782
P. Kumari and S.M.S. Chauhan
Vol 45
residue was chromatographed on neutral alumina. The elution of
column with chloroform/pertroleum ether (varying ratio) gave
the corresponding corrole as a green-violet solid. The used
Amberlyst 15 was washed thoroughly with methanol:
chloroform mixture (1:1, v/v) followed by refluxing for 30 min.
Amberlyst 15 was reactivated and reused for catalyzing other
condensation reactions.
5,10,15-Tris(2,6-dichlorophenyl)corrole (2g) [33]. UV-vis
(CH2Cl2): λmax (log ε) = 409 (4.78), 423 (4.69), 566 (3.97), 604
(3.74), 632 nm (3.17). IR (KBr): 3391, 1557, 1428, 1279, 1253,
1189, 1031, 957, 797, 777, 713 cm-1. 1H NMR (CDCl3): δ = 8.91
(d, J = 4 Hz, 2H), 8.49 (d, J = 4.7 Hz, 2H), 8.35 (m, 4H), 7.72
(m, 6H), 7.33(m, 3H), -1.70 (s, 3H). MS (ESI): m/z = Calculated
(C37H20Cl6N4), 733.30; Observed (M + H+), 734.34. Anal. Calc
for C37H20Cl6N4: C, 60.60; H, 2.75; N, 7.64. Found: C, 60.45; H,
2.67; N, 7.58.
5,10,15-Tris(2,3,4,5,6-pentafluorophenyl)corrole (2h) [33].
UV-vis (CH2Cl2): λmax (log ε) = 408 (4.61), 563 (3.89), 604 nm
(3.67). IR (KBr): 3417, 1651, 1521, 1495, 1436, 1380, 1274,
1056, 986, 928, 795, 766 cm-1. 1H NMR (CDCl3): δ = 9.10 (d, J
= 4.4 Hz, 2H), 8.75 (d, J = 4.4 Hz, 2H), 8.57 (d, J = 4.4 Hz, 4H)
-2.25 (s, 3H).MS (ESI): m/z = Calculated (C37H11F15N4), 796.48;
Observed (M + H+), 797.50. Anal. Calc for C37H11F15N4: C,
55.79; H, 1.39; N, 7.03. Found: C, 55.66; H, 1.42; N, 7.12.
5,10,15-Tris(2-naphthyl)corrole (2i). UV-vis (CH2Cl2): λmax
(log ε) = 424 (5.06), 584 (4.29), 623 (4.26), 657 nm (4.22). IR
(Film): 3391, 3198, 3118, 3054, 1693, 1596, 1502, 1357, 1272,
1051, 970, 946, 901, 802, 746 cm-1. 1H NMR (CDCl3): δ = 8.90-
8.80 (m, 4H), 8.85 (m, 4H), 8.54 (m, 4H), 8.16 (m, 8H), 7.90-
7.71 (m, 16H), -2.10 (s, 3H). MS (ESI): m/z = Calculated
(C44H32N4), 676.81; Observed (M + H+), 677.81. Anal. Calc for
C44H32N4: C, 86.96; H, 4.77; N, 8.28. Found: C, 86.75; H, 4.80;
N, 8.34.
Selected characterization data 5,10,15-triphenylcorrole
(2a) [11]. UV-vis (CH2Cl2): λmax (log ε) = 414 (4.73), 575
(3.95), 615 (3.88), 646 nm (3.79). IR (KBr): 3421, 1685, 1595,
1577, 1550, 1491, 1377, 1330, 1269, 1222, 1039, 1010, 960,
1
794, 752, 699 cm-1. H NMR (CDCl3): δ = 8.83 (br s, 4H), 8.50
(br s, 4H), 8.33 (d, J = 5 Hz, 4H), 8.15 (d, J = 5 Hz, 2H), 7.85-
7.70 (m, 9H), -2.90 (s, 3H). MS (ESI): m/z = Calculated
(C37H26N4), 526.63; Observed (M + H+), 527.59. Anal. Calc for
C37H26N4: C, 84.38; H, 4.98; N, 10.64. Found: C, 84.26; H, 4.94;
N, 10.59.
5,10,15-Tris(4-nitrophenyl)corrole (2b) [11]. UV-vis
(CHCl3): λmax (log ε) = 426 (4.22), 592 nm (3.64). IR (KBr):
3427, 1654, 1594, 1517, 1343, 1059, 1028, 846, 792, 719 cm-1.
1H NMR (CDCl3): δ = 9.11 (d, J = 4 Hz, 2H), 8.88 (d, J = 4 Hz,
2H), 8.82 (s, 1H), 8.71 (d, J = 8 Hz, 4H), 8.65 (m, 2H), 8.57-
8.54 (m, 6H), 8.37 (t, J = 9 Hz, 3H), -2.82 (s, 3H). MS (ESI):
m/z = Calculated (C37H23N7O6), 661.62; Observed (M + H+),
662.34. Anal. Calc for C37H23N7O6: C, 67.17; H, 3.50; N, 14.82.
Found: C, 67.12; H, 3.42; N, 14.52.
5,10,15-Tris(4-chlorophenyl)corrole (2c). UV-vis (CH2Cl2):
λmax (log ε) = 416 (4.65), 577 (3.77), 616 (3.68), 648 nm (3.61).
IR (KBr): 3318, 1586, 1487, 1395, 1222, 1174, 1091, 1012, 963,
5,10,15-Tris(4-methoxyphenyl)corrole (2j) [9]. UV-vis
(CH2Cl2): λmax (log ε) = 419 (4.69), 523 (3.77), 566 (3.88), 621
(3.84), 652 nm (3.78). IR (KBr): 3401, 1676, 1601, 1509, 1459,
1247, 1173, 1031, 786 cm-1. MS (ESI): m/z = Calculated
(C40H32N4O3), 616.71; Observed (M + H+), 617.82. Anal. Calc
for C40H32N4O3: C, 77.90; H, 5.23; N, 9.08. Found: C, 78.21; H,
5.32; N, 8.92.
