G.-Y. Yang et al. / Journal of Fluorine Chemistry 168 (2014) 1–8
7
121.8(q, J = 269.9 Hz), 121.9, 122.3 (q, J = 35.2 Hz), 129.5, 131.5,
135.9, 143.6, 145.8, 153.1, 157.1; HRMS (ESI): calcd for
C17H11BrF3N2O2 [M+H]+: m/z = 410.9956, found 410.9953; IR
117.1, 118.8, 122.0 (q, J = 270.0 Hz), 122.9 (q, J = 35.6 Hz), 125.3,
129.7, 133.8, 140.4, 147.3, 154.2, 156.5, 157.7, 158.9; HRMS (ESI)
calcd for C17H11F4N2O2 [M+H]+: m/z = 351.0757, found 351.0752;
IR (KBr, cmꢀ1
) n 3283 (m), 1699 (s), 1611 (m), 1520 (m), 1504 (m),
(KBr, cmꢀ1
)
n
= 3293 (w), 1717 (s), 1603 (s), 1560 (m), 1493
(m), 1476 (m), 1335 (w), 1304 (w), 1259 (m), 1187 (s), 1151 (m),
1109 (m), 1064 (m), 1067 (m), 960 (w), 934 (w), 923 (w), 814 (w),
777 (w), 752 (m), 683 (m).
1400 (m), 1213 (m), 1189 (m), 1119 (m), 1071 (m), 978 (w), 956
(w), 945 (w), 831 (m), 782 (w), 760 (m), 469 (w).
4.4.9. 3-(4-Chlorophenylhydrazonotrifluoroethyl)coumarin (3i)
Yield 57%, yellow powder, mp 176.0–177.4 8C. 1H NMR
4.4.4. 3-(Phenylhydrazonotrifluoroethyl)-6,8-(dichloro)coumarin
(3d)
(400 MHz, DMSO):
d = 7.16 (d, J = 8.8 Hz, 2H), 7.35 (d, J = 8.8 Hz,
Yield 97%, yellow solid, mp 197.0–199.1 8C. 1H NMR (400 MHz,
2H), 7.47 (d, J = 7.6 Hz, 1H), 7.55 (d, J = 8.4 Hz, 1H), 7.77
(t, J = 7.6 Hz, 1H), 7.86 (d, J = 8.0 Hz, 1H), 8.40 (s, 1H, CH55), 10.51
(s, 1H, NH); 13C NMR (100 MHz, DMSO):
d = 115.4, 116.9, 117.2,
DMSO):
d = 6.96 (t, J = 7.6 Hz, 1H), 7.15 (d, J = 8.0 Hz, 2H), 7.31
(t, J = 7.6 Hz, 2H), 7.98 (d, J = 2.0 Hz, 1H), 8.12 (d, J = 2.0 Hz, 1H),
8.36 (s, 1H, CH55), 10.43 (s, 1H, NH). 13C NMR (100 MHz, DMSO):
119.0, 122.0 (q, J = 270.0 Hz), 124.0 (q, J = 35.2 Hz), 125.4, 125.6,
d
= 113.7, 119.1, 121.0, 121.2, 121.7 (q, J = 33.8 Hz), 121.8
129.6, 129.9, 134.0, 142.9, 147.6, 154.4, 157.8; HRMS (ESI) calcd for
(q, J = 269.9 Hz), 122.0, 127.7, 128.8, 129.5, 132.6, 143.5, 145.8,
C
17H11ClF3N2O2 [M+H]+: m/z = 367.0461, found 367.0454; IR (KBr,
148.5, 156.4; HRMS (ESI) calcd for C17H10Cl2F3N2O2 [M+H]+:
cmꢀ1):
n = 3444 (m), 1694 (s), 1661 (s), 1638 (s), 1611 (s), 1455 (s),
1400 (m), 1250 (w), 1193 (w), 1159 (w), 1122 (w), 1092 (m), 1089
(w), 972 (w), 953 (w), 823 (m), 784 (w), 757 (w), 591 (w).
m/z = 401.0071, found 401.0075; IR (KBr, cmꢀ1):
n
= 3441 (w),
1715 (s), 1603 (s), 1556 (s), 1488 (m), 1456 (m), 1335 (w), 1245 (s),
1225 (s), 1185 (s), 1147 (s), 1100 (s), 1067 (s), 984 (w), 931 (w),
837 (w), 775 (w), 749 (w), 730 (w), 681 (w), 477 (m).
