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G. Zie˛ba et al.
5-[4-[4,4-Bis(ethoxycarbonyl)butyloxy]phenyl]-
10,15,20-tritolylporphyrin (9, C57H52N4O5)
1.84 (q, 2H), 1.69 (q, 2H), 1.31 (t, 3H), -2.76 (bs, 2H) ppm;
13C NMR (125 MHz, CDCl3): d = 173.75, 158.89, 139.36,
137.32, 135.61, 134.54, 129.60, 129.07, 127.43, 120.10,
112.72, 67.98, 60.35, 34.40, 29.23, 25.90, 24.90, 21.55,
14.35 ppm; ESI–MS: m/z = 815 (100) [M ? H]?.
1
Yield 27%; H NMR (400 MHz, CDCl3): d = 8.84 (m,
8H), 8.10 (d, 2H, J = 8.4 Hz), 8.09 (d, 6H, J = 7.6 Hz),
7.54 (d, 6H, J = 7.6 Hz), 7.24 (d, 2H, J = 8.4 Hz), 4.27
(q, 4H), 3.56 (t, 1H), 2.69 (s, 9H), 2.27 (q, 2H), 2.04
(q, 2H), 1.51 (bs, 2H), 1.33 (t, 6H), -2.76 (bs, 2H) ppm;
ESI–MS: m/z = 873 (100) [M ? H]?.
General procedure for 5-(4-carboxyalkyloxyphenyl)-
10,15,20-tritolylporphyrins from ethyl ester
5-(4-Pentyloxyphenyl)-10,15,20-tritolylporphyrin
(10, C52H46N4O)
5-[4-(x-Ethoxycarbonylalkyloxy)phenyl]-10,15,20-tritolyl-
porphyrin (0.03 g, *0.04 mmol) dissolved in 10 cm3
dichloromethane was added to a solution of sodium eth-
oxide (1 g sodium dissolved in 10 cm3 ethanol). One drop
of water was added to the mixture. The reaction mixture
was stirred for 3 h at room temperature. The solution was
then acidified to pH 7 with 1 M HCl, washed with water
(3 9 30 cm3), dried over Na2SO4, and concentrated.
Purification by column chromatography on silica gel (elu-
tion with CH2Cl2–EtOH, 25:1 (v/v) afforded the product.
1
Yield 14%; H NMR (400 MHz, CDCl3): d = 8.87 (m,
8H), 8.11 (d, 2H, J = 8.4 Hz), 8.10 (d, 6H, J = 8.0 Hz),
7.55 (d, 6H, J = 8.0 Hz), 7.27 (d, 2H, J = 8.4 Hz), 4.23 (t,
2H), 2.71 (s, 9H), 1.99 (q, 2H), 1.62 (q, 2H), 1.53 (q, 2H),
1.05 (t, 3H), -2.73 (bs, 2H) ppm; ESI–MS: m/z = 765
(100) [M ? Na]?, 743 (100) [M ? H]?; UV–Vis
(CH2Cl2): kmax (log e) = 422 (5.54), 519 (4.13), 555
(3.89), 593 (3.63), 650 (3.60) nm.
General procedure for 5-[4-[x-(ethoxycarbonyl)-
alkyloxy]phenyl]-10,15,20-tritolylporphyrins
5-[4-(4-Carboxybutyloxy)phenyl]-10,15,20-
tritolylporphyrin (4, C52H44N4O3)
Yield 24%; 1H NMR (400 MHz, CDCl3): d = 8.85 (d,
8H), 8.09 (d, 8H, J = 8.0 Hz), 7.54 (d, 6H, J = 8.0 Hz),
7.24 (d, 2H, J = 8.0 Hz), 4.26 (t, 2H), 2.76 (s, 9H), 2.59
(q, 2H), 2.03 (q, 2H), 1.62 (m, 2H), -2.76 (bs, 2H) ppm;
ESI–MS: m/z = 773 (100) [M ? H]?.
