J. Zhu et al. / Journal of Fluorine Chemistry 171 (2015) 139–147
145
(t, J = 3.9 Hz, 2F), À107.4 (t, J = 4.0 Hz, 2F); 13C NMR (CDCl3,
1089 cmÀ1; MS (EI, m/z, %): 270 (M+, 46.12), 127 (100.00), 107
(23.37), 77 (40.33), 57 (15.55); HRMS (EI): Calcd. for C14H10F4O
(M+): 270.0668; Found: 270.0668.
75 MHz):
d 152.3, 138.2, 132.4, 124.7, 114.3 (tt, J = 233, 26 Hz),
113.0 (tt, J = 224, 27 Hz); IR (film): 3853, 3112, 1946, 1537, 1367,
1255, 1183 cmÀ1; MS (EI, m/z, %): 367 (M+, 0.33), 186 (100.00), 122
(31.54), 76 (16.41), 75 (13.49); HRMS (EI): Calcd. for C8H4NSF4O4Br
(M+): 366.8960; Found: 366.8965.
1-Nitro-4-(1,1,2,2-tetrafluoro-2-phenylethoxy)benzene (12d)
O2N
F F
4.3. Typical procedures for copper(0)-mediated coupling reaction of
2-bromo-1,1,2,2-tetrafluoroethyl compounds with iodobenzene
O
F
F
Under a nitrogen atmosphere, into a 15-mL sealed tube was
added 1-(2-bromo-1,1,2,2-tetrafluoroethoxy)-4-methoxybenzene
(9c) (0.151 g, 0.5 mmol), iodobenzene (0.102 g, 0.5 mmol), Cu
powder (0.064 g, 1.0 mmol), and DMSO (3.0 mL). The reaction
mixture was vigorously stirred at 130–140 8C for 36 h. After
cooling to room temperature, the reaction mixture was quenched
by adding water (10 mL) and extracted with diethyl ether
(10 mL Â 3). The combined organic phase was washed with water,
then dried over anhydrous Na2SO4. After filtration and solvent
removal, the crude product was purified by silica gel chromatog-
raphy (petroleum ether/ethyl acetate, 20:1 v/v) to give 1-methoxy-
4-(1,1,2,2-tetrafluoro-2-phenylethyl)benzene (12e) (0.102 g, 68%
yield) as a pale yellow liquid.
70% yield. Pale yellow liquid. 1H NMR (CDCl3, 300 MHz):
(d, J = 9.1 Hz, 2H), 7.70 (d, J = 9.0 Hz, 2H), 7.59–7.28 (m, 5H); 19F
NMR (CDCl3, 282 MHz):
À87.9 (t, J = 3.5 Hz, 2F), À114.0 (t,
J = 4.6 Hz, 2F); 13C NMR (CDCl3, 75 MHz):
153.9, 145.5, 131.5,
129.8 (t, J = 20 Hz), 128.5, 126.7 (t, J = 5 Hz), 125.6, 121.5, 120.0–
110.0 (m, 2C); IR (film): 1618, 1595, 1529, 1439, 1351, 1286,
1187 cmÀ1; MS (EI, m/z, %): 315 (M +, 25.01), 127 (100.00), 122
(5.35), 77 (7.75), 75 (3.07); HRMS (EI): Calcd. for C14H9NF4O3 (M+):
315.0510; Found: 315.0519.
d 8.26
d
d
1-Methoxy-4-(1,1,2,2-tetrafluoro-2-phenylethoxy)benzene (12e)
MeO
F F
1,1,2,2-Tetrafluoro-1,2-diphenylethane (12a) [20]
O
F F
F
F
67% yield. Colorless liquid. 1H NMR (CDCl3, 300 MHz):
J = 7.8 Hz, 2H), 7.65–7.61 (m, 3H), 7.12 (d, J = 7.5 Hz, 2H), 6.95 (d,
d 7.92 (d,
F
F
J = 7.4 Hz, 2H), 3.90 (s, 3H); 19F NMR (CDCl3, 282 MHz):
d
À86.9 (t,
J = 4.9 Hz, 2F), À113.5 (t, J = 4.8 Hz, 2F); 13C NMR (CDCl3, 75 MHz):
77% yield. Colorless liquid. 1H NMR (CDCl3, 300 MHz):
7.25 (m, 10H); 19F NMR (CDCl3, 282 MHz):
m/z, %): 254 (M+, 12.92), 127 (100.00), 77 (9.03).
