C. Sun et al. / Dyes and Pigments 96 (2013) 130e137
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2H, OH); 9.10e9.12 (d, 2H, 3-, 8-H); 10.04, 10.09, 10.15 (3s, 4H, 5-,
10-, 15, 20-CH). ESI-MS/MS: [M þ H]þ m/z (%) ¼ 627.1695 (100),
recrystallized from hot methanol and dried in vacuo at 100 ꢁC for
3 h to afford DP hydrazide (0.30 g, 0.56 mmol, 95%). 1H NMR
[M þ Na]þ m/z (%) ¼ 649.1521 (5). IR (KBr,
n
/cmꢀ1): 3418 (s), 3312
(500 MHz, CDCl3):
d/ppm ¼ ꢀ4.05 (s, 2H, NH); 3.29e3.32 (t, 4H,
(m), 2919 (m), 1729 (s), 1619 (w), 1387 (m), 1271 (w), 1232 (w), 1167
(s), 1057 (m), 976 (m), 842 (m), 732 (m), 675 (w), 560 (w). Anal.
Calcd for (C36H42N4O6): C, 68.99; H, 6.75; N, 8.94. Found: C, 68.91;
H, 6.80; N, 8.90. UVevis (CH2Cl2): 398, 496, 529, 565, 618.
J ¼ 7.0 Hz, CH2CH2CO); 3.55e3.56 (d, 4H, NH2) 3.62, 3.66, 3.73, 3.77
(4s, 12H, 4CH3); 4.40e4.41 (m, 4H, CH2CH2CO); 5.76 (s, 2H, CONH);
9.33e9.35 (d, 2H, 3-, 8-H); 10.27e10.34 (3s, 4H, 5-, 10-, 15, 20-CH).
ESI-MS/MS: [M þ H]þ m/z (%) ¼ 539.0544 (100). Anal. Calcd for
(C30H34N8O2): C, 66.89; H, 6.36; N, 20.80; Found: C, 65.71; H, 6.98;
N, 20.61. UVevis (DMF): 396, 495, 527, 565, 617.
2.2.4. Synthesis of deuteroporphyrin-niacin dyads (DPEDN, DPPDN
and DPBDN)
The synthesis of DPEDN, DPPDN and DPBDN were similar to
that of DPDN except that dichloromethane/ethyl acetate ¼ 5/3 (v/v)
for DPBDN was used instead of dichloromethane/ethyl acetate ¼ 5/
2 (v/v) as the eluent. DPEDN: 0.37 g (0.46 mmol, 91%); 1H NMR
2.2.6. Synthesis of 2,7,12,18-tetramethyl-13,17-di(3-aminoethyl)
porphyrin (DAPP)
A solution of sodium nitrite (0.20 g, 2.90 mmol) in water
(5 mL) was slowly added to a solution of the DP hydrazide
(0.25 g, 0.46 mmol) in 0.5 M HCl (60 mL) at 0 ꢁC. After dropping,
the reaction was stirred for 20 min. The suspension was filtered,
and the residue was washed with ice water and dried in vacuo at
ambient temperature to give a puce solid. Toluene (20 mL) was
added to the solid and refluxed for 5 min to generate N2 gas and
the concentrated HCl (1.5 mL) was added and refluxed for
another 10 min to generate CO2. Finally, the toluene was removed
under reduced pressure to give the sticky liquid, which was
neutralized with saturated aqueous NaHCO3. The suspension was
filtered and washed with water. The residue was purified by
recrystallization from methanol to give DAPP (0.12 g, 0.27 mmol,
(500 MHz, CDCl3):
d
/ppm ¼ ꢀ3.99 (s, 2H, NH); 3.32e3.35 (t, 4H,
J ¼ 7.5 Hz, CH2CH2CO); 4.41e4.4 (t, 4H, J ¼ 7.5 Hz, CH2CH2CO);
4.34e4.35 (br, 8H, CH2CH2OH); 3.61e3.63, 3.73e3.74 (2d, 12H,
4CH3); 6.50e6.55 (m, 2H, Py-5-H); 7.48e7.81 (d, 2H, Py-4-H);