5-(4-Hydroxyphenyl)-10,15,20-tritolylporphyrin (100 mg,
0.15 mmol), 5 mg NaH (0.2 mmol), and 50 cm3 DMF
were placed in a round-bottomed flask and stirred at room
temperature for 30 min. Then 1 mmol ethyl x-bro-
moalkylcarboxylate was added and the resulting mixture
was stirred at 80 °C for 48 h. After evaporation of the
DMF under reduced pressure 50 cm3 dichloromethane was
added to the residue. The resulting solution was washed
with water (3 9 50 cm3) and dried over MgSO4. After
evaporation of the solvent the crude product was washed
with petroleum ether (20 cm3) and chromatographed on
silica with dichloromethane–ethanol 30:1 (v/v).
5-[4-(5-Carboxypentyloxy)phenyl]-10,15,20-tritolylpor-
phyrin (5) was obtained by this method in 19% yield.
Acknowledgments Financial support by the Polish State Commit-
tee for Scientific Research (grant no. R 05 043 03) is gratefully
acknowledged. The work of two authors (Marcin Rojkiewicz and
Grzegorz Zie˛ba) was partially supported by a PhD scholarship within
the framework of the ‘‘University as a Partner of the Economy Based
on Science’’ (UPGOW) project, subsidized by the European Social
Fund (EFS) of the European Union.
5-[4-[4-(Ethoxycarbonyl)butyloxy]phenyl]-10,15,20-
tritolylporphyrin (11, C54H48N4O3)
Open Access This article is distributed under the terms of the
Creative Commons Attribution Noncommercial License which per-
mits any noncommercial use, distribution, and reproduction in any
medium, provided the original author(s) and source are credited.
1
Yield 33%; H NMR (400 MHz, CDCl3): d = 8.85 (m,
8H), 8.11 (d, 2H, J = 8.0 Hz), 8.09 (d, 6H, J = 7.6 Hz),
7.55 (d, 6H, J = 7.6 Hz), 7.27 (d, 2H, J = 8.0 Hz), 4.28 (t,
2H), 4.21 (q, 2H), 2.71 (s, 9H), 2.52 (q, 2H), 2.03 (m, 4H),
1.33 (t, 3H), -2.76 (bs, 2H) ppm; 13C NMR (125 MHz,
CDCl3): d = 173.19, 155.75, 139.33, 137.32, 135.68,
134.57, 134.53, 130.89, 127.42, 120.09, 120.05, 113.67,
60.44, 33.36, 33.03, 32.04, 23.55, 21.53, 14.26 ppm;
ESI–MS: m/z = 801 (100) [M ? H]?.
References
1. Schaffer M, Schaffer PM, Hofstetter A, Du¨hmke E, Jori G (2002)
Photochem Photobiol Sci 1:438
2. Nyman ES, Hynninen PH (2004) J Photochem Photobiol B 73:1
3. Bonnett R (1995) Chem Soc Rev 24:19
5-[4-[5-(Ethoxycarbonyl)pentyloxy]phenyl]-10,15,20-
tritolylporphyrin (12, C55H50N4O3)
4. Sternberg ED, Dolphin D, Bru¨ckner C (1998) Tetrahedron
54:4151
5. Ballut S, Makky A, Loock B, Michael J-P, Maillard P, Rosilio V
(2009) Chem Commun 8:224
6. Ricchelli F (1995) J Photochem Photobiol B 29:109
1
Yield 29%; H NMR (400 MHz, CDCl3): d = 8.85 (m,
8H), 8.11 (d, 2H, J = 8.0 Hz), 8.10 (d, 6H, J = 7.6 Hz),
7.55 (d, 6H, J = 7.6 Hz), 7.27 (d, 2H, J = 8.0 Hz), 4.26
(t, 2H), 4.19 (q, 2H), 2.71 (s, 9H), 2.44 (t, 2H), 2.01 (q, 2H),
´
7. Voszka I, Galantai R, Maillard P, Csik G (1999) J Photochem
Photobiol B 52:92
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