January 2012
An Efficient Synthetic Approach to Novel Nickel(II) 2-Benzazolo-
5,10,15,20-tetraphenylporphyrins
91
1598, 1441, 1351, 1272, 1073, 1008, 796, 750, 700 cmꢀ1;1H-
NMR (CDCl3): d 7.08–7.13 (m, 4H, ArH), 7.55–7.69 (m, 10H,
meso-ArH), 7.75–7.81 (m, 3H, meso-ArH), 7.91–7.98 (m, 7H,
meso-ArH), 8.14 (s, 1H, NH), 8.39 (d, 1H, b-pyrrolic H, J ¼
4.98 Hz), 8.61 (d, 1H, b-pyrrolic H, J ¼ 4.98 Hz), 8.67–8.74
(m, 4H, b-pyrrolic H), 9.21 (s, 1H, b-pyrrolic H) ppm; HRMS:
mass calculated for C51H32N6Ni (M)þ: 786.2043; found:
786.4633. Anal. Calcd. for C51H32N6Niꢂ0.5H2O: C, 76.90; H,
4.18; N, 10.55. Found: C, 76.64; H, 4.53; N, 10.33.
(586800), 538 (51100), 574 (27700) nm; IR (film): 1597,
1460, 1442, 1351, 1260, 1215, 1180, 1075, 1009, 850, 797,
1
754, 701 cmꢀ1; H-NMR (CDCl3): d 2.49 (s, 3H, CH3), 6.90–
7.06 (m, 2H, ArH), 7.15–7.20 (m, 2H, meso-ArH), 7.47 (s, 1H,
ArH), 7.66–7.68 (m, 10H, meso-ArH), 7.88 (d, 2H, meso-ArH,
J ¼ 7.2 Hz), 7.99–8.01 (m, 6H, meso-ArH), 8.50 (d, 1H, b-
pyrrolic H, J ¼ 5.01 Hz), 8.64 (d, 1H, b-pyrrolic H, J ¼ 4.8
Hz), 8.67–8.76 (m, 4H, b-pyrrolic H), 9.20 (s, 1H, b-pyrrolic
H) ppm; HRMS: mass calculated for C52H34N5NiO (M þ
H)þ: 802.2117; found: 802.2360. Anal. Calcd. for
C52H33N5NiOꢂH2O: C, 76.11; H, 4.30; N, 8.53. Found: C,
76.54; H, 4.66; N, 8.88.
Nickel(II) 2-(6-chloro-1H-benzimidazol-2-yl)-5,10,15,20-tet-
)
raphenylporphyrin (3b). Yield: 90%; UV: kmax (e, Mꢀ1 cmꢀ1
425 (608600), 538 (53800), 569 (21000) nm; IR (film): 3370,
1594, 1439, 1405, 1349, 1258, 1302, 1214, 1070, 1008, 902,
847, 795, 752, 700 cmꢀ1; H-NMR (CDCl3): d 7.12–7.20 (m,
Nickel(II)
2-(benzthiazol-2-yl)-5,10,15,20-tetraphenylpor-
1
phyrin (3g). Yield: 95%; UV: kmax (e, Mꢀ1 cmꢀ1) 422
(420800), 539 (22700), 572 (6400) nm; IR (film): 1598, 1441,
1351, 1261, 1214, 1178, 1074, 1009, 968, 899, 799, 753, 700
3H, ArH), 7.64–7.76 (m, 12H, meso-ArH), 7.855 (d, J ¼ 5.4
Hz, 2H, meso-ArH), 7.94–8.04 (m, 6H, meso-ArH), 8.09 (s,
1H, NH), 8.43 (d, 1H, b-pyrrolic H, J ¼ 4.8 Hz), 8.64 (d, 1H,
b-pyrrolic H, J ¼ 4.5 Hz), 8.70–8.74 (m, 4H, b-pyrrolic H),
9.22 (s, 1H, b-pyrrolic H) ppm; HRMS: mass calculated for
C51H32ClN6Ni (M þ H)þ: 821.1660; found: 821.4358. Anal.
