5
1292, 1197, 1130, 1023, 986, 810 cm-1; Anal. Calcd. for
C18H14N2O2(%): C 74.47, H 4.86, N 9.65; Found: C 74.21, H
4.86, N 9.67; EI-MS: calcd for C18H14N2O2: 290.11; Found:
289.1(M-1).
H 1.92, N 6.65; EI-MS:calcd for C16H8Br2N2O2: 420.05;
Found: 419/417(M-1,isotope).
ACCEPTED MANUSCRIPT
4.2.8 (2'Z)-4,4'-Dichloroindirubin (14)
Indirubin (14) was prepared by the above procedure and was
purified by recrystallization from 95% C2H5OH to afford 1.31 g
(79.4%) of 14 as purplish red solid. m.p.>300 oC; UV:
4.2.4 (2'Z)-5,5'-Dichloroindirubin (10)
Indirubin (10) was prepared by the above procedure and was
purified by recrystallization from 95% C2H5oOH to afford 1.38 g
(83.6%) of 10 as purplish solid. m.p.>300 C; UV: λ(CH3CN):
296(max), 549nm; 1H NMR (800 MHz, DMSO-d6) δ(ppm):
11.11 (s, 2H), 8.75 (s, 1H), 7.65 (s, 1H), 7.61 (d, J = 7.8 Hz, 1H),
7.44 (d, J = 8.3 Hz, 1H), 7.27 (d, J = 7.8 Hz, 1H), 6.88 (d, J = 8.0
Hz, 1H); 1H NMR is in accordance with the literature37; 13C NMR
(201 MHz, DMSO-d6) δ(ppm): 187.97 (s), 170.91 (s), 151.44 (s),
139.09 (s), 136.55 (s), 128.62 (s), 125.52 (s), 124.87 (s), 123.88
(s), 123.73 (s), 123.08 (s), 120.30 (s), 115.40 (s), 110.96 (s),
106.29 (s); IR: 3414, 3160, 1678, 1624, 1594, 1486, 1400, 1277,
1256, 1218, 1192, 1149, 1016, 954, 879, 830cm-1; Anal. Calcd.
for C16H8Cl2N2O2(%): C 58.03, H 2.44, N 8.46; Found: C 58.15,
H 2.43, N 8.44; EI-MS:calcd for C16H8Cl2N2O2: 330.00; Found:
329.0(M-1).
1
λ(CH3CN): 290(max), 552nm; H NMR (600 MHz, DMSO-d6)δ
(ppm): 11.18 (s, 1H), 11.05 (s, 1H), 8.72 (dd, J = 13.7, 7.5 Hz,
1H), 7.58 – 7.47 (m, 1H), 7.39 (t, J = 5.7 Hz, 1H), 7.06 (d, J = 7.9
Hz, 1H), 7.01 (t, J = 5.5 Hz, 1H), 6.90 (d, J = 4.4 Hz, 1H); IR:
3340, 3327, 3142, 1671, 1613, 1585, 1475, 1400, 1257, 1214,
1110, 1068, 1020, 846cm-1; Anal. Calcd. for C16H8Cl2N2O2(%): C
58.03, H 2.44, N 8.46; Found: C 58.19, H 2.44, N 8.42; EI-MS:
calcd for C16H8Cl2N2O2: 330.00; Found: 329.0(M-1).
