analogous
experiments.
Cation 26: 19F NMR d (in SO2ClF): 99.0 (3F, CF3); 89.1
(2F, F1, F8); 70.2(2F, F3, F6); 54.1 (2F, F4, F5); 19.5 (2F, F2,
F7) ppm (JCF
43 Hz).
F1
3
Acknowledgements
We gratefully acknowledge the Russian Foundation for
Basic Researches (project N 99-03-32876a) for ®nancial
support.
References
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9-Hydroxyper¯uoro-9-methyl¯uorene (6): mp 105.5±
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SSSR, Ser. Khim. (1990) 645.
1078C (from hexane). MS: Found:
M
393.98538.
C14HF11O requires: M 393.98516. 19F NMR d: 84.9 (3F,
[4] V.M. Karpov, T.V. Mezhenkova, V.E. Platonov, G.G. Yakobson, Izv.
Akad. Nauk SSSR, Ser. Khim. (1990) 1114.
CF3); 29.3 (2F, F4, F5); 23.1 (2F, F1, F8); 13.6 (2F, F3, F6);
10.9 (2F, F2, F7) ppm (JCF
19 Hz).
[5] V.M. Karpov, T.V. Mezhenkova, V.E. Platonov, Izv. Akad. Nauk, Ser.
Khim. (1992) 1419.
F1
3
Per¯uoro-1,2,3,4,5,6,7,8-octahydroanthracene (9) (cf.
[17]): mp (in a sealed capillary) 128.5±129.58C (from
hexane). MS: Found: M 509.96884. C14F18 requires: M
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(1996) 101.
[7] V.M. Karpov, T.V. Mezhenkova, V.E. Platonov, Zh. Org. Khim. 33
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509.97124. 19F NMR d: 54.4 (8F, F1, F4, F5, F8); 51.9 (2F, F9,
F10); 27.2 (8F, F2, F3, F6, F7) ppm.
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Chem. 65 (1993) 223.
Per¯uoro-10-methyl-9(10H)anthracenone (10): mp (in a
sealed capillary) 166.5±1688C (from hexane). MS: Found:
[10] V.M. Karpov, T.V. Mezhenkova, V.E. Platonov, L.N. Shchegoleva,
Izv. Akad. Nauk SSSR, Ser. Khim. (1991) 2618.
[11] R.D. Chambers, M. Salisbury, G. Apsey, T.F. Holmes, S. Modena, J.
Chem. Soc., Chem. Commun. (1988) 679.
M
423.97648. C15F12O requires: M 423.97574. 19F NMR
d: 82.3 (3F, CF3); 28.4 (2F, F4, F5); 25.2 (2F, F1, F8); 19.5
(2F, F3, F6); 15.2 (2F, F2, F7); 11.4 (1F, F10) ppm (J4;10
[12] R.D. Chambers, M. Salisbury, G. Apsey, G. Moggi, J. Chem. Soc.,
Chem. Commun. (1988) 680.
CF3 F4
57:5; J12 J23 J34 J56 J67 J78 20; J
CF3 F10
[13] V.D. Shteingarts, Yu.V. Pozdnyakovich, G.G. Yakobson, Zh. Org.
Khim. 7 (1971) 2002.
12:5; J13 J68 11:5; J
10; J24 J57 8:5 Hz).
10-H-per¯uoro-10-methyl-9(10H)anthracenone (11): MS:
Found: M 405.98494. C15HF11O requires: M 405.98516.
[14] Yu.V. Pozdnyakovich, T.V. Chuikova, V.D. Shteingarts, Zh. Org.
Khim. 11 (1975) 1689.
1H NMR d: 5.4 ppm (quartet, JH
7 Hz). 19F NMR d:
CF3
90.9 (3F, CF3); 25.1 (2F, F1, F8); 22.2 (2F, F4, F5); 16.5 (2F,
[15] G.G. Belen'kii, Yu.L. Kopaevich, L.S. German, I.L. Knunyants, Izv.
Akad. Nauk SSSR, Ser. Khim. (1972) 983.
F3, F6); 11.9 (2F, F2, F7) ppm (J12 J23 J34 J56
[16] Yu.V. Pozdnyakovich, V.D. Shteingarts, Zh. Org. Khim. 14 (1978)
2237.
CF3 F4
J67 J78 20; J14 J58 14; J13 J68 10; J
[17] S. Cohen, J. Am. Chem. Soc. 79 (1957) 1499.
[18] Yu.V. Pozdnyakovich, V.D. Shteingarts, Zh. Org. Khim. 14 (1978)
603.
9; JCF
7; J24 J57 5 Hz).
H
3
3.5. Perfluoro-9-methylfluorenyl cation (26)
[19] J. Burdon, J.R. Knights, I.W. Parsons, J.C. Tatlow, Tetrahedron 30
(1974) 3499.
Fluorene 5 (0.2 g) was dissolved in 0.97 g SbF5 (1:8.9)
and the spectrum was recorded. The solution was diluted
[20] Yu.V. Pozdnyakovich, V.D. Shteingarts, J. Fluorine Chem. 4 (1974)
283.