G Model
FLUOR-8582; No. of Pages 5
4
X.-Y. Deng et al. / Journal of Fluorine Chemistry xxx (2015) xxx–xxx
J = 30.7, 26.4 Hz, 1F), ꢀ83.84 (dd, J = 30.7, 3.5 Hz, 1F). GC–MS(EI)
calcd. for C14H10F2 [M]+ 216.1. Found 216.1.
Methyl
(3m): 61%; Light yellow liquid. 1H NMR (400 MHz, CDCl3)
40-(2,2-difluorovinyl)-[1,10-biphenyl]-2-carboxylate
7.83
d
Methyl 4-(2,2-difluorovinyl)-2-methoxybenzoate (3d): 53%;
(d, J = 7.7 Hz, 1H), 7.53 (t, J = 7.1 Hz, 1H), 7.45–7.33 (m, 4H), 7.30–
7.20 (m, 2H), 5.31 (dd, J = 26.4, 3.7 Hz, 1H), 3.66 (s, 3H). 19F NMR
Light yellow liquid. 1H NMR (400 MHz, CDCl3)
d
7.78 (d, J = 8.0 Hz,
1H), 6.96–6.91 (m, 2H), 5.30 (dd, J = 25.1, 3.6 Hz, 1H), 3.91 (s, 3H),
(376 MHz, CDCl3)
d
ꢀ81.80 (dd, J = 30.6, 26.4 Hz, 1F), ꢀ83.86 (dd,
168.95 (s), 156.33
3.88 (s, 3H). 19F NMR (376 MHz, CDCl3)
d
ꢀ79.00 (t, J = 25.1, 1F),
J = 30.6, 3.7 Hz, 1F). 13C NMR (101 MHz, CDCl3)
d
ꢀ81.12 (dd, J = 25.1, 3.6 Hz, 1F). 13C NMR (101 MHz, CDCl3)
d
(dd, J = 298.6, 288.5 Hz), 141.94 (s), 140.00 (t, J = 2.1 Hz), 131.37 (s),
130.65 (s), 129.91 (s), 129.34 (dd, J = 7.0, 5.9 Hz), 128.81 (s), 128.66
(s), 128.18 (s), 127.28 (dd, J = 6.3, 3.7 Hz), 82.00 (dd, J = 29.3,
166.17 (s), 159.42 (s), 156.78 (dd, J = 300.2, 290.7 Hz), 135.94 (dd,
J = 7.3, 6.4 Hz), 132.16 (s), 119.51 (dd, J = 6.5, 3.5 Hz), 118.46 (s),
111.05 (dd, J = 7.0, 3.5 Hz), 82.16 (dd, J = 29.8, 12.9 Hz), 55.99 (s),
13.6 Hz), 52.01 (s). IR (neat)
n = 3032, 2952, 2664, 1728, 1599,
51.97 (s). IR (neat)
n
= 2953, 1725, 1611, 1566, 1508, 1465, 1435,
1575, 1519, 1482, 1448, 1433, 1410, 1351, 1290, 1248, 1191, 1168,
1127, 1089, 1048, 1006, 940, 853, 795, 764, 735, 714, 668, 578, 565,
527, 447 cmꢀ1. HRMS (EI): calcd. for C16H12F2O2: 204.0805. Found:
204.0801.
1413, 1354, 1300, 1261, 1220, 1185, 1165, 1089, 1037, 982, 923,
894, 859, 817, 779, 754 cmꢀ1. HRMS (EI): calcd. for C11H10F2O3:
228.0598. Found: 228.0595.
Methyl 4-(2,2-difluorovinyl)benzoate (3e): 71%; 1H NMR
2-(2,2-Difluorovinyl)naphthalene (3o): 65%; 1H NMR
(400 MHz, CDCl3)
d
7.98 (d, J = 8.4 Hz, 2H), 7.37 (d, J = 8.4 Hz, 2H),
(300 MHz, CDCl3)
d 7.85–7.73 (m, 4H), 7.51–7.43 (m, 3H), 5.43
5.31 (dd, J = 25.8, 3.6 Hz, 1H), 3.89 (s, 3H). 19F NMR (376 MHz, CDCl3)
(dd, J = 26.3, 3.9 Hz, 1H). 19F NMR (376 MHz, CDCl3)
d
ꢀ81.90 (dd,
d
ꢀ79.16 (dd, J = 25.8, 23.8 Hz, 1F), ꢀ81.11 (dd, J = 23.8, 3.6 Hz, 1F).
J = 30.8, 26.3 Hz, 1F), ꢀ83.64 (dd, J = 30.8, 3.9 Hz, 1F). GC–MS(EI)
GC–MS(EI) calcd. for C10H8F2O2 [M]+ 198.1. Found 198.1.
calcd. for C12H8F2 [M]+ 190.1. Found 190.1.
1-(4-(2,2-Difluorovinyl)phenyl)ethanone (3f): 61%; 1H NMR
(400 MHz, CDCl3)
d 7.93 (d, J = 8.4 Hz, 2H), 7.41 (d, J = 8.4 Hz, 2H),
Acknowledgements
5.34 (dd, J = 25.9, 3.5 Hz, 1H), 2.59 (s, 3H). 19F NMR (376 MHz,
CDCl3)
d
ꢀ79.01 (dd, J = 25.9, 23.1 Hz, 1F), ꢀ80.83 (dd, J = 23.1,
This work was financially supported by the National Natural
Science Foundation (21172240, 21421002, 21472222), National
Basic Research Program of China (2015CB931900, 2012CBA01200),
and the Chinese Academy of Sciences.