4.2.9 (2'Z)-5,5'-Ditrifluoromethoxyindirubin (15)
Indirubin (15) was prepared by the above procedure and was
purified by recrystallization from 95% C2H5OH to afford 1.78 g
(82.8%) of 15 as purplish red solid. m.p.>300 oC; UV:
1
λ(CH3CN): 292(max), 542nm; H NMR (800 MHz, DMSO-d6)
δ(ppm): 11.26 (s, 1H), 11.10 (s, 1H), 8.76 (s, 1H), 7.66 (s, 1H),
7.63 (d, J = 10.2 Hz, 1H), 7.53 (d, J = 8.7 Hz, 1H), 7.27 (d, J =
10.0 Hz, 1H), 6.98 (d, J = 8.4 Hz, 1H); 13C NMR (201 MHz,
DMSO-d6) δ(ppm): 187.97, 170.58, 151.22, 142.62, 139.83,
139.40, 130.38, 130.38, 122.17, 120.92, 120.74, 119.52, 117.36,
117.29, 115.00, 110.22, 109.20, 106.31; IR: 3414, 3160, 1678,
1624, 1594, 1487, 1400, 1277, 1256, 1219, 1149, 1015, 879,
830cm-1; Anal. Calcd. for C18H8F6N2O4(%): C 50.25, H 1.87, N
6.51; Found: C 50.39, H 1.87, N 6.49; EI-MS:calcd for
C18H8F6N2O4: 430.04; Found: 429.0(M-1).
4.2.5 (2'Z)-7,7'-Dichloroindirubin (11)
Indirubin (11) was prepared by the above procedure and was
purified by recrystallization from 95% C2H5OH to afford 1.26 g
(76.4%) of 11 as purplish red solid. m.p.>300 oC; UV:
1
λ(CH3CN): 290(max), 549nm; H NMR(600 MHz, DMSO-d6)
δ(ppm): 11.50 (s, 1H), 10.74 (s, 1H), 8.65 (dd, J = 7.8, 0.7 Hz,
1H), 7.78 (dd, J = 7.9, 0.7 Hz, 1H), 7.72 (dd, J = 7.5, 0.8 Hz, 1H),
7.38 (dd, J = 8.1, 0.6 Hz, 1H), 7.12 (dt, J = 12.9, 7.8 Hz, 2H); IR:
3414, 3127, 1682, 1619, 1593, 1482, 1401, 1297, 1208, 1166,
1136, 1016, 852, 750cm-1; Anal. Calcd. for C16H8Cl2N2O2(%): C
58.03, H 2.44, N 8.46; Found: C 58.18, H 2.43, N 8.43; EI-
MS:calcd for C16H8Cl2N2O2: 330.00; Found: 329.0(M-1).
4.2.10 (2'Z)-7,7'-Ditrifluoromethyindirubin (16)
Indirubin (16) was prepared by the above procedure and was
purified by recrystallization from 95% C2H5OH to afford 1.76 g
(88.4%) of 16 as purplish red solid. m.p.>300 oC; UV:
4.2.6 (2'Z)-5,5'-Dibromoindirubin (12)
1
Indirubin (12) was prepared by the above procedure and was
λ(CH3CN): 309(max), 564nm; H NMR (800 MHz, DMSO-d6)
purified by recrystallization from 95% C2H5OH to afford 1.68 g
(80.0%) of 12 as purplish solid. m.p.>300 C; UV: λ(CH3CN):
δ(ppm): 11.59 (s, 1H), 11.11 (s, 1H), 8.96 (d, J = 7.7 Hz, 1H),
8.03 (d, J = 7.4 Hz, 1H), 7.97 (d, J = 7.7 Hz, 1H), 7.60 (d, J = 7.9
Hz, 1H), 7.28 (q, J = 8.0 Hz, 2H); IR: 3419, 3158, 1681, 1617,
1596, 1494, 1440, 1402, 1332, 1307, 1178, 1132, 1110, 1055,
1019, 763cm-1; Anal. Calcd. for C18H8F6N2O2(%): C 54.29, H
2.02, N 7.03; Found: C 54.18, H 2.02, N 7.05; EI-MS:calcd for
C18H8F6N2O2: 398.05; Found: 397.0(M-1).
