1180 Bull. Chem. Soc. Jpn., 77, No. 6 (2004)
The Synthesis of ꢀ-Substituted Thiaporphyrins
tralized with triethylamine. The solvent was removed using a rota-
ry evaporator, and TLC analysis of the crude compound showed
the formation of the expected three porphyrins. The crude com-
pound was loaded on a silica-gel column and eluted with a petro-
leum ether/CH2Cl2 mixture. The N4 porphyrin moved as the first
band followed by the desired N3S porphyrin 4 collected with petro-
leum ether/CH2Cl2 (4:6). The solvent was removed to afford 4 as a
purple solid in 8% yield (31 mg). mp >300 ꢁC; 1H NMR (CDCl3, ꢂ
in ppm) 8.84 (s, 2H, pyrrole), 8.50 (q, 4H, pyrrole), 8.16 (d,
J ¼ 6:22, 4H, o-phenyl), 8.06 (d, J ¼ 3:66, 4H, o-phenyl), 7.65–
7.73 (m, 12H, m; p-phenyl), 4.15 (t, 6H, –OCH2), ꢄ2:57 (s, 1H,
–NH); ESMS Calcd exact mass 703.8. Found 704.2 (Mþ). Anal.
Calcd for C47H33N3O2S: C, 80.20; H, 4.73; N, 5.97%. Found: C,
79.95; H, 4.84; N, 6.05%.
This research was supported by Department of Atomic Ener-
gy (No. 2001/37/21/BRNS/797) Government of India, New
Delhi. Mass and NMR spectra were obtained at RSIC and
The Department of Chemistry, IIT-Bombay.
References
1
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2
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ꢀ-2,3-Bis(2,2-diethylpropane-1,3-diyldioxy)-meso-5,10,15,20-
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mg, 0.235 mmol), benzaldehyde (50 mL, 0.471 mmol), and pyrrole
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argon at room temperature for 10 min. The reaction was initiated
3
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with a catalytic amount of Et2O BF3 (10 mL of 2.5 M solution
ꢂ
in CH2Cl2) and stirred under an argon atmosphere for 1 h. DDQ
(65 mg, 0.286 mmol) was added, and the reaction mixture was stir-
red for an additional 1 h. The crude porphyrin mixture was purified
by silica-gel column chromatography, and the desired N3S porphy-
rin 5 was collected as the second band with a petroleum ether/
CH2Cl2 (6:4) mixture. The solvent was removed using a rotary
evaporator, giving 5 as a purple solid in 9% yield (16 mg). mp
ꢁ
1
>300 C; H NMR (CDCl3, ꢂ in ppm) 8.83 (s, 2H, pyrrole), 8.49
(q, J ¼ 4:02, 4H, pyrrole), 8.16 (d, J ¼ 5:85, 4H, o-phenyl), 8.04
(d, J ¼ 3:29, 4H, o-phenyl), 7.64–7.66 (m, 12H, m; p-phenyl),
4.06 (s, 4H, –OCH2), 1.25 (s, 4H, –CH2), 0.87 (t, J ¼ 7:32, 6H,
–CH3), ꢄ2:55 (s, 1H, –NH); FAB-MS Calcd exact mass 759.9.
Found 759. Anal. Calcd for C51H41N3O2S: C, 80.60; H, 5.44; N,
5.53%. Found: C, 80.77; H, 5.53; N, 5.59%.
ꢀ-2,3-Bis(2,2-dibenzylpropane-1,3-diyldioxy)-meso-5,10,15,
20-tetraphenyl-21-monothiaporphyrin 6. A solution of diol 12
(100 mg, 0.182 mmol), benzaldehyde (0.040 mL, 0.37 mmol), and
pyrrole (0.040 mL, 0.55 mmol) in 25 mL of CH2Cl2 were stirred
for 10 min at room temperature under argon atmosphere.
4
L. Latos-Grazynski, in ‘‘The Porphyrin Handbook,’’ ed by
K. M. Kadish, K. M. Smith, and R. Guilard, Academic Press,
New York (2000), Vol. 2, pp. 361–416, and references cited
therein.
Et2O BF3 (10 mL of 2.5 M solution in CH2Cl2) was added, and
5
N. Agarwal, S. P. Mishra, A. Kumar, C.-H. Hung, and M.
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a) D. M. Welsh, A. Kumar, E. W. Meijer, and J. R.
ꢂ
the reaction mixture was stirred for 1 h. DDQ (35 mg, 0.154 mmol)
was added, and the reaction mixture was stirred in open air at room
temperature for an additional 1 h. The crude porphyrin mixture of
the three porphyrins were separated by silica-gel column chroma-
tography, with the desired N3S porphyrin 6 as the second band with
petroleum ether/CH2Cl2 (7:3). The solvent was removed using a
rotary evaporator to afford the purple compound 6 in 8% yield
6
Reynolds, Adv. Mater., 11, 1379 (1999). b) K. Krishnamoorthy,
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7
(1975).
8
A. Ulman and J. Manassen, J. Am. Chem. Soc., 97, 6540
ꢁ
1
(12 mg). mp >300 C; H NMR (CDCl3, ꢂ in ppm) 8.83 (s, 2H,
pyrrole), 8.49 (q, 4H, pyrrole), 8.15 (d, J ¼ 5:80, 4H, o-phenyl),
8.04 (d, J ¼ 6:22, 4H, o-phenyl), 7.71–7.76 (m, 12H, m; p-phenyl),
7.30–7.34 (m, 6H, m; p-outerphenyl), 7.10 (d, J ¼ 6:59, 4H, o-out-
erphenyl), 4.07 (s, 4H, –OCH2), 2.80 (s, 8H, –CH2), ꢄ2:59 (s, 1H,
–NH); 13C NMR 44.9, 39.4, 124.0, 126.6, 126.3, 127.0, 127.8,
128.2, 132.0, 132.5, 132.9, 134.3, 134.9, 136.6, 138.6, 142.4,
152.5, 158.4; FAB-MS: Calcd exact mass 884.10. Found 884
(Mþ). Anal. Calcd for C61H45N3O2S: C, 82.87; H, 5.13; N,
4.75%. Found: C, 82.96; H, 5.23; N, 4.87%.
R. P. Pandian, D. Reddy, N. Chidambaram, and T. K.
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(1990).
9
R. P. Pandian, T. K. Chandrashekar, G. S. S. Saini, and A.
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