3.5 Hz, 1F). GC–MS(EI) calcd. for C10H8F2O [M]+ 182.1. Found 182.1.
40-(2,2-Difluorovinyl)-[1,10-biphenyl]-2-carbonitrile (3g): 62%;
A white solid. M.p. 91–92 8C. 1H NMR (400 MHz, CDCl3)
d 7.76 (d,
J = 7.6 Hz, 1H), 7.64 (t, J = 7.6 Hz, 1H), 7.57–7.41 (m, 6H),
d
5.34 (dd,
J = 27.2, 3.2 Hz, 1H). 19F NMR (376 MHz, CDCl3)
d
ꢀ80.93 (t,
J = 27.2 Hz, 1F), ꢀ82.77 (dd, J = 27.2, 3.2 Hz, 1F). 13C NMR
Appendix A. Supplementary data
(101 MHz, CDCl3)
d 156.51 (dd, J = 299.1, 289.4 Hz), 144.80 (s),
Supplementary data associated with this article can be found,
136.66 (t, J = 2.0 Hz), 133.80 (s), 132.88 (s), 130.93 (t, J = 6.6 Hz),
129.90 (s), 129.05 (s), 127.88 (dd, J = 6.5, 3.6 Hz), 127.64 (s), 118.68
(s), 111.10 (s), 81.85 (dd, J = 29.5, 13.4 Hz). IR (neat) n = 3854, 3079,
3033, 2221, 1728, 1685, 1654, 1612, 1596, 1477, 1445, 1415, 1366,
1324, 1289, 1254, 1198, 1179, 1168, 1006, 958, 941, 879, 857, 820,
763, 723, 708, 593, 582, 575, 562, 544, 512, 486 cmꢀ1. HRMS (EI):
calcd. for C15H9F2N: 241.0703. Found: 241.0701.
References
1,2-Dichloro-4-(2,2-difluorovinyl)benzene (3i): 53%; Light yel-
low liquid. 1H NMR (400 MHz, CDCl3)
d
7.43–7.37 (m, 2H), 7.15 (dd,
J = 8.4, 2.1 Hz, 1H), 5.22 (dd, J = 25.9, 3.3 Hz, 1H). 19F NMR
(376 MHz, CDCl3)
ꢀ79.98 (t, J = 25.9 Hz, 1F), ꢀ81.81 (dd,
J = 25.9, 3.3 Hz, 1F). 13C NMR (101 MHz, CDCl3)
156.54 (dd,
d
d
J = 299.3, 290.4 Hz), 132.82 (s), 130.93 (t, J = 2.6 Hz), 130.58 (s),
130.41 (dd, J = 7.3, 6.1 Hz), 129.22 (dd, J = 6.9, 3.7 Hz), 126.77 (dd,
J = 6.6, 3.5 Hz), 80.87 (dd, J = 30.7, 13.5 Hz). IR (neat)
n = 3853,
3042, 1728, 1594, 1556, 1474, 1396, 1351, 1275, 1240, 1175, 1136,
1095, 1033, 956, 882, 866, 826, 747, 723, 697, 680, 671, 598, 566,
516, 506, 440 cmꢀ1. HRMS (EI): calcd. for C8H4Cl2F2: 207.9658.
Found: 207.9662.
1,3-Dibromo-5-(2,2-difluorovinyl)benzene (3k): 54%; 1H NMR
(300 MHz, CDCl3)
d 7.54 (t, J = 1.6 Hz, 1H), 7.40 (d, J = 1.6 Hz, 2H),
5.19 (dd, J = 24.4, 3.3 Hz, 1H). 19F NMR (376 MHz, CDCl3)
d
ꢀ78.62
(t, J = 24.4, 1F), ꢀ80.61 (dd, J = 24.4, 3.3 Hz, 1F). GC–MS(EI) calcd.
for C8H4Br2F2 [M]+ 297.9. Found 298.0.
(E)-Methyl 3-(4-(2,2-difluorovinyl)phenyl)acrylate (3l): 75%; A
yellow solid. M.p. 56–57 8C. 1H NMR (400 MHz, CDCl3)
J = 16.0 Hz, 1H), 7.49 (d, J = 8.2 Hz, 2H), 7.34 (d, J = 8.2 Hz, 2H), 6.43
(d, J = 16.0 Hz, 1H), 5.30 (dd, J = 26.1, 3.3 Hz, 1H), 3.81 (s, 3H). 19F
NMR (376 MHz, CDCl3)
J = 26.1, 3.3 Hz, 1F). 13C NMR (101 MHz, CDCl3)
(dd, J = 299.9, 290.1 Hz), 144.11 (s), 133.01 (t, J = 2.2 Hz), 132.50 (t,
J = 6.6 Hz), 128.40 (s), 127.98 (dd, J = 6.7, 3.6 Hz), 117.72 (s), 82.06
(dd, J = 29.7, 13.3 Hz), 51.75 (s). IR (neat)
d 7.66 (d,
d
ꢀ80.06 (t, J = 26.1 Hz, 1F), ꢀ82.12 (dd,
167.42 (s), 156.58
d
n = 3406, 3034, 2955,
1716, 1636, 1606, 1559, 1513, 1435, 1421, 1320, 1252, 1213, 1169,
1072, 1003, 981, 941, 850, 836, 819, 724, 710, 688, 521, 508 cmꢀ1
HRMS (EI): calcd. for C12H10F2O2: 224.0649. Found: 224.0646.
.