Calcd. for C51H31ClN6Ni: C, 74.52; H, 3.80; N, 10.22. Found:
C, 74.39; H, 3.65; N, 9.89.
cmꢀ1 1H-NMR (CDCl3): d 6.99–7.04 (m, 2H, ArH), 7.25–
;
7.40 (m, 2H, ArH), 7.59–7.62 (m, 12H, meso-ArH), 7.92–7.94
(m, 8H, meso-ArH), 8.45 (d, 1H, b-pyrrolic H, J ¼ 4.9 Hz),
8.56 (d, 1H, b-pyrrolic H, J ¼ 4.9 Hz), 8.61–8.67 (m, 4H, b-
pyrrolic H), 8.92 (s, 1H, b-pyrrolic H) ppm; HRMS: mass cal-
culated for C51H31N5NiS (M)þ: 803.1654; found: 803.1700.
Anal. Calcd. for C51H31N5NiSꢂ2H2O: C, 72.87; H, 4.20; N,
8.33. Found: C, 72.56; H, 4.36; N, 8.53.
Nickel(II) 2-(1H-imidazo[4,5-b]pyridin-2-yl)-5,10,15,20-tet-
raphenylporphyrin (3h). Yield: 82%; UV: kmax (e, Mꢀ1 cmꢀ1
425 (773100), 538 (64700), 569 (34000) nm; IR (film): 3367,
3400, 1598, 1414, 1350, 1263, 1072, 1008, 794, 776, 699
;
cmꢀ1 1H-NMR (CDCl3): d 6.98–7.05 (m, 3H, ArH), 7.57–
Nickel(II) 2-(6-benzoyl-1H-benzimidazol-2-yl)-5,10,15,20-
tetraphenylporphyrin (3c). Yield: 88%; UV: kmax (e, Mꢀ1
cmꢀ1) 425 (456500), 538 (44300), 570 (19300) nm; IR (film):
3360, 1653, 1617, 1598, 1441, 1350, 1308, 1238, 1073, 1008,
)
797, 753, 701 cmꢀ1
;
1H-NMR (CDCl3): d 7.02–7.13 (m, 5H,
ArH), 7.46–7.49 (m, 3H, ArH), 7.61–7.72 (m, 12H, meso-
ArH), 7.79–7.86 (m, 2H, meso-ArH), 7.90–7.93 (m, 6H, meso-
ArH), 8.21–8.24 (m, 1H, b-pyrrolic H), 8.39 (m, 1H, b-pyr-
rolic H), 8.52 (s, 1H, NH), 8.59–8.71 (m, 4H, b-pyrrolic H),
9.20 (s, 1H, b-pyrrolic H) ppm; HRMS: mass calculated for
C58H36N6NiO (M)þ: 890.2304; found: 890.2327. Anal. Calcd.
for C58H36N6NiOꢂH2O: C, 76.58; H, 4.21; N, 9.24. Found: C,
76.55; H, 4.42; N, 9.53.
7.69 (m, 12H, meso-ArH), 8.02 (s, 8H, meso-ArH), 8.45 (s,
1H, b-pyrrolic H), 8.65 (s, 1H, b-pyrrolic H), 8.72–8.78 (m,
4H, b-pyrrolic H), 9.2370 (s, 1H, b-pyrrolic H), 10.25 (s, 1H,
NH) ppm; HRMS: mass calculated for C50H31N7Ni (M)þ:
787.1994; found: 787.1434. Anal. Calcd. for C50H31N7Ni: C,
76.16; H, 3.96; N, 12.43. Found: C, 76.26; H, 4.32; N, 11.88.
Nickel(II) 2-(1H-imidazo[4,5-b]phenazin-2-yl)-5,10,15,20-
tetraphenylporphyrin (4). Yield: 80%; UV: kmax (e, Mꢀ1
cmꢀ1) 430 (346200), 540 (51600), 578 (29700) nm; IR (film):
3400, 1598, 1420, 1351, 1305, 1218, 1160, 1073, 1009, 796,
Nickel(II) 2-(6-cyano-1H-benzimidazol-2-yl)-5,10,15,20-tet-
raphenylporphyrin (3d). Yield: 75%; UV: kmax (e, Mꢀ1 cmꢀ1
)
425 (589500), 538 (70100), 569 (37000) nm; IR (film): 3400,
2224, 1599, 1441, 1350, 1306, 1073, 1007, 797, 753, 701
cmꢀ1
;
1H-NMR (CDCl3): d 7.36–7.39 (m, 2H, ArH), 7.57–
752, 701 cmꢀ1; H-NMR (CDCl3): d 7.05–7.10 (t, 2H, ArH, J
1
7.68 (m, 13H, meso-ArH and ArH), 7.91–7.97 (m, 8H, meso-
ArH), 8.08 (s, 1H, NH), 8.40 (d, 1H, b-pyrrolic H, J ¼ 5.1
Hz), 8.61 (d, 1H, b-pyrrolic H, J ¼ 4.8 Hz), 8.67–8.73 (m,
4H, b-pyrrolic H), 9.20 (s, 1H, b-pyrrolic H) ppm; HRMS:
mass calculated for C52H32N7Ni (M þ H)þ: 812.2008; found:
812.9039. Anal. Calcd. for C52H31N7Ni: C, 76.86; H, 3.85; N,
12.07. Found: C, 77.21; H, 3.53; N, 11.81.
¼ 7.30 Hz), 7.49–7.61 (m, 12H, meso-ArH), 7.69–7.72 (m, 2H,
ArH), 7.80–7.90 (m, 8H, meso-ArH), 8.10 (s, 1H, ArH), 8.18 (s,
1H, ArH), 8.32 (d, 1H, b-pyrrolic H, J ¼ 5.1 Hz), 8.37 (s, 1H,
NH), 8.53–8.66 (m, 5H, b-pyrrolic H), 9.24 (s, 1H, b-pyrrolic
H) ppm; HRMS: mass calculated for C57H36N8Ni (M þ 2H)þ:
890.2416; found: 890.3008. Anal. Calcd. for C57H34N8Ni: C,
76.95; H, 3.85; N, 12.60. Found: C, 76.74; H, 3.65; N, 11.45.
Nickel(II) 2-(1H-imidazo[4,5-b]anthraquinone-2-yl)-5,10,15,
20-tetraphenylporphyrin (5). Yield: 89%; UV: kmax (e, Mꢀ1
cmꢀ1) 420 (369500), 540 (47800), 576 (24200) nm; IR (film):
3384, 1664, 1647, 1589, 1491, 1440, 1350, 1325, 1291, 1160,
Nickel(II)
2-(benzoxazol-2-yl)-5,10,15,20-tetraphenylpor-
phyrin (3e). Yield: 92%; UV: kmax (e, Mꢀ1 cmꢀ1) 425
(435400), 538 (40900), 574 (23700) nm; IR (film): 1598,
1453, 1351, 1242, 1076, 1008, 850, 796, 752, 700 cmꢀ1 1H-
;
NMR (CDCl3): d 6.99 (m, 1H, ArH), 7.14–7.16 (m, 3H, ArH),
7.67–7.68 (m, 12H, meso-ArH), 7.89 (d, 2H, meso-ArH, J ¼
6.99 Hz), 7.99 (s, 6H, meso-ArH), 8.55 (d, 1H, b-pyrrolic H, J
¼ 4.89 Hz), 8.65 (d, 1H, b-pyrrolic H, J ¼ 4.89 Hz), 8.68–
8.75 (m, 4H, b-pyrrolic H), 9.22 (s, 1H, b-pyrrolic H) ppm;
HRMS: mass calculated for C51H31N5NiO (M)þ: 787.1882;
found:787.0692. Anal. Calcd. for C51H31N5NiO: C, 77.68; H,
3.96; N, 8.88. Found: C, 77.95; H, 4.31; N, 9.20.
1074, 1007, 798, 753, 702 cmꢀ1 1H-NMR (CDCl3): d 6.58–
;
6.62 (m, 1H, ArH), 6.85–6.90 (m, 2H, ArH), 7.36 (s, 2H,
ArH), 7.45 (s, 1H, ArH), 7.67 (s, 8H, meso-ArH), 7.73 (s, 4H,
meso-ArH), 7.89–8.00 (m, 6H, meso-ArH), 8.21 (s, 2H, meso-
ArH), 8.33 (d, 1H, b-pyrrolic H, J ¼ 4.76 Hz,), 8.52 (d, 1H,
b-pyrrolic H, J ¼ 4.69 Hz), 8.80–8.67 (m, 4H, b-pyrrolic H),
9.12 (s, 1H, b-pyrrolic H), 10.04 (s, 1H, NH) ppm; HRMS:
mass calculated for C59H34N6NiO2 (M)þ: 916.2097; found:
916.2141. Anal. Calcd. for C59H34N6NiO2ꢂH2O: C, 75.57; H,
4.08; N, 8.96. Found: C, 75.42; H, 3.88; N, 8.57.
Nickel(II) 2-(6-methylbenzoxazol-2-yl)-5,10,15,20-tetraphe-
nylporphyrin (3f). Yield: 80%; UV: kmax (e, Mꢀ1 cmꢀ1) 425
Journal of Heterocyclic Chemistry
DOI 10.1002/jhet