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MS (EI, 70 eV): m/z (%) = 311 (M+ – I, 47), 109 (100).
HRMS: m/z [M]+ calcd for C9H12ClF4I: 357.9608; found: 357.9604.
Anal. Calcd for C9H13ClF4IO3P: C, 24.65; H, 2.99. Found: C, 24.94;
H, 3.09.
1-Chloro-1,1,2,2-tetrafluoro-4-iodoundec-4-ene (3j)
Colorless oil.
Diethyl (E)-4,4,5,5,6,6,7,7,7-Nonafluoro-2-iodohept-1-enyl-
phosphonate (3f)
Colorless oil.
IR (KBr): 2959, 2930, 2859, 1635, 1460, 1424, 1380, 1255, 1205,
1154, 1094, 938 cm–1.
1H NMR (CDCl3): d (E-isomer) = 0.88–0.89 (m, 3 H), 1.26–1.53
(m, 8 H), 2.13–2.20 (m, 2 H), 3.38 (t, J = 16.8 Hz, 2 H), 6.61 (t,
J = 2.7 Hz, 1 H); d (Z-isomer) = 0.88–0.89 (m, 3 H), 1.26–1.53 (m,
8 H), 2.13–2.20 (m, 2 H), 3.38 (t, J = 16.8 Hz, 2 H), 5.82 (t, J = 6.6
Hz, 1 H).
IR (KBr): 2986, 2940, 2911, 1602, 1394, 1349, 1240, 1199, 1169,
1135, 1053, 1026, 972 cm–1.
1H NMR (CDCl3): d = 1.33 (t, J = 7.5 Hz, 6 H), 4.08–4.26 (m, 6 H),
6.86 (d, J = 8.4 Hz, 1 H).
13C NMR (75 MHz, CDCl3): d = 14.02, 14.10, 22.72, 22.73, 27.86,
28.05, 28.78, 28.92, 31.77, 31.97, 34.20, 37.04, 39.35 (t, JC-F = 61.2
Hz), 45.23 (t, JC-F = 60.77 Hz), 79.15, 87.06, 145.04, 150.29.
19F NMR (282 MHz, CDCl3): d = –80.98 (t, J = 10.7 Hz, 3 F),
–112.76 (m, 2 F), –124.40 (m, 2 F), –125.99 (m, 2 F).
31P NMR (162 MHz, CDCl3): d = 10.89.
19F NMR (282 MHz, CDCl3): d (E-isomer) = –71.39 (m, 2 F),
–113.05 (m, 2 F); d (Z-isomer) = –70.91 (m, 2 F), –112.67 (m, 2 F).
MS (EI, 70 eV): m/z (%) = 525 (8), 394 (52), 109 (100).
MS (EI, 70 eV): m/z (%) = 386 (M+, 6), 302 (9), 69 (68), 41 (100).
Anal. Calcd for C11H13F9IO3P: C, 25.31; H, 2.51. Found: C, 25.51;
H, 2.52.
HRMS: m/z [M]+ calcd for C11H16ClF4I: 385.9921; found:
385.9929.
Ethyl (E)-8-Chloro-5,5,6,6,7,7,8,8-octafluoro-3-iodooct-2-en-
oate (3g)
Colorless oil.
8-Chloro-5,5,6,6,7,7,8,8-octafluoro-3-iodooct-2-en-1-ol (3k)
Colorless oil.
IR (KBr): 2990, 1723, 1617, 1421, 1371, 1326, 1282, 1190, 1117,
1039, 1018 cm–1.
IR (KBr): 3346, 2922, 1635, 1428, 1357, 1313, 1188, 1134, 1091,
1023, 971 cm–1.
1H NMR (CDCl3): d = 1.28 (t, J = 7.2 Hz, 3 H), 4.31–4.15 (m, 4 H),
7.04 (s, 1 H).
1H NMR (CDCl3): d (E-isomer) = 1.52 (t, J = 5.4 Hz, OH), 3.37–
3.55 (m, 2 H), 4.13 (t, J = 6.0 Hz, 2 H), 6.87 (t, J = 6.0 Hz, 1 H); d
(Z-isomer) = 1.63 (t, J = 5.7 Hz, OH), 3.37–3.55 (m, 2 H), 4.25 (t,
J = 4.8 Hz, 2 H), 6.20 (t, J = 4.8 Hz, 1 H).
19F NMR (282 MHz, CDCl3): d = –67.98 (m, 2 F), –112.72 (t,
J = 13.8 Hz, 2 F), –119.87 (m, 2 F), –122.82 (m, 2 F).
MS (EI, 70 eV): m/z (%) = 475 (M+ + 1, 11), 347 (41), 69 (100).
13C NMR (75 MHz, CDCl3): d = 40.19 (t, JC-F = 48.22 Hz), 45.26 (t,
JC-F = 47.94 Hz), 60.56, 67.47, 82.38, 86.44, 143.67, 148.20.