8.26e8.28 (t, 2H, Py-6-H); 8.84e8.85 (d, 2H, Py-2-H); 9.07e9.09 (d,
2H, 3-, 8-H); 9.98, 10.06 (2s, 2H, 5-, 10-CH); 10.09e10.10 (d, 2H, 5-,
10-CH). ESI-MS/MS: [M þ H]þ m/z (%) ¼ 809.2950 (100), [M þ Na]þ
m/z (%) ¼ 831.2905 (20). IR (KBr,
n
/cmꢀ1): 3310 (m), 2916 (m), 1725
(s), 1617 (w), 1590 (m), 1418 (m), 1378 (w), 1282 (s), 1237 (w), 1167
(m), 1135 (m),1108 (m),1025 (w), 946 (w), 897 (w), 840 (m), 738 (s),
704 (m), 677 (w), 621 (w). Anal. Calcd for (C46H44N6O8): C, 68.30; H,
5.48; N, 10.39; Found: C, 66.03; H, 5.51; N, 10.65. UVevis (CH2Cl2):
398, 496, 529, 566, 618. DPPDN: 0.35 g (0.42 mmol, 87.5%); 1H NMR
57%) as a black powder: 1H NMR (500 MHz, CF3COOD):
d/
ppm ¼ ꢀ4.25 (s, 2H, NH); 3.23 (t, 4H, J ¼ 7.5 Hz, CH2CH2NH2);
3.79e3.87 (4s, 12H, 4CH3); 4.02 (s, 4H, CH2CH2NH2); 4.66, 4.83
(2s, 4H, NH2); 9.62e9.65 (t, 2H, 3-, 8-H), 10.97, 11.01, 11.09, 11.14
(500 MHz, CDCl3):
d/ppm ¼ ꢀ3.91 (s, 2H, NH); 1.59 (br, 4H,
OCH2CH2CH2Opy); 3.28e3.31 (t, 4H, J ¼ 7.5 Hz, CH2CH2CO);
4.01e4.04 (q, 4H, CH2CH2CO); 4.14e4.17 (t, 4H, J ¼ 6.5 Hz,
OCH2CH2CH2Opy); 4.43 (t, 4H, J ¼ 6.5 Hz, OCH2CH2CH2Opy);
3.62e3.65, 3.71e3.74 (2d, 12H, 4CH3); 7.10e7.13 (t, 2H, Py-5-H);
7.88e7.89 (d, 2H, Py-4-H); 8.63 (s, 2H, Py-6-H); 8.98 (s, 2H, Py-2-H);
9.06e9.07 (d, 2H, 3-, 8-H); 10.01e10.02, 10.10e10.11 (2d, 4H, 5-, 10-,
15, 20-CH). ESI-MS/MS: [M þ H]þ m/z (%) ¼ 837.2686 (100). IR (KBr,
(4s, 4H, 5-, 10-, 15, 20-CH). ESI-MS/MS: [M
þ
H]þ m/z
(%) ¼ 453.0865 (100). Anal. Calcd for (C28H32N6): C, 74.30; H, 7.13;
N, 18.57; Found: C, 73.80; H, 7.82; N, 18.38. UVevis (CH3OH): 394,
495, 526, 565, 617.
2.2.7. Synthesis of 2,7,12,18-tetramethyl-13,17-di(3-aminoethyl-
nicotinate)porphyrin (DAPPN)
n
/cmꢀ1): 3312 (m), 2921 (m), 1726 (s), 1592 (m), 1421 (w), 1383 (w),
1287 (s), 1234 (w), 1192 (w), 1164 (m), 1136 (m), 1050 (w), 1026 (w),
931 (w), 842 (w), 739 (m), 705 (w). Anal. Calcd for (C48H48N6O8): C,
68.88; H, 5.78; N, 10.04. Found: C, 69.01; H, 5.94; N, 9.76. UVevis
(CH2Cl2): 397, 496, 529, 565, 618. DPBDN: 0.35 g (0.41 mmol,
The synthesis of DAPPN was similar to that of DPDN except that
dichloromethane/methanol ¼ 10/1 (v/v) was used instead of
dichloromethane/ethyl acetate ¼ 5/2 (v/v) as the eluent. DAPPN:
(0.31 g, 0.47 mmol, 71%), 1H NMR (500 MHz, CDCl3):
d
/ppm ¼ ꢀ3.85
88%); 1H NMR (500 MHz, CDCl3):
d
/ppm ¼ ꢀ3.83 (s, 2H, NH);
(s, 2H, NH); 4.21 (br, 4H, CH2CH2NH); 4.32 (br, 4H, CH2CH2NH);
3.62e3.64, 3.71e3.74 (2d, 12H, 4CH3); 5.30 (s, 2H, CH2CH2NH);
7.62e7.68 (br, 2H, Py-5-H); 7.99e8.00 (d, 2H, Py-4-H); 8.71 (s, 2H,
Py-6-H); 9.04 (s, 2H, Py-2-H); 9.08e9.09 (d, 2H, 3-, 8-H); 10.02,
10.06,10.13,10.38 (4s, 4H, 5-,10-,15-, 20-CH); ESI-MS/MS: [M þ H]þ
1.28e1.35 (m, 4H, COCH2CH2CH2CH2OH); 1.43e1.48 (m, 4H,
COCH2CH2CH2CH2OH); 3.29e3.32 (t, 4H, J ¼ 7.5 Hz, CH2CH2CO);
3.77e3.81 (m, 4H, CH2CH2CO); 4.03e4.06 (m, 4H, COCH2CH2CH2
-
CH2OH); 4.43e4.47 (q, 4H, COCH2CH2CH2CH2Opy); 3.64, 3.68, 3.72,
3.75 (4s, 12H, 4CH3); 7.13e7.16 (q, 2H, Py-5-H); 7.87e7.90 (m, 2H,
Py-4-H); 8.64e8.66 (m, 2H, Py-6-H); 8.96e8.98 (2d, 2H, Py-2-H);
9.07e9.09 (d, 2H, 3-, 8-H); 10.03e10.04,10.14e10.15 (2d, 4H, 5-,10-,
15, 20-CH). ESI-MS/MS: [M þ H]þ m/z (%) ¼ 865.3849 (100),
m/z (%) ¼ 663.1509 (100). IR (KBr,
n
/cmꢀ1): 3312 (w), 3059 (w), 2920
(m), 1655 (s), 1591 (s), 1543 (m), 1474 (w), 1417 (w), 1383 (w), 1269
(m), 1235 (m), 1195 (w), 1153 (w), 1023 (m), 977 (m), 850 (m), 735
(m), 705 (m), 625 (w). Anal. Calcd for (C40H38N8O2): C, 72.49; H,
5.78; N, 16.91 Found: C, 71.89; H, 5.97; N, 17.22. UVevis (CH2Cl2):
400, 498, 530, 568, 618, 655.
[M þ Na]þ m/z (%) ¼ 887.5361 (5). IR (KBr,
n
/cmꢀ1): 3312 (m), 2956
(m), 1724 (s), 1590 (m), 1419 (w), 1386 (w), 1285 (s), 1234 (w), 1164
(m),1129 (m),1025 (m), 972 (w), 840 (w), 739 (m), 704 (w), 676 (w),
619 (w). Anal. Calcd for (C50H52N6O8): C, 69.43; H, 6.06; N, 9.72
Found: C, 68.92; H, 6.19; N, 9.86. UVevis (CH2Cl2): 397, 496, 529,
566, 618.
2.2.8. Synthesis of manganese porphyrins
The process of metalation of porphyrin was based on the
method of Adler et al. [20]. Metalloporphyrins were synthesized by
the reaction of deuteroporphyrin-niacin dyads (0.20 g) with
MnCl2$5H2O (0.50 g) in tetrahydrofuran (50 mL) to afford high
yields of more than 97%. The reaction conditions were stirred for
4 h under reflux. The process of metalation was monitored by
UVevis until the free base porphyrin was almost disappeared. After
the completion of the reaction, the mixture was extracted with
CH2Cl2 (300 mL). The organic layer was dried with magnesium
sulfate and the solvents were evaporated. The crude compound was
purified by chromatography on silica gel using CH2Cl2 and meth-
anol (10/1 to 10/3) as the mobile phase.
2.2.5. Synthesis of deuteroporphyrin hydrazide (DP hydrazide)
To a stirred solution of 50 mL of dry CH2Cl2 containing 0.30 g of
deuteroporphyrin DP, 0.5 mL of SOCl2 was added. The resulting
mixture was refluxed for 4 h. After evaporation of the CH2Cl2 (more
than 40 mL), excess hydrazine hydrate (10 mL, wt, 80%) was added
dropwise and stirring was continued at ambient temperature for
30 min. Then, dilute sulfuric acid was added dropwise to the
vigorously stirred suspension until the pH was brought to 8.0. The
suspension was filtered and washed with water. The residue was