Liquid Crystals Based on Hypervalent Sulfur Fluorides
FULL PAPER
[8] P. Kirsch, M. Bremer, A. Kirsch, J. Osterodt, J. Am. Chem.
Soc. 1999, 121, 11277–11280.
[9] J. H. Clark, C. W. Jones, A. P. Kybett, M. A. McClinton, J. M.
Miller, D. Bishop, R. J. Blade, J. Fluorine Chem. 1990, 48, 249–
253.
[10] a) A. J. Beaumont, J. H. Clark, J. Fluorine Chem. 1991, 52,
295–300; b) L. M. Yagupolskii, N. V. Kondratenko, V. P. Sam-
bur, Synthesis 1975, 721–723.
[11] Organikum, 16th ed., VEB Deutscher Verlag der Wissensch-
aften, Berlin, 1986, p. 549f.
[12] a) Gaussian 98, Revision A.6: M. J. Frisch, G. W. Trucks, H. B.
Schlegel, G. E. Scuseria, M. A. Robb, J. R. Cheeseman, V. G.
Zakrzewski, J. A. Montgomery, Jr., R. E. Stratmann, J. C. Bu-
rant, S. Dapprich, J. M. Millam, A. D. Daniels, K. N. Kudin,
M. C. Strain, O. Farkas, J. Tomasi, V. Barone, M. Cossi, R.
Cammi, B. Mennucci, C. Pomelli, C. Adamo, S. Clifford, J.
Ochterski, G. A. Petersson, P. Y. Ayala, Q. Cui, K. Morokuma,
D. K. Malick, A. D. Rabuck, K. Raghavachari, J. B. Foresman,
J. Cioslowski, J. V. Ortiz, B. B. Stefanov, G. Liu, A. Liashenko,
P. Piskorz, I. Komaromi, R. Gomperts, R. L. Martin, D. J. Fox,
T. Keith, M. A. Al-Laham, C. Y. Peng, A. Nanayakkara, C.
Gonzalez, M. Challacombe, P. M. W. Gill, B. Johnson, W.
Chen, M. W. Wong, J. L. Andres, C. Gonzalez, M. Head-Gor-
don, E. S. Replogle, J. A. Pople, Gaussian, Inc., Pittsburgh, PA,
USA, 1998. The geometries were optimized on the B3LYP/6-
31G(d) level of theory, and were verified to have only positive
eigenfrequencies. The energies were calculated on the B3LYP/
6-311+G(2d,p) level of theory, using the B3LYP/6-31G(d) ge-
ometries and zero point energies; b) For the prediction of di-
electric anisotropy (∆ε) and birefringence (∆n) of liquid crys-
tals: M. Bremer, K. Tarumi, Adv. Mater. 1993, 5, 842–848; c)
M. Klasen, M. Bremer, A. Götz, A. Manabe, S. Naemura, K.
Tarumi, Jpn. J. Appl. Phys. 1998, 37, L945–L948.
of 11 (350 mg, 23%) were obtained, m.p. 196 °C (96.6% purity by
HPLC). H NMR (300 MHz, CDCl3, 303 K): δ = 7.91–7.87 (m, 6
1
H, ar-H), 6.76 (d, J = 9.2 Hz, 2 H, ar-H), 3.11 [s, 6 H, N(CH3)2]
ppm. 19F NMR (235 MHz, CDCl3, 300 K; standard CFCl3): δ =
41.7 (q, J = 25.0 Hz, 4F, SFeq), –62.8 (quint, J = 25.0 Hz, 3F, CF3)
ppm. MS (EI, 70 eV): m/z (%) = 401 [M+] (58), 313 (4), 224 (5), 148
(13), 120 (100), 105 (13), 77 (11). C15H14F7N3S (401.347): calcd. C
44.9, H 3.5, N 10.5; found C 44.7, H 3.3, N 10.1.
12: Preparation in analogy to 11, starting from 10 (6.0 g,
27.4 mmol).[5b] Yield: Dark red crystals of 12 (3.5 g, 36%), m.p.
180 °C; (99.0% purity by HPLC). 1H NMR (300 MHz, CDCl3,
303 K): δ = 7.91–7.85 (m, 6 H, ar-H), 6.75 (d, J = 9.1 Hz, 2 H, ar-
H), 3.10 [s, 6 H, N(CH3)2]. 19F NMR (235 MHz, CDCl3, 300 K;
standard CFCl3): δ = 84.8 (quint, J = 148 Hz, 1F, SFax: ), 63.4 (d,
J = 148 Hz, 4F, SFeq). MS (EI, 70 eV): m/z (%) = 351 [M+] (14),
224 (6), 148 (10), 120 (100), 105 (18), 95 (8), 91 (8), 77 (15).
C14H14F5N3S (351.339): calcd. C 47.9, H 4.0, N 12.0; found C 48.0,
H 3.9, N 12.0.
Acknowledgments
We thank J. Haas, H. Heldmann and K. Altenburg for the physical
characterization of the new compounds, Dr. C. Saal and Dr. N.
Fichtner for analytical support, and Dr. M. Bremer for valuable
advice on the quantum chemical calculations. We are indebted to
I. Svoboda (Technical University of Darmstadt, group of Prof. Dr.
Fuess) for the X-ray structure analysis.
[1] a) P. Kirsch, A. Hahn, Eur. J. Org. Chem. 2005, 3095–3100; b)
P. Kirsch, M. Bremer, M. Heckmeier, K. Tarumi, Angew.
Chem. 1999, 111, 2174–2178; Angew. Chem. Int. Ed. 1999, 38,
1989–1992.