Anal. Calcd for C10H8ClF8IO2: C, 25.31; H, 1.70. Found: C, 25.63;
H, 1.71.
19F NMR (282 MHz, CDCl3): d = –68.05 (m, 2 F), –113.49 (m, 2 F),
–119.75 (m, 2 F), –122.52 (m, 2 F).
Ethyl (E)-5,5,6,6,7,7,8,8,8-Nonafluoro-3-iodooct-2-enoate (3h)
Colorless oil.
MS (EI, 70 eV): m/z (%) = 433 (M+ + 1, 1), 416 (35), 304 (47), 69
(100).
IR (KBr): 2991, 1724, 1617, 1421, 1372, 1348, 1325, 1282, 1237,
1194, 1135, 1117, 1033, 1010 cm–1.
Anal. Calcd for C8H6ClF8IO: C, 22.22; H, 1.40. Found: C, 22.57; H,
1.47.
1H NMR (CDCl3): d = 1.28 (t, J = 7.2 Hz, 3 H), 4.32–4.15 (m, 4 H),
7.05 (s, 1 H).
Acknowledgment
19F NMR (282 MHz, CDCl3): d = –81.04 (m, 3 F), –112.90 (m, 2 F),
–124.40 (m, 2 F), –125.90 (m, 2 F).
Financial support from the National Natural Science Foundation of
China (No. 20572124) is gratefully acknowledged.
MS (EI, 70 eV): m/z (%) = 461 (53), 330 (77), 69 (100).
Anal. Calcd for C10H8F9IO2: C, 26.22; H, 1.76. Found: C, 26.61; H,
1.76.
References
(1) (a) Uneyama, K. Organofluorine Chemistry; Blackwell:
Oxford, 2006. (b) Fluorine-Containing Synthons;
1-Chloro-1,1,2,2-tetrafluoro-4-iodonon-4-ene (3i)
Colorless oil.
Soloshonok, V. A., Ed.; American Chemical Society:
Washington, 2005. (c) Chambers, R. D. Fluorine in Organic
Chemistry; Blackwell: Oxford, 2004. (d) Hiyama, T.
Organofluorine Compounds — Chemistry and Applications;
Springer Verlag: Berlin, 2000. (e) Chambers, R. D.
Organofluorine Chemistry — Fluorinated Alkenes and
Reactive Intermediates; Springer Verlag: Berlin, 1997.
(f) Organofluorine Chemistry: Techniques and Synthons;
Chambers, R. D., Ed.; Springer: Berlin, 1997.
IR (KBr): 2959, 2930, 2859, 1640, 1467, 1424, 1380, 1254, 1205,
1135, 1094, 938 cm–1.
1H NMR (CDCl3): d (E-isomer) = 0.89–0.91 (m, 3 H), 1.34–1.45
(m, 4 H), 2.14–2.21 (m, 2 H), 3.38 (t, J = 18.0 Hz, 2 H), 6.63 (t,
J = 3.3 Hz, 1 H); d (Z-isomer) = 0.89–0.91 (m, 3 H), 1.34–1.45 (m,
4 H), 2.14–2.21 (m, 2 H), 3.38 (t, J = 18.0 Hz, 2 H), 5.82 (t, J = 6.9
Hz, 1 H).
13C NMR (75 MHz, CDCl3): d = 13.75, 13.89, 22.20, 22.71, 29.75,
30.97, 31.45, 36.75, 39.34 (t, JC-F = 62.60 Hz), 45.25 (t, JC-F = 62.04
Hz), 79.15, 87.06, 150.00, 150.25.
(2) (a) Ma, J.-A.; Cahard, D. Chem. Rev. 2004, 104, 6119.
(b) Brace, N. O. J. Fluorine Chem. 2001, 108, 147. (c)Ryu,
I.; Kreimerman, S.; Nihuma, T.; Minakata, S.; Komatsu, M.;
Luo, Z.; Curran, D. P. Tetrahedron Lett. 2001, 42, 947.
(d) Hu, Q.-S.; Hu, C.-M. J. Fluorine Chem. 1996, 76, 117.
(e) Foulard, G.; Brigaud, T.; Portella, C. Tetrahedron 1996,
52, 6187. (f) Davis, D. R.; Burton, D. J.; Yang, Z.-Y. J.
19F NMR (282 MHz, CDCl3): d (E-isomer) = –71.26 (m, 2 F),
–112.61 (m, 2 F); d (Z-isomer) = –70.74 (m, 2 F), –112.96 (m, 2 F).
MS (EI, 70 eV): m/z (%) = 358 (M+, 13), 302 (10), 55 (100).
Synthesis 2007, No. 5, 739–743 © Thieme Stuttgart · New York