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M. Yaseen, M. Ali, M. NajeebUllah, M. Ali Munawar, and I. Khokhar
Vol 46
subjected to microwave irradiation according to solventless
heating with controlled temperature method (i) (Table 1). After
cooling, the reaction mixture was applied onto silica column
and eluted with chloroform: n-hexane (1:2). The fast moving
band was collected and the solvent was evaporated to get Por-
phyrin [2] (20%). mp > 350ꢀC; Anal. Calcd. for C76H94N4: C,
85.82; H, 8.90; N, 5.20. Found: C, 85.66; H, 8.87; N, 5.23.
IR(KBr):mmax 3320 (NAH), 3060, 2960, 2900, 2860, 1600,
1470, 1420 cmꢁ1; UV(CHCl3) kmax 420, 520, 555, 590, 645
nm; 1H NMR (CDCl3): d ꢁ2.67 (bs, 2NH), 1.51 (s, 8t-Bu),
7.74 (t, J ¼ 1.7 Hz, 4p-PhH), 8.07 (d, J ¼ 1.7 Hz, 8o-PhH),
8.87 (s, b-pyrrolic H 2, 3, 7, 8, 12, 13, 17, 18). MS (m/z, %):
1063 (Mþ, 100%), 189 (5%).
Porphyrin [2] (2B). A mixture of pyrrole (0.04 mole, 2.68
g) and 3,5-di-tert-butylbenzaldehyde (0.04 mole, 8.73 g) was
supported on propanoic acid/silica gel (5 g) and subjected to
microwave irradiation according to dry media procedure (ii)
(Table 2). After cooling, the reaction mixture was applied as
such onto silica column and eluted with chloroform: n-hexane
(1:2). The fast moving band was collected and the solvent was
evaporated to get Porphyrin [2] (32%).
Metalloporphyrin [4] (3D). Silica gel obtained directly
from Experiment-2B having adsorbed crude Porphyrin [2] was
thoroughly washed with 50 mL of saturated solution of nickel
acetate in methanol. Silica gel was dried and heated under
microwave according dry media procedure (ii) (Table 3). After
cooling, the reaction mixture was applied as such onto silica
column and eluted with chloroform: petroleum ether; b.p 60–
90ꢀC (1:3). The fast moving band was collected, and the sol-
vent was evaporated to get Metalloporphyrin [4] (92%).
Metalloporphyrin [5] (3E). Experiment-3A procedure was
repeated with copper acetate (1 mmole, 181.63 mg) to get
Metalloporphyrin [5] (Table 3) (94%). mp > 350ꢀC; Anal.
Calcd. for C56H52CuN4: C, 79.62; H, 6.21; N, 6.63. Found: C,
79.50; H, 6.23; N, 6.65. IR(KBr):mmax 2922, 1670, 1460, 1342,
1000, 802, 722 cmꢁ1; UV(CHCl3) kmax 415, 540 nm. MS (m/
z, %): 844.6 (Mþ, 15.85%), 842.6 (72%), 837.6 (100%).
Metalloporphyrin [5] (3F). Silica gel obtained directly
from experiment 1-B having crude synthesized Porphyrin 1
was washed thoroughly with 50 mL of a saturated solution of
copper acetate in methanol. After drying, silica gel was irradi-
ated with microwave (Table 3). Pure Metalloporphyrin [5] was
obtained by column chromatography using chloroform: petro-
leum ether; b.p 60–90ꢀC (1:3) as mobile phase. The fast mov-
ing band was collected and the solvent was evaporated to get
pure Metalloporphyrin [5] (94%).
Metalloporphyrin [6] (3G). Experiment-3C procedure was
repeated with copper acetate (1 mmole, 181.63 mg) to get
Metalloporphyrin [6] (Table 3) (93%). mp > 350ꢀC; Anal.
Calcd. for C76H92CuN4: C, 81.13; H, 8.24; N, 4.98. Found: C,
81.20; H, 8.22; N, 5.0. IR.(KBr)mmax 3060, 2980, 2940, 2860,
1600, 1520, 1480, 1440, 1400 cmꢁ1; UV(CHCl3) kmax 420,
540 nm. MS (m/z, %) 1123 (Mþ, 23%), 57 (34%).
Metalloporphyrin [6] (3H). Silica gel obtained directly
from the experiment 2-B having crude synthesized Porphyrin 2
was washed thoroughly with 50 mL of a saturated solution of
copper acetate in methanol. After drying, silica gel was irradi-
ated with microwave (Table 3). Purification was done by col-
umn chromatography using chloroform: petroleum ether; b.p
60–90ꢀC (1:3) as mobile phase. The fast moving band was col-
lected, and the solvent was evaporated to get pure Metallopor-
phyrin [6] (93%).