[2] P. Kirsch, M. Bremer, Angew. Chem. 2000, 112, 4384–4405; An-
gew. Chem. Int. Ed. 2000, 39, 4216–4235, and references
therein.
[3] a) W. Maier, G. Meier, Z. Naturforschung, Teil A 1961, 16, 262–
267; b) D. Demus, G. Pelzl, Z. Chem. 1982, 21, 1; c) J. Michl,
E. W. Thulstrup, Spectroscopy with Polarized Light: Solute
Alignment by Photoselection, in: Liquid Crystals, Polymers, and
Membranes, VCH, Weinheim, 1995, 171–221.
[4] P. Kirsch, Modern Fluoroorganic Chemistry: Synthesis Reac-
tivity, Applications, Wiley-VCH, Weinheim, Germany, 2004.
[5] a) W. A. Sheppard, J. Am. Chem. Soc. 1960, 82, 4751–4752; b)
W. A. Sheppard, J. Am. Chem. Soc. 1962, 84, 3064–3071; c)
W. A. Sheppard, J. Am. Chem. Soc. 1962, 84, 3072–3076; d)
A. M. Sipyagin, C. P. Bateman, Y.-T. Tan, J. S. Thrasher, J. Flu-
orine Chem. 2001, 112, 287–295; e) A. M. Sipyagin, S. V. En-
shov, S. A. Kashtanov, C. P. Bateman, B. D. Mullen, Y.-T. Tan,
J. S. Thrasher, J. Fluorine Chem. 2004, 125, 1305–1316.
[6] a) G. A. Silvey, G. H. Cady, J. Am. Chem. Soc. 1950, 72, 3624–
3626; b) A. F. Clifford, H. K. El-Shamy, H. J. Emeléus, R. N.
Haszeldine, J. Chem. Soc. 1953, 2372–2375; c) R. D. Dresdner,
J. A. Young, J. Am. Chem. Soc. 1959, 81, 574–577; d) J. A.
Young, R. D. Dresdner, J. Org. Chem. 1959, 24, 1021–1022; e)
M. T. Rogers, J. D. Graham, J. Am. Chem. Soc. 1962, 84, 3666–
3670; f) J. I. Darragh, G. Haran, D. W. A. Sharp, J. Chem. Soc.,
Dalton Trans. 1973, 2289–2293; g) G. Haran, D. W. H. Sharp,
J. Fluorine Chem. 1974, 3, 423–428; h) S.-L. Yu, J. M. Shreeve,
J. Fluorine Chem. 1975, 6, 259–266; i) K. Alam, J. M. Shreeve,
[13] The “virtual” parameters TNI,virt, ∆εvirt and ∆nvirt were deter-
mined by linear extrapolation from a 10% w/w solution in the
commercially available Merck mixture ZLI-4792 (TNI
=
92.8 °C, ∆ε = 5.3, ∆n = 0.0964). The extrapolated values are
corrected empirically for differences in the order parameter
which are induced by the analyte. For the pure substances, the
phase-transition temperatures were measured by differential
scanning calorimetry (DSC), the phase type was assigned by
optical polarization microscopy.
[14] Crystal structure data for trans-3 (C7H4F7NO2S), by crystalli-
zation from acetonitrile: orthorhombic, Pnma, a = 8.096(2) Å,
b = 10.059(1) Å, c = 11.967(3) Å, α = β = γ = 90°, V =
974.6(4) Å3, Z = 4, ρcalcd. = 2.039 g·cm–1, R(F) = 14.9% for
1041 observed independent reflections (4.24° Յ ϑ Յ 26.36°).
The data were collected at 100 K, additional diffuse scattering
was observed. CCDC-283724 contains the supplementary crys-
tallographic data for this paper. These data can be obtained
free of charge from The Cambridge Crystallographic Data
Centre via www.ccdc.cam.ac.uk/data_request/cif.
[15] a) T. Fujita, J. Iwasa, C. Hansch, J. Am. Chem. Soc. 1964, 86,
5175; b) C. Hansch, R. M. Muir, T. Fujita, P. P. Maloney, F.
Geiger, M. Streich, J. Am. Chem. Soc. 1963, 85, 2817; c) C.
Hantsch, A. Leo, Substituent Constants for Correlation Analy-
sis in Chemistry and Biology, John Wiley & Sons, New York,
1979.
[16] R. B. Silverman, The Organic Chemistry of Drug Design and
Drug Action, Academic Press, San Diego, 1992.
[17] Annex of EC Directive 92/69/EEC, method A.8 (published on
Dec. 29, 1992).
[18] L. M. Yagupolskii, L. Z. Gandelsman, Zh. Obsh. Khim. 1965,
35, 1252–1260.
H. G. Mack, H. Oberhammer, J. Mol. Struct. 1988, 178, 207– [19] J. C. Biffinger, H. W. Kim, S. G. DiMagno, ChemBioChem
216.
[7] W. T. Sturges, T. J. Wallington, M. D. Hurley, K. P. Shine, K.
Shira, A. Engel, D. E. Oram, S. A. Penkett, R. Mulvaney,
C. A. M. Brenninkmeijer, Science 2000, 289, 611–613.
2004, 5, 622–627.
[20] D. Peters, R. Miethchen, J. Fluorine Chem. 1996, 79, 161–165.
Received: September 21, 2005
Published Online: December 21, 2005
Eur. J. Org. Chem. 2006, 1125–1131
© 2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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