Amberlyst 15 catalyzed condensation of 4-chlorobenz-
aldehyde (1c) and pyrrole under different dilution condition.
The 4-chlorobenzaldehyde (1c) (2 mmol) and pyrrole (4 mmol)
were dissolved in dichloromethane (20, 100 or 300 equiv vs. 1c)
at room temperature and activated Amberlyst 15 (200 mg) was
added. The above reaction mixture was stirred for 1 hr at room
temperature. Resin was filtered off after diluting the reaction
mixture with 10 mL dichloromethane and washed with
dichloromethane (3 × 5 mL). The dichloromethane solutions was
collected and a solution of DDQ (2 mmol) in tetrahydrofuran (5
mL) was added with stirring. The reaction mixture was stirred
for additional 15 min at room temperature. The solvent was
removed under reduced pressure and the residue was
chromatographed on neutral alumina. The elution of column
with chloroform/petroleum ether (20: 80, v/v) gave 5,10,15-
1
845, 796, 722 cm-1. H NMR (CDCl3): δ = 8.97 (br s, 2H), 8.83
(br s, 2H), 8.54 (m, 4H), 8.26 (m, 4H), 8.11 (br s, 2H), 7.75 (m,
6H), -2.82 (s, 3H). MS (ESI): m/z = Calculated (C37H23Cl3N4),
629.97; Observed (M + H+), 630.97. Anal. Calc for C37H23Cl3N4:
C, 70.54; H, 3.68; N, 8.89. Found: C, 70.42; H, 3.54; N, 8.80.
5,10,15-Tris(4-carbomethoxyphenyl)corrole (2d) [9]. UV-
vis (CH2Cl2): λmax (log ε) = 420 (5.09), 515 (3.93), 584 (4.14),
619 (4.00), 652 nm (3.89). IR (KBr): 3435, 1723, 1654, 1607,
1459, 1437, 1278, 1113, 1074, 794, 794, 767, 733 cm-1. 1H NMR
(CDCl3): δ = 9.01 (br s, 2H), 8.87 (br s, 2H), 8.82 (s, 1H), 8.58
(m, 4H), 8.43 (m, 8H), 8.29 (m, 3H), 4.10 (s, 9H). Anal. Calc for
C43H32N4O6: C, 73.70; H, 4.60; N, 8.00. Found: C, 73.60; H,
4.53; N, 7.92.
5,10,15-Tris(3-bromophenyl)corrole (2e) [11]. UV-vis
(CH2Cl2): λmax (log ε) = 417 (4.78), 515 (3.47), 578 (3.85), 614
(3.69), 648 nm (3.62). IR (KBr): 3408, 1653, 1588, 1557, 1468,
1404, 1336, 1291, 1057, 1026, 782, 691 cm-1. 1H NMR (CDCl3):
δ = 9.04, 8.88, 8.62, 8.56 (each d, J = 4 Hz, 2H), 8.51 (s, 2H),
8.35 (d, J = 8 Hz, 2H), 8.28 (d, J = 8 Hz, 2H), 8.15 (m, 4H), 7.87
(m, 2H), -2.82 (s, 3H). MS (ESI): m/z
= Calculated
(C37H23Br3N4), 763.32; Observed (M + H+), 764.03. Anal. Calc
for C37H23Br3N4: C, 58.22; H, 3.04; N, 7.34. Found: C, 58.05; H,
3.00; N, 7.50.
tris(4-chlorophenyl)corrole (2c) and 5,10,15,20-tetrakis(4-
chlorophenyl)porphyrin (6c) in different yields.
5,10,15,20-Tetrakis(4-chlorophenyl)porphyrin (6c) [20].
UV-vis (CH2Cl2): λmax (log ε) = 418 (5.55), 515 (4.14), 549
(3.74), 590 (3.58), 648 nm (3.56). IR (KBr): 3312, 1714, 1594,
1557, 1488, 1236, 1090, 1015, 966, 798 cm-1. 1H NMR (CDCl3):
δ = 8.83 (s, 8H, β-pyrrolic-H), 8.14 (d, J= 8.2 Hz, 8H, o-Ph),
7.76 (d, J= 8.2 Hz, 8H, m-Ph), -2.16 (s, 2H, internal NH). MS
(ESI): m/z = Calculated (C44H26Cl4N4), 752.52; Observed (M +
H+), 753.44.
5,10,15-Tris(4-fluorophenyl)corrole (2f) [32]. UV-vis
(CH2Cl2): λmax (log ε) = 415 (4.55), 573 (3.58), 613 (3.49), 646
nm (3.43). IR (KBr): 3421, 1656, 1599, 1505, 1305, 1227, 1157,
1
1055, 1028, 805, 728 cm-1. H NMR (CDCl3): δ = 8. 96 (d, J =
4.1Hz, 2H), 8.82 (d, J = 4.6 Hz, 2H), 8.54 (d, J = 4.1 Hz, 2H),
8.51 (d, J = 4.7 Hz, 2H), 8.30 (m, 4H), 8.22 (d, J = 2.8 Hz, 2H),
7.44 (m, 6H), -2.81 (s, 3H). MS (ESI): m/z = Calculated
(C37H23F3N4), 580.61; Observed (M + H+), 581.43. Anal. Calc
for C37H23F3N4: C, 76.54; H, 3.99; N, 9.65. Found: C, 76.34; H,
4.22; N, 9.82.
Acknowledgement. The authors are grateful to the Council
of Scientific and Industrial Research (CSIR), New Delhi, India
for financial assistance.