o
298(max), 549nm; 1H NMR (800 MHz, DMSO-d6) δ(ppm):
11.17 (s, 1H), 11.02 (s, 1H), 8.89 (s, 1H), 7.77 (s, 1H), 7.73 (d, J
= 7.6 Hz, 1H), 7.40 (dd, J = 13.4, 8.2 Hz, 2H), 6.85 (d, J = 7.2
Hz, 1H); 1H NMR is in accordance with the literature38; 13C NMR
(201 MHz, DMSO-d6) δ(ppm): 187.56 , 170.36 , 151.41 , 140.03
, 139.26 , 138.76 , 131.50 , 126.76 , 126.64 , 123.32 , 120.75 ,
115.79 , 113.20 , 112.96 , 111.39, 105.82; IR: 3487, 3100, 1668,
1611, 1462, 1270, 1206, 1121, 1014, 820cm-1; Anal. Calcd. for
C16H8Br2N2O2(%): C 45.75, H 1.92, N 6.67; Found: C 45.82, H
1.92, N 6.65; EI-MS:calcd for C16H8Br2N2O2: 420.05; Found:
419/417(M-1,isotope).
4.2.11 5,5'-Dimethoxyisoindigo (17)
Compound 17 was prepared by the above procedure and the
crude product was chromatographed over silica gel
(CH2Cl2:CH3OH=100:1) to afford 1.07 g (63.3%) of 17 as
o
purplish solid. m.p.>300 C; UV: λ(CH3CN): 303(max), 577nm;
1H NMR (600 MHz, DMSO-d6) δ (ppm): 10.86 (s, 1H), 10.68 (s,
1H), 8.49 (d, J = 2.5 Hz, 1H), 7.36 (d, J = 8.7 Hz, 1H), 7.23 –
7.17 (m, 2H), 6.86 (dd, J = 8.4, 2.6 Hz, 1H), 6.80 (d, J = 8.4 Hz,
1H), 3.78 (d, J = 4.1 Hz, 6H); 13C NMR (201 MHz, DMSO-d6)
δ(ppm): 185.13, 160.02, 155.78, 145.13, 125.34, 118.57 , 113.69,
109.25 , 56.26; IR: 3323, 3154, 2980, 2829, 1663, 1625, 1597,
1494, 1401, 1319, 1285, 1197, 1156, 1015, 889, 823cm-1; Anal.
Calcd. for C18H14N2O4(%): C 67.08, H 4.38, N 8.69; Found: C
67.28, H 4.37, N 8.72; EI-MS:calcd for C18H14N2O4: 322.31;
Found: 321.1(M-1).
4.2.7 (2'Z)-6,6'-Dibromoindirubin (13)
Indirubin (13) was prepared by the above procedure and was
purified by recrystallization from 95% C2H5oOH to afford 1.71 g
(81.4%) of 13 as purplish solid. m.p.>300 C; UV: λ(CH3CN):
297(max), 548nm; 1H NMR(800 MHz, DMSO-d6) δ(ppm):
11.19 (s, 1H), 11.03 (s, 1H), 8.91 (d, J = 1.9 Hz, 1H), 7.78 (d, J =
1.8 Hz, 1H), 7.74 (dd, J = 8.5, 1.9 Hz, 1H), 7.42 (dd, J = 8.2, 1.9
1
Hz, 1H), 7.40 (d, J = 8.5 Hz, 1H), 6.86 (d, J = 8.2 Hz, 1H); H
NMR is in accordance with the literature39; 13C NMR (201 MHz,
DMSO-d6) δ(ppm): 187.60, 170.37, 151.43, 140.04, 139.29,
138.79, 131.51, 126.76, 126.67, 123.34, 120.77, 115.81, 113.21,
112.96, 111.41, 105.81; IR: 3482, 3146, 1673, 1611, 1588, 1444,
1406, 1286, 1212, 1109, 1053, 1010, 963, 822cm-1; Anal. Calcd.
for C16H8Br2N2O2(%): C 45.75, H 1.92, N 6.67; Found: C 45.86,
4.2.12 (2'Z)-5,5'- Diethylindirubin (18)
Indirubin (18) was prepared by the above procedure and was
purified by recrystallization from 95% C2H5OH to afford 1.33 g
(77.3%) of 18 as purplish red solid. m.p.>300 oC; UV: