M.V. Ponomarenko et al. / Journal of Fluorine Chemistry 135 (2012) 68–74
73
with aqueous NaHCO3 and the organic layer dried over NaSO4. The
solvent was removed and the crude product was purified by
filtration through a short column of silica gel (n-hexane). Removal
of solvent provided white crystals of 9a–c.
37.2, 39.9, 45.0, 79.9 (q, J = 8.1 Hz), 88.9 (qd, J = 41.3 Hz, J = 4.0 Hz),
114.1, 128.0, 133.2, 152.8; 19F NMR (188 MHz, CDCl3):
d 75.5–78.9
(9 lines, 1F, A-part), 82.9–83.9 (m, 4F, B4-part); HRMS for [M+]
(C17H21F5S): calcd. 352.1284, found 352.1283.
4.6.1. 4-[(E)-1-chloro-2-(pentafluoro-l6-sulfanyl)vinyl]-40-propyl-
1,10-bi(cyclohexyl) (9a)
4.7.3. 1-[(Pentafluoro-l6-sulfanyl)ethynyl]-4-(4-
pentylcyclohexyl)benzene (10c)
Colourless solid, mp 51–52 8C (92% yield). 1H NMR (200 MHz,
Colourless solid, mp 48–52 8C (72% yield). 1H NMR (200 MHz,
CDCl3):
(m, 1H, JHF = 8.8 Hz, HCSF5); 13C NMR (50 MHz, CDCl3):
29.3, 30.4, 30.5, 33.9, 38.0, 40.2, 42.8, 43.3, 43.7, 135.9 (quin, CSF5,
J = 20.6 Hz), 152.7 (quin, J = 7.0 Hz); 19F NMR (188 MHz, CDCl3):
67.1 (dm, 4F, J = 152.0 Hz, B4-part), 83.1 (9 lines, 1F, A-part); MS (EI,
70 eV, 200 8C): m/z (%) 394 (19, M+), 359 (3, M+–Cl), 231 (11), 125
(81), 83 (61), 69 (100); HRMS for [M+] (C17H28ClF5S): calcd.
394.1520, found 394.1534.
d
0.70–1.45 (m, 17H), 1.55–1.80 (m, 9H), 3.06 (m, 1H), 6.53
CDCl3):
2.51 (tm, 1H, J = 12.2 Hz), 7.25 (d, 2H, J = 8.8 Hz), 7.50 (d, 2H,
J = 8.8 Hz); 13C NMR (50 MHz, CDCl3):
14.5, 23.1, 27.1, 32.0, 32.6,
33.8, 34.4, 37.7, 45.2, 78.9 (q, J = 8.0 Hz), 89.8 (qd, J = 41.3 Hz,
d 0.91 (t, 3H, J = 6.8 Hz), 1.00–1.70 (m, 13H), 1.89 (m, 4H),
d
14.8, 20.5,
d
d
J = 4.3 Hz), 115.0, 127.7, 133.1, 152.1; 19F NMR (188 MHz, CDCl3):
d
75.5–78.9 (p, 1F), 82.9–83.9 (m, 4F); HRMS for [M+] (C19H25F5S):
calcd. 380.1597, found 380.1595.
Acknowledgements
4.6.2. 1-[(E)-1-chloro-2-(pentafluoro-l6-sulfanyl)vinyl]-4-(4-
propylcyclohexyl)benzene (9b)
This work was supported by the Deutsche Forschungsge-
meinschaft (436 UKR 113/99/0-1). The authors are grateful to the
University of Bremen for working facilities.
Colourless solid, mp 52–55 8C (83% yield). 1H NMR (200 MHz,
CDCl3):
2.51 (tm, 1H, J = 12.2 Hz), 6.93 (q, 1H, J = 7.8 Hz), 7.24 (d, 2H,
J = 8.8 Hz), 7.30 (d, 2H, J = 8.8 Hz); 13C NMR (50 MHz, CDCl3):
14.8, 20.4, 33.9, 34.5, 37.4, 40.1, 44.9, 127.1, 128.0, 133.3, 138.0 (q,
d 0.92 (t, 3H, J = 7.2 Hz), 1.00–1.70 (m, 9H), 1.91 (m, 4H),
d
References
J = 21 Hz), 142.7 (q, J = 6.8 Hz), 150.4; 19F NMR (188 MHz, CDCl3):
68.6 (dm, 4F, J = 150.1 Hz), 81.2 (p, 1F); HRMS for [M+]
d
[1] M. Hird, Chem. Soc. Rev. 36 (2007) 2070–2095.
[2] H. Takatsu, Mol. Cryst. Liq. Cryst. 458 (2006) 17–26.
[3] P. Kirsch, Modern Fluoroorganic Chemistry: Synthesis, Reactivity, Applications,
Wiley-VCH, Weinheim, Germany, 2004.
(C17H22ClF5S): calcd. 388.1051, found 388.1056.
[4] P. Kirsch, G.-V. Ro¨schenthaler, in: V.A. Soloshonok, K. Mikami, T. Yamazaki, J.T.
Welch, J.F. Honek (Eds.), Current Fluoroorganic Chemistry – New Synthetic
Directions, Technologies, Materials and Biological Applications, 949, ACS Press,
Washington, 2007, pp. 221–243.
[5] P. Kirsch, J.T. Binder, E. Lork, G.-V. Ro¨schenthaler, J. Fluorine Chem. 127 (2006)
610–619.
[6] Ch. Ye, G.L. Gard, R.W. Winter, R.G. Syvret, B. Twamley, J.M. Shreeve, Org. Lett. 9
(2007) 3841–3844, and references therein.
[7] R.W. Winter, R.A. Dodean, G.L. Gard, in: V.A. Soloshonok (Ed.), ACS Symposium
Series, 911: Fluorine-Containing Synthons, ACS Press, Washington, DC, 2005, pp.
87–118.
4.6.3. 1-[(E)-1-chloro-2-(pentafluoro-l6-sulfanyl)vinyl]-4-(4-
pentylcyclohexyl)benzene (9c)
Colourless solid, mp 54–57 8C (86% yield). 1H NMR (200 MHz,
CDCl3):
2.51 (tm, 1H, J = 12.2 Hz), 6.93 (q, 1H, J = 7.8 Hz), 7.24 (d, 2H,
J = 8.8 Hz), 7.30 (d, 2H, J = 8.8 Hz); 13C NMR (50 MHz, CDCl3):
d 0.92 (t, 3H, J = 7.2 Hz), 1.00–1.70 (m, 13H), 1.91 (m, 4H),
d
14.5, 23.1, 27.1, 32.7, 33.9, 34.5, 37.7, 44.9, 127.1, 128.0, 133.3,
138.0 (q, J = 21 Hz), 143.7 (m, J = 6.8 Hz), 150.4; 19F NMR (188 MHz,
[8] G.S. Lal, R.G. Syvret, Chim. Oggi 26 (2008) 26–27.
[9] D. Lentz, K. Seppelt, in: K. Akiba (Ed.), Chemistry of Hypervalent Compounds,
Wiley-VCH, 1999, pp. 295–325.
CDCl3):
d
68.6 (dm, 4F, J = 150.1 Hz), 81.2 (p, 1F); HRMS for [M+]
(C19H26ClF5S): calcd. 416.1364, found 416.1367.
[10] (a) R. Salmon, WO 9306089 (1993).;
(b) M.N. Howard Jr., T.M. Sevenson, WO 9516676 (1995).;
(c) N. Shigeyoshi, S. Hidetaka, WO 2009028514 (2009).;
(d) P. Kirsch, K. Tarumi, J. Krause, DE19748108 (1999).;
(e) M.J. Goulding, W. Duffy, K. Adlem, P. Kirsch, A. Hahn, E. Poetsch, W. Binder, V.
Meyer, M. Klasen-Memmer, M. Heckmeier, G. Lu¨ssem, EP 1482022 A1 (2004).
(f) J.A. Smith, R.A. DiStasio Jr., N.A. Hannah, R.W. Winter, T.J.R. Weakley, G.L. Gard,
S.B. Rananavare, J. Phys. Chem. B 108 (2004) 19940–19948.
[11] P. Kirsch, A. Hahn, Eur. J. Org. Chem. (2005) 3095–3100.
[12] M. Petrzilka, Mol. Cryst. Liq. Cryst. 111 (1984) 347–358.
[13] R. Buchecker, G. Marck, M. Schadt, Mol. Cryst. Liq. Cryst. 260 (1995) 93–105.
[14] R.J. Terjeson, J.A. Canich, G.L. Gard, M.R. Colsman, M.A. Uremovich, S.H. Strauss,
Inorg. Synth. 27 (1990) 329–332.
[15] (a) J.A.M. Canich, M.M. Ludvig, W.W. Paudler, G.L. Gard, J.M. Shreeve, Inorg.
Chem. 24 (1985) 3668–3670;
(b) G.S. Lal, K.E. Minnich, US 6479645B1 (2002).