Formyl porphyrin [7] (4A). Urotropine (1 mmole, 140.19
mg) and Metalloporphyrin [3] (0.04 mmole, 33.59 mg) were
powder together in an agate mortar. These were doped on
H2SO4/silica gel (15 g) and heated under microwave according
to dry media procedure (ii) (Table 4). After cooling, 50 mL of
water was added and reaction mixture was stirred at room tem-
perature for 30 min. Water was removed by filtration and resi-
due was dried in vacuum desiccator. It was applied onto silica
column and eluted with chloroform: petroleum ether; b.p 60–
90ꢀC (2:1). The fast moving band was collected and the sol-
vent was evaporated to get 2-formyl-5,10,15,20-tetrakis(40-iso-
propylphenyl)porphyrinatonickel(II) [7] (54%). mp > 350ꢀC;
Anal.Calcd. for C57H52N4NiO: C, 78.90; H, 6.04; N, 6.46.
Found: C, 78.80; H, 6.03; N, 6.50. IR(KBr)mmax 2956, 2923,
1669 (C¼¼O), 1545, 1507, 1459, 1351, 1056, 1001, 937, 813,
797, 719 cmꢁ1; UV(CHCl3)kmax 435, 545, 585 nm. 1H
NMR(CDCl3): d 1.48 (d, J ¼ 6.7 Hz, 8CH3), 3.18 (sep, J ¼
6.7 Hz, 4CH), 7.52 (d, J ¼ 6.9 Hz, 4m-Ph2H), 7.89 (d, J ¼
6.9 Hz, 4o-Ph2H), 8.72 (m, b-pyrrolic H 7, 8, 12, 13, 17, 18),
9.20 (s, CH 3), 9.34 (s, CHO). MS (m/z, %), 867 (Mþ, 1%),
413 (100%), 277 (24%).
Metalloporphyrin [3] (3A). A mixture of Porphyrin [1]
(0.04 mmole, 31.32 mg) and nickel acetate (1 mmole, 176.78
mg) was supported on propanoic acid/silica gel (5 g) and sub-
jected to microwave irradiation according to dry media proce-
dure (ii) (Table 3). After cooling, the reaction mixture was
applied as such onto silica column and eluted with chloroform:
petroleum ether; b.p 60–90ꢀC (1:3). The fast moving band was
collected, and the solvent was evaporated to get Metallopor-
phyrin [3] (90%). mp > 350ꢀC; Anal. Calcd. for C56H52N4Ni:
C, 80.10; H, 6.25; N, 6.67. Found: C, 80.05; H, 6.28; N, 6.68.
IR(KBr):mmax 2956, 1654, 1660, 1351, 1261, 1055, 1004, 812
1
cmꢁ1; UV(CHCl3) kmax 420, 445, 530 nm. H NMR (CDCl3):
d 1.48 (d, J ¼ 6.9 Hz, 8CH3), 3.18 (sep, J ¼ 6.9 Hz, 4CH),
7.50 (d, J ¼ 7.9 Hz, 4m-Ph2H), 7.90 (d, J ¼ 7.9 Hz, 4o-
Ph2H), 8.74 (s, b-pyrrolic H 2, 3, 7, 8, 12, 13, 17, 18). MS
(m/z, %): 839 (Mþ, 75%) 837.7 (100%), 55.1 (16.79%).
Metalloporphyrin [3] (3B). Silica gel obtained directly
from Experiment-1B having adsorbed crude Porphyrin [1] was
thoroughly washed with 50 mL of a saturated solution of
nickel acetate in methanol. Silica gel was dried and heated
under microwave according dry media procedure (ii) (Table
3). After cooling, the reaction mixture was applied as such
onto silica column and eluted with chloroform: petroleum
ether; b.p 60–90ꢀC (1:3). The fast moving band was collected,
and the solvent was evaporated to get Metalloporphyrin [3]
(90%).
Metalloporphyrin [4] (3C). A mixture of Porphyrin [2]
(0.04 mmole, 42.54 mg) and nickel acetate (1 mmole, 176.78
mg) was supported on propanoic acid/silica gel (5 g) and sub-
jected to microwave irradiation according to dry media proce-
dure (ii) (Table 3). After cooling, the reaction mixture was
applied as such onto silica column and eluted with chloroform:
petroleum ether; b.p 60–90ꢀC (1:3). The fast moving band was
collected, and the solvent was evaporated to get Metallopor-
phyrin [4] (92%). mp >350ꢀC; Anal. Calcd. for C76H92N4Ni:
C, 81.48; H, 8.28; N, 5.00. Found: C, 81.52; H, 8.30; N, 5.01.
IR(KBr):mmax 3060, 2960, 2900, 2860, 1600, 1480, 1440, 1400
cmꢁ1; UV(CHCl3) kmax 415, 530 nm. 1H NMR (CDCl3): d
1.46 (s, 8t-Bu), 7.70 (t, J ¼ 2.0 Hz, 4p-PhH), 7.86 (d, J ¼ 2.0
Hz, 8o-PhH), 8.79 (s, b-pyrrolic H 2, 3, 7, 8, 12, 13, 17, 18).
MS (m/z, %) 1118 (Mþ, 100%), 57 (84%).
Journal of Heterocyclic Chemistry
DOI 10.1002/jhet