4.4.10. 3-(4-Bromophenylhydrazonotrifluoroethyl)coumarin (3j)
Yield 61%, yellow powder, mp 171.5–172.3 8C. 1H NMR
4.4.5. 3-(Phenylhydrazonotrifluoroethyl)-6,8-(dibromo)coumarin
(3e)
(400 MHz, DMSO): d = 7.12 (d, J = 8.4 Hz, 2H), 7.47 (t, J = 8.8 Hz,
3H), 7.55 (d, J = 8.4 Hz, 1H), 7.77 (t, J = 8.0 Hz, 1H), 7.87 (d,
J = 7.6 Hz, 1H), 8.40 (s, 1H, CH55), 10.51 (s, 1H, NH); 13C NMR
Yield 96%, yellow powder, mp 175.3–178.0 8C. 1H NMR
(400 MHz, CDCl3):
d
= 7.02 (t, J = 7.2 Hz, 1H), 7.17 (d, J = 8.0 Hz,
(100 MHz, DMSO): d = 113.4, 115.9, 116.9, 117.1, 119.0, 122.0 (q,
2H), 7.26–7.32 (m, 2H), 7.70 (d, J = 2.4 Hz, 1H), 7.91 (s, 1H, NH),
7.99 (d, J = 2.0 Hz, 1H), 8.31 (s, 1H, CH55). 13C NMR (100 MHz,
J = 270.0 Hz), 124.1 (q, J = 35.2 Hz), 125.4, 129.9, 132.5, 134.0,
143.3, 147.6, 154.4, 157.8; HRMS (ESI) calcd for C17H11BrF3N2O2
[M+H]+: m/z = 410.9956, found 410.9951; IR (KBr, cmꢀ1):
n = 3460
CDCl3):
d
= 111.5, 114.2, 118.0, 118.4, 120.2, 121.5 (q, J = 271.2 Hz),
121.7 (q, J = 35.2 Hz), 123.0, 129.3, 130.5, 139.0, 142.6, 144.8,
149.9, 156.6; HRMS (ESI) calcd for C17H10Br2F3N2O2 [M+H]+: m/
(m), 1714 (s), 1602 (s), 1484 (w), 1401 (s), 1246 (m), 1182 (m),
1120 (m), 1066 (m), 961 (w), 824 (w), 756 (m), 470 (w).
z = 488.9061, found 488.9084; IR (KBr, cmꢀ1):
n = 3276 (w), 1734
(s), 1572 (w), 1550 (w), 1498 (w), 1442 (w), 1333 (w), 1227 (w),
1180 (m), 1108 (m), 1067 (m), 960 (w), 755 (w), 696 (w), 471 (w).
4.4.11. 3-(3-Nitrophenylhydrazonotrifluoroethyl)coumarin (3k)
Yield 46%, yellow powder, mp 149.5–151.7 8C. 1H NMR
(400 MHz, DMSO):
7.75 (d, J = 6.4 Hz, 2H), 7.85 (d, J = 7.6 Hz, 1H), 7.89 (s, 1H), 8.42 (s,
1H, CH55), 10.75 (s, 1H, NH); 13C NMR (100 MHz, DMSO):
= 107.9,
d = 7.45 (d, J = 7.6 Hz, 1H), 7.54–7.58 (m, 3H),
4.4.6. 3-(Phenylhydrazonotrifluoroethyl)-8-(methoxy)coumarin (3f)
Yield 88%, yellow powder, mp 175.8–178.0 8C. 1H NMR
d
(400 MHz, DMSO):
7.15 (d, J = 8.4 Hz, 2H), 7.30 (t, J = 7.6 Hz, 2H), 7.40 (s, 2H),
7.44–7.46 (m, 1H), 8.35 (s, 1H, CH55), 10.39 (s, 1H, NH); 13C NMR
d
= 3.97 (s, 3H, CH3), 6.94 (t, J = 7.2 Hz, 1H),
116.0, 116.5, 116.7, 118.6, 119.6, 121.5 (q, J = 270.0 Hz), 125.3,
125.7 (q, J = 35.2 Hz), 129.8, 131.1, 133.9, 144.9, 147.6, 148.8,
154.2, 157.5; HRMS (ESI) calcd for C17H11F3N3O4 [M+H]+: m/
z = 378.0702, found 378.0696; IR (KBr, cmꢀ1):
n = 3427 (s), 1693
(100 MHz, DMSO):
d
= 56.5, 113.6, 115.7, 117.4, 119.3, 120.6,
121.8, 122.0 (q, J = 269.8 Hz), 122.8 (q, J = 32.2 Hz), 125.1, 129.5,
143.4, 143.7, 146.7, 147.4, 157.4; HRMS (ESI) calcd for
C18H14F3N2O3 [M+H]+: m/z = 363.0957, found 363.0952; IR (KBr,
(m), 1661 (m), 1613 (s), 1530 (m), 1454 (m), 1400 (m), 1350 (m),
1191 (w), 1125 (w), 1062 (w), 765 (w), 669 (w), 613 (w), 461 (w).
cmꢀ1
)
n
= 3433 (s), 3311 (m), 2974 (w), 1727 (s), 1598 (s), 1472
4.4.12. 3-(3,5-Dichlorophenylhydrazonotrifluoroethyl)coumarin (3l)
Yield 43%, yellow powder, mp 183.4–185.0 8C. 1H NMR
(m), 1350 (m), 1183 (s), 1105 (s), 929 (m), 756 (m), 696 (m), 466 (s).
(400 MHz, DMSO):
d = 7.11 (s, 3H), 7.47 (t, J = 7.6 Hz, 1H), 7.55
4.4.7. 3-(Phenylhydrazonotrifluoroethyl)-8-(ethoxy)coumarin (3g)
Yield 84%, yellow powder, mp 166.3–168.0 8C. 1H NMR
(d, J = 8.0 Hz, 1H), 7.78 (t, J = 8.0 Hz, 1H), 7.86 (d, J = 7.6 Hz, 1H),
8.42 (s, 1H, CH55), 10.61 (s, 1H, NH); 13C NMR (100 MHz, DMSO):
(400 MHz, DMSO):
d
= 1.44 (t, J = 6.8 Hz, 3H), 4.24 (q, J = 6.8 Hz,
d = 112.1, 116.4, 116.8, 118.6, 120.8, 121.4 (q, J = 270.7 Hz), 125.5,
2H), 6.94 (t, J = 7.2 Hz, 1H), 7.16 (d, J = 8.0 Hz, 2H), 7.31 (t, J = 7.6 Hz,
2H), 7.34–7.44 (m, 3H), 8.34 (s, 1H, CH55), 10.39 (s, 1H, NH); 13C
126.2 (q, J = 35.3 Hz), 129.8, 134.1, 135.1, 146.0, 147.8, 154.2,
157.4; HRMS (ESI) calcd for C17H10Cl2F2N2O2 [M+H]+: m/
z = 401.0071, found 401.0070; IR (KBr, cmꢀ1):
n = 3443 (s), 1707
NMR (100 MHz, DMSO):
d
= 14.8, 64.7, 113.6, 116.5, 117.3, 119.4,
120.5, 121.7, 121.9 (q, J = 270.0 Hz), 122.8 (q, J = 35.2 Hz), 125.0,
(m), 1593 (s), 1567 (m), 1454 (w), 1344 (w), 1252 (m), 1189 (s),
1078 (s), 803 (w), 758 (w), 475 (w).
129.4, 143.5, 143.7, 145.9, 147.3, 157.4; HRMS (ESI) calcd for
C
19H15F3N2O3Na [M+Na]+: m/z = 399.0932, found 399.0930; IR
(KBr, cmꢀ1
)
n
= 3282 (m), 2983 (w), 1707 (s), 1601 (s), 1470 (m),
4.4.13. 3-(4-Methoxylphenylhydrazonotrifluoroethyl)coumarin (3m)
Yield 78%, yellow powder, mp 159.0–159.8 8C. 1H NMR
1349 (m), 1278 (m), 1248 (m), 1189 (m), 1151 (m), 1099 (m), 1059
(m), 967 (w), 940 (w), 736 (m), 696 (m), 493 (s).
(400 MHz, DMSO):
d = 3.71 (s, 3H, CH3), 6.90 (d, J = 8.8 Hz, 2H),
7.08 (d, J = 8.8 Hz, 2H), 7.45 (t, J = 8.0 Hz, 1H), 7.53 (d, J = 8.4 Hz,
1H), 7.75 (td, J = 7.6, 1.6 Hz, 1H), 7.85 (dd, J = 7.6, 1.2 Hz, 1H), 8.34
(s, 1H, CH55), 10.26 (s, 1H, NH); 13C NMR (100 MHz, DMSO):
4.4.8. 3-(4-Fluorophenylhydrazonotrifluoroethyl)coumarin (3h)
Yield 73%, yellow powder, mp 180.3–182.2 8C. 1H NMR
(400 MHz, DMSO):
d
= 7.15 (d, J = 6.8 Hz, 4H), 7.46 (t, J = 7.2 Hz,
d = 55.4, 114.7, 114.8, 116.5, 117.3, 118.8, 121.3 (q, J = 35.2 Hz),
1H), 7.55 (d, J = 8.0 Hz, 1H), 7.77 (td, J = 7.6, 1.6 Hz, 1H), 7.86 (dd,
J = 7.8, 1.2 Hz, 1H), 8.37 (s, 1H, CH55), 10.43 (s, 1H, NH); 13C NMR
122.1 (q, J = 269.6 Hz), 125.0, 129.5, 133.5, 137.4, 147.0, 154.0,
154.6, 157.6; HRMS (ESI) calcd for C18H13F3N2O3Na [M+Na]+: m/
z = 385.0776, found 385.0778; IR (KBr, cmꢀ1):
n = 3455 (m), 3125
(100 MHz, DMSO):
d
= 115.0 (d, J = 7.8 Hz), 116.1, 116.3, 116.7,