[16] F.W. Hoover, D.D. Coffman, J. Org. Chem. 29 (1964) 3567–3570.
[17] V.K. Brel, J. Fluorine Chem. 128 (2007) 862–867.
4.7. Dehydrochlorination of 9a–c: general procedure
To a solution of 9a–c (4.23 mmol) in Me2SO (35 mL) was added
LiOH (5 equiv.). The mixture was stirred for 12 h at 50 8C, then
poured into ice water (ꢀ100 mL), extracted with n-hexane (4ꢂ
20 mL). The organic layers were combined, washed with brine, and
dried over NaSO4. The solvent was removed under reduced
pressure, and then the residue was purified by chromatography
(silica gel; n-hexane), giving alkynes 10a–c.
4.7.1. 4-[(Pentafluoro-l6-sulfanyl)ethynyl]-40-propyl-1,10-
bi(cyclohexyl) (10a)
Colourless solid, mp 49–50 8C (65% yield). 1H NMR (200 MHz,
[18] V.K. Brel, Synthesis (2005) 1245–1250.
CDCl3):
CDCl3):
d
d
0.70–2.15 (m, 26H), 2.29 (m, 1H); 13C NMR (50 MHz,
14.7, 20.4, 29.1, 29.5, 30.3, 32.1, 33.9, 38.0, 40.2, 42.6,
[19] J.R. Case, N.H. Ray, H.L. Roberts, J. Chem. Soc. (1961) 2066–2070.
[20] S. Aı¨t-Mohand, W.R. Dolbier Jr., Org. Lett. 4 (2002) 3013–3015.
[21] W.R. Dolbier Jr., A. Mitani, W. Xu, I. Ghiviriga, Org. Lett. 8 (2006) 5573–5575.
[22] W.R. Dolbier Jr., S. Aı¨t-Mohand, T.D. Schertz, T.A. Sergeeva, J.A. Cradlebaugh, A.
Mitani, G.L. Gard, R.W. Winter, J.S. Thrasher, J. Fluorine Chem. 127 (2006) 1302–
1310.
43.5, 82.2 (quind, CSF5, J = 40.8 Hz, J = 4.0 Hz), 84.1 (m, J = 7.5 Hz);
19F NMR (188 MHz, CDCl3):
76.4–79.7 (9 lines, 1F, A-part), 82.8–
d
83.9 (m, 4F, B4-part); MS (EI, 70 eV, 200 8C): m/z (%) 358 (4, M+),
315 (15, M+–Pr), 231 (9, M+–SF5), 123 (33), 83 (63), 69 (100); HRMS
for [M+] (C17H27F5S): calcd. 358.1754, found 358.1752.
[23] M.V. Ponomarenko, Y.A. Serguchev, G.-V. Ro¨schenthaler, J. Fluorine Chem. 131
(2010) 270–273.
[24] M.V. Ponomarenko, Y.A. Serguchev, G.-V. Roschenthaler, Synthesis (2010) 3906–
¨
3912.
4.7.2. 1-[(Pentafluoro-l6-sulfanyl)ethynyl]-4-(4-
propylcyclohexyl)benzene (10b)
[25] (a) W.D. Pfeiffer, in: E. Schaumann (Ed.), Science of Synthesis, vol. 35, Thieme,
Stuttgart, 2007, pp. 423–434;
(b) H. Dauben, L. McCoy, J. Org. Chem. 24 (1959) 1577–1579;
(c) H. Stetter, E. Tresper, Chem. Ber. 104 (1971) 71–74.
[26] (a) W. Quaglia, M. Pigini, S.K. Tayebati, A. Piergentili, M. Giannella, G. Marucci, C.
Melchiorre, J. Med. Chem. 36 (1993) 1520–1528;
Colourless solid, mp 43–48 8C (70% yield). 1H NMR (200 MHz,
CDCl3):
2.51 (tm, 1H, J = 12.2 Hz), 7.25 (d, 2H, J = 8.8 Hz), 7.50 (d, 2H,
J = 8.8 Hz); 13C NMR (50 MHz, acetone-d6):
14.2, 20.2, 33.6, 34.1,
d 0.91 (t, 3H, J = 6.8 Hz), 1.00–1.70 (m, 9H), 1.89 (m, 4H),
(b) F. Grellepois, F. Chorki, M. Oure´vitch, B. Crousse, D. Bonnet-Delpon, J.-P.
Be´gue´, Tetrahedron Lett. 43 (2002) 7837–7840;
d