1-Methoxy-4-(1,1,2,2-tetrafluoro-2-phenylethyl)benzene (12b)
[21]
d 7.51–
À111.7 (s, 4F); MS (EI,
d
157.7, 142.2, 131.1, 130.6 (t, J = 19 Hz), 128.3, 126.8, 123.0, 114.6,
d
121.0–110.0 (m, 2 C), 55.5; IR (film): 2964, 1509, 1261, 1179, 1090,
1020, 800 cmÀ1; MS (EI, m/z, %): 300 (M+, 100), 127 (52.62), 123
(55.44), 107 (23.37); HRMS (EI): Calcd. for C15H12F4O2 (M +):
300.0773; Found: 300.0770.
1-Chloro-4-(1,1,2,2-tetrafluoro-2-phenylethoxy)benzene (12f)
F
F
Cl
MeO
F F
F
F
O
40% yield. Colorless liquid. 1H NMR (CDCl3, 300 MHz):
7.19 (m, 7H), 6.83 (d, J = 7.5 Hz, 2H), 3.75 (s, 3H); 19F NMR (CDCl3,
282 MHz):
75 MHz):
128.3, 127.2 (t, J = 5 Hz), 123.1 (t, J = 21 Hz), 121.0–115.0 (m, 2 C),
113.7, 55.5; IR (film): 2963, 1614, 1517, 1418, 1261, 1094,
800 cmÀ1; MS (EI, m/z, %): 284 (M+, 7.29), 158 (8.76), 157 (100.00),
127 (6.68); HRMS (EI): Calcd. for C15H12F4O (M+): 284.0824;
Found: 284.0824.
d 7.41–
F
F
54% yield. Colorless liquid. 1H NMR (CDCl3, 300 MHz):
(d, J = 6.0 Hz, 2H), 7.56–7.23 (m, 5H), 7.05 (d, J = 6.1 Hz, 2H); 19F
NMR (CDCl3, 270 MHz):
À87.3 (t, J = 6.1 Hz, 2F), À113.9 (t,
J = 6.1 Hz, 2F); 13C NMR (CDCl3, 75 MHz):
147.6, 131.9, 131.3,
130.3 (t, J = 18 Hz), 129.6, 128.3, 126.7, 123.0, 117.7 (tt, J = 206,
27 Hz), 114.5 (tt, J = 189, 27 Hz); IR (film): 1891, 1590, 1489, 1322,
1286, 1192, 1090 cmÀ1; MS (EI, m/z, %): 304 (M +, 33.82), 127
(100.00), 128 (8.15), 111 (16.04); HRMS (EI): Calcd. for C14H9ClF4O
(M+): 304.0278; Found: 304.0280.
d 7.676
d
À110.8 (s, 2F), À111.9 (s, 2F); 13C NMR (CDCl3,
d
161.7, 131.5 (t, J = 19 Hz), 131.1, 128.7 (t, J = 5 Hz),
d
d
(1,1,2,2-Tetrafluoro-2-phenoxyethyl)benzene (12c)
4-Allyl-2-methoxy-1-(1,1,2,2-tetrafluoro-2-phenylethoxy)ben-
zene (12g)
F F
O
F
F
F F
O
64% yield. Colorless liquid. 1H NMR (CDCl3, 300 MHz):
8.05 (m, 2H), 7.94–7.85 (m, 3H), 7.73–7.58 (m, 3H), 7.49 (d,
J = 9.1 Hz, 2H); 19F NMR (CDCl3, 282 MHz):
À86.5 (s, 2F), À113.3
(s, 2F); 13C NMR (CDCl3, 75 MHz):
149.2, 131.2, 130.5 (t,
d 8.06–
F
F
OMe
d
50% yield. Pale yellow liquid. 1H NMR (CDCl3, 300 MHz):
d7.72 (d,
d
J = 18 Hz), 129.5, 128.3, 126.8 (t, J = 5 Hz), 126.2, 121.6, 121.0–
114.3 (m, 2 C); IR (film): 3071, 1594, 1493, 1332, 1286, 1191,
J = 9.0 Hz, 2H), 7.51–7.47 (m, 3H), 7.04 (d, J = 6.1 Hz, 1H), 6.73–6.71
(m, 3H), 6.01–5.76 (m, 1H), 5.07 (d, J = 15.1 Hz, 2H), 3.69 (s, 3H), 3.34