R. Vaidyanathaswamy et al. / Journal of Fluorine Chemistry 169 (2015) 38–49
47
1
9
1
F NMR (470 MHz, CDCl
J = 268 Hz, –C–CF
3
)
d
ꢀ128.3 and ꢀ122.7 (AB quartet,
–OPh).
H NMR (500 MHz, CDCl
3
)
d
4.63 (1H, d, J = 7.5 Hz, –NH), 5.20
2
), ꢀ83.54 (2F, s, CF
2
(1H, dt, J = 18 and 8.0 Hz, respectively, –CH), 6.68 (2H, d, J = 8.0 Hz,
arom) 6.82 (1H, t, J = 7.5 Hz, arom) 7.11 (2H, d, J = 8 Hz, arom) 7.21
(2H, m, arom) 7.30 (1H, m, arom) 7.38 (4H, m, arom) 7.45 (1H, d,
J = 7.0 Hz, arom) 7.58 (1H, s, arom).
+
+
EI–MS: 346 (M) 153 (M ꢀ CF
2
2
CF OPh) , 109, 77.
+
+
+
CI–MS (isobutane): 403 (M + C
4
9
H ) , 385 (M + K) , 347 (M + H) ,
+
3
29 (M ꢀ OH) .
1
9
F NMR (470 MHz, CDCl
3
)
d
ꢀ125.54, ꢀ116.87 (AB quartet,
4
.27. N-Phenyl-1-phenyl-2,2,3,3-tetrafluoro-3-phenoxypropylamine
8a)
J = 276 Hz, –C–CF
CF –OPh).
2
), ꢀ83.82 and ꢀ82.4 (AB quartet, J = 147 Hz, –
(
2
+
EI–MS: 411, 409 (ratio 1:3, M) 218, 216 (ratio 1:3,
+
Solid, m.p. 93–94.5 8C.
IR (KBr) 3408, 3059, 3034, 1605, 1515, 1496, 1184, 1102, 749,
M ꢀ CF
2 2
CF OPh) 104, 77, 65.
+
CI–MS (isobutane): 412, 410 (ratio 1:3, M + H) .
ꢀ1
6
91 cm
1
.
3
H NMR (500 MHz, CDCl ) d 4.60 (1H, s, –NH) 5.20 (1H, dd,
4
.31. N-(4-Trifluoromethylphenyl)-1-phenyl-2,2,3,3-tetrafluoro-3-
J = 17.5 and 8 Hz, –CH) 6.68 (2H, d, J = 8 Hz, arom) 6.77 (1H, t,
J = 7.5 Hz, arom) 7.09 (2H, d, J = 8 Hz, arom) 7.19 (2H, m, arom) 7.28
phenoxypropylamine (8e)
(1H, m, arom) 7.33 to 7.45 (5H, m, arom) 7.54 (2H, d, J = 7.5 Hz,
arom).
Colourless oil.
19
IR (film) 3445, 3070, 1618, 1532, 1492, 1329, 1190, 1111, 1066,
F NMR: (470 MHz, CDCl
J = 268 Hz, C–CF
) ꢀ83.7 and ꢀ82.5 (AB quartet, J = 142 Hz,
CF OPh).
EI–MS: 375 (M) , 182 (M ꢀ CF
3
)
d
ꢀ125.7, ꢀ117.6 (AB quartet,
ꢀ
1
1017, 824, 744 cm
.
2
1
H NMR:(500 MHz, CDCl
dt, J = 17.5 and 8.5 Hz, respectively), 6.70 (2H, d, J = 8.5 Hz, arom)
.07 (2H, d, J = 8 Hz, arom) 7.29 (1H, m, arom) 7.37 (2H, m, arom)
7.42 (5H, m, arom) 7.52 (2H, d, J = 7 Hz, arom).
3
) d 4.92 (1H, d, J = 8 Hz, NH) 5.22 (1H,
2
+
+
2
2
CF OPh) 104, 77.
+
7
CI–MS (isobutane): 376 (M + H) .
HRMS: 376.1316 calculated mass for C21
H
4
18NOF is 376.1325.
1
9
F NMR (470 MHz, CDCl
J = 276 Hz, –CF
–C–) ꢀ83.38, ꢀ82.64 (AB quartet, J = 147 Hz, –CF
).
3
)
d
ꢀ125.1 ꢀ117.78 (AB quartet,
4.28. N-Phenyl-1-(4-methoxyphenyl)-2,2,3,3-tetrafluoro-3-
2
2
–
phenoxypropylamine (8b)
OPh) ꢀ61.4 (s, CF
3
+
+
EI–MS: 443 (M) , 424 (M ꢀ F) , 250 (M ꢀ CF
2 2
CF OPh) 172, 145,
Colourless oil.
77
+
IR (film) 3424, 3058, 2838, 1603, 1513, 1491, 1251, 1183, 1115,
CI–MS (isobutane): 444 (M + H) .
ꢀ
1
1
029, 749, 690 cm
1
.
H NMR (500 MHz, CDCl
J = 7.5 Hz, NH, partially disappears on D
collapses to dd, J = 17 and 9 Hz upon D
J = 8 Hz, arom) 6.77 (1H, t, 7.5 Hz, arom) 6.96 (2H, m, arom) 7.11
3
)
d
3.84 (3H, s, OCH
O shake) 5.16 (1H, m, CH,
O shake) 6.69 (2H, d,
3
) 4.57 (1H, d,
4
.32. N(3-Trifluoromethylphenyl)-1-(4-methoxyphenyl) 2,2,3,3-
tetrafluoro-3-phenoxypropyl amine (8f)
2
2
Colourless oil.
(
(
2H, d, J = 8 Hz, arom) 7.18 (2H, t, J = 7.5 Hz) 7.28 (1H, m, arom) 7.37
2H, m, arom) 7.46 (2H, d, J = 8 Hz, arom).
IR (film): 3438, 3073, 2934, 2841, 1614, 1514, 1252, 1181, 1122,
ꢀ1
1
027, 786, 738 cm
.
19
F NMR: (470 MHz, CDCl
3
)
d
ꢀ125.3 and ꢀ117.6 (AB quartet,
1
H NMR (500 MHz, CDCl
J = 8 Hz, NH), 5.19 (1H, dt, 17.0 and 8.5 Hz, respectively, –CH–) 6.83
1H, d, J = 8.5 Hz, arom) 6.94 (1H, s, arom) 6.98 (2H, d, J = 8.5 Hz,
arom) 7.03 (1H, d, J = 7.5 Hz, arom) 7.13 (2H, d, J = 8.0 Hz, arom)
.28 (2H, m, arom) 7.38 (2H, d, J = 7.5 Hz, arom) 7.47 (2H, d,
J = 8.5 Hz, arom).
3 3
) d 3.85 (3H, s, OCH ) 4.79 (1H, d,
J = 268 Hz, C–CF
OPh).
2
) ꢀ83.7 and ꢀ82.4 (AB quartet, J = 143 Hz, CF
2
–
(
+
+
EI–MS: 405 (M) , 212 (M ꢀ CF
2 2
CF OPh) , 77.
+
CI–MS (isobutane): 406 (M + H) .
7
4.29. N-(3-Trifluoromethyl phenyl)-1-phenyl 2,2,3,3-tetrafluoro-3-
19
F NMR (470 MHz, CDCl
J = 275 Hz, –CF
–C–), ꢀ83.60, -82.6 (AB quartet, J = 147 Hz, –
CF ).
OPh) ꢀ62.87 (s, CF
EI–MS: 473 (M) , 280 (M ꢀ CF
3
)
d
ꢀ124.82, ꢀ118.1 (AB quartet,
phenoxypropylamine (8c)
2
2
3
Colourless oil.
+
+
2
2
CF OPh) , 205, 172, 145, 77.
IR (film): 3440, 3036, 2926, 1617, 1599, 1492, 1343, 1187, 1123,
+
+
CI–MS (isobutane): 474 (M + H) , 313 (M ꢀ NH ꢀ C
6
H
4
3
ꢀ CF ) .
ꢀ
1
1
017, 696 cm
.
1
H NMR (500 MHz, CDCl
3
):
d
4.83 (1H, d, J = 8 Hz, NH), 5.23 (1H,
O shake), 6.83 (1H,
m, –CH, collapses to dd, J = 17.5 and 8.5 Hz on D
2
4.33. N-(2-Methyphenyl)-1-(4-methoxyphenyl)-2,2,3,3-tetrafluoro-
dd, J = 8.0 and 2.5 Hz, arom) 6.93 (1H, s, arom), 7.02 (1H, d,
J = 7.5 Hz, arom), 7.10 (2H, d, J = 8 Hz, arom) 7.29 (2H, m, arom)
3-phenoxypropylamine (8g)
7
.38 (2H, m, arom) 7.44 (3H, m, arom), 7.55 (2H, d, J = 7.5 Hz, arom).
Colourless oil.
19
F NMR (470 MHz, CDCl
J = 275 Hz, –CF
–C–) ꢀ83.74, ꢀ82.6 (AB quartet, J = 150 Hz, –
CF
3
)
d
ꢀ124.7, ꢀ118 (AB quartet,
IR (film) 3452, 3018, 2960, 2933, 1608, 1589, 1513, 1491, 1193,
ꢀ
1
2
1117, 1027, 748 cm
.
1
2
OPh) ꢀ62.99 (s, CF
3
)
H NMR (500 MHz, CDCl
3 3
) d 2.32 (3H, s, CH ) 3.86 (3H, s,
+
+
+
EI–MS: 443 (M) , 424 (M ꢀ F) , 250 (M ꢀ CF
2
CF
2
ꢀ OPh) , 172,
OCH ), 4.59 (1H, d, J = 7.5 Hz, NH) 5.26 (1H, dt, J = 16 Hz, 7.5 Hz,
3
1
45, 77.
respectively, –C–H) 6.60 (1H, d, J = 8.5 Hz, arom) 6.75 (1H, t,
J = 7.0 Hz, arom) 7.00 (2H, m, arom) 7.09 (1H, m, arom) 7.15 (3H,
m, arom) 7.31 (1H, m, arom) 7.41 (2H, m, arom) 7.52 (2H, d,
J = 8.5 Hz, arom).
+
CI–MS (isobutane): 444 (M + H) .
4.30. N-Phenyl-1-(3-chlorophenyl)-2,2,3,3-tetrafluoro-3-phenoxy-
1
9
propylamine (8d)
F NMR (470 MHz, CDCl
J = 275 Hz, –C–CF
-), ꢀ83.50, ꢀ82.17 (AB quartet, J = 146 Hz,
CF OPh).
EI–MS: 419 (M) , 226 (M ꢀ CF
3
)
d
ꢀ125.7, ꢀ116.7 (AB quartet,
2
Colourless oil.
2
+
+
IR (film) 3435, 3059, 2926, 2853, 1602, 1509, 1491, 1299, 1194,
2 2
CF OPh) 205, 118, 91, 77.
ꢀ
1
+
1
120, 771, 749, 690 cm
.
CI–MS (isobutane): 420 (M + H) .