Preparation of Water-Soluble Porphyrin Receptors
J. Am. Chem. Soc., Vol. 121, No. 49, 1999 11431
H), 10.57 (s, 1H, CHO). Anal. Calcd for C15H16O9: C, 52.95; H, 4.74.
Found: C, 52.66; H, 4.82.
24H, CO2Me), 4.05 (s, 12H, CO2Me), 4.33 (s, 16H, CH2), 7.57 (s, 8H,
phenyl-H), 8.84 (s, 8H, â-pyrrole); UV-vis (CH2Cl2) λmax (log ꢀ) 423
(5.71), 555 (4.29), 592 (3.51); HRMS (FAB) calcd for C76H68N4O32Zn
(M+) 1612.3106, found 1612.3073.
Methyl 4-Formyl-3,5-bis(4-methoxycarbonylbutoxy)benzoate (7b).
A solution of powdered 6b (1.35 g, 2.76 mmol) in DMSO (30 mL)
and NaHCO3 (3.9 g) was heated at 90 °C under N2 with vigorous stirring
for 10 min. The same workup described for 7c gave 7b in 75% yield
(0.88 g): 1H NMR (CDCl3) δ 1.85 (m, 8H, CH2), 2.39 (t, J ) 7.0 Hz,
4H, CH2), 3.66 (s, 6H, CO2Me), 3.92 (s, 3H, CO2Me), 4.09 (t, J ) 5.8
Hz, 4H, CH2), 7.18 (s, 2H, phenyl-H), 10.50 (s, 1H, CHO); HRMS
(FAB) calcd for C21H29O9 (MH+) 425.1829, found 425.1812. Anal.
Calcd for C21H28O9: C, 59.43; H, 6.65. Found: C, 59.17; H, 6.54.
Methyl 4-Formyl-3,5-bis(10-methoxycarbonyldecyloxy)benzoate
(7c). A solution of powdered 6c (3.0 g, 4.6 mmol) in DMSO (60 mL)
and NaHCO3 (6.0 g) was heated at 120 °C under N2 with vigorous
stirring for 10 min. The reaction mixture was then immediately cooled
in an ice bath, poured into saturated aqueous NaCl (100 mL), and
extracted with AcOEt (100 mL × 2). The organic layers were combined
and dried over MgSO4. Evaporation of the solvent and recrystallization
from benzene/hexane afforded a white solid of 7c (2.26 g, 84%): 1H
NMR (CDCl3) δ 1.27 (m, 20H, CH2), 1.45 (quintet, J ) 7.4 Hz, 4H,
CH2), 1.60 (quintet, J ) 7.5 Hz, 4H, CH2), 1.81 (quintet, J ) 7.0 Hz,
4H, CH2), 2.28 (t, J ) 7.5 Hz, 4H, CH2), 3.65 (s, 6H, CO2Me), 3.92
(s, 3H, CO2Me), 4.06 (t, J ) 6.8 Hz, 4H, CH2), 7.18 (s, 2H, phenyl-
H), 10.51 (s, 1H, CHO); HRMS (FAB) (MH+) calcd for C33H53O9
593.3689, found 593.3702. Anal. Calcd for C33H52O9: C, 66.87; H,
8.84. Found: C, 66.21; H, 8.89.
[5,10,15,20-Tetrakis(4-methoxycarbonyl-3,5-bis(4-methoxycarbo-
nylbutoxy)phenyl)porphyrinato]zinc(II) (9b). This compound was
prepared from 8b (91 mg, 48 µmol) in a manner similar to that described
for 9c: yield 83% (78 mg); 1H NMR (CDCl3) δ 0.64 (quintet, J ) 7.5
Hz, 16H, CH2), 0.92 (quintet, J ) 7.5 Hz, 16H, CH2), 1.01 (t, J ) 7.0
Hz, 16H, CH2), 2.61 (s, 24H, CO2Me), 3.88 (t, J ) 6.5 Hz, 16H, CH2),
4.08 (s, 12H, CO2Me), 7.64 (s, 8H, phenyl-H), 8.66 (s, 8H, â-pyrrole);
UV-vis (CH2Cl2) λmax (log ꢀ) 425 (5.64), 552 (4.32), 592 (3.23); HRMS
(FAB) calcd for C100H116N4O32Zn (M+) 1948.6862, found 1948.6614.
[5,10,15,20-Tetrakis(4-methoxycarbonyl-3,5-bis(10-methoxycar-
bonyldecyloxy)phenyl)porphyrinato]zinc(II) (9c). A solution of 8c
(97 mg, 38 µmol) and Zn(OAc)2-saturated methanol (15 mL) in CHCl3
(110 mL) was refluxed for 3 h. After cooling, the solution was washed
with saturated aqueous NaHCO3 (100 mL × 2) and saturated aqueous
NaCl (100 mL × 2) and dried over Na2SO4. Evaporation of the solvent
and purification by flash column chromatography (SiO2, CHCl3/AcOEt
) 1/1) and recrystallization from CH2Cl2/hexane afforded a pink solid
of 9c (80 mg, 80%): 1H NMR (CDCl3) δ 0.55 (quintet, J ) 7.5 Hz,
16H, CH2), 0.71 (m, 32H, CH2), 0.82 (quintet, J ) 7.5 Hz, 16H, CH2),
0.93 (m, 32H, CH2), 1.03 (quintet, J ) 7.5 Hz, 16H, CH2), 1.43 (quintet,
J ) 7.5 Hz, 16H, CH2), 2.17 (t, J ) 7.5 Hz, 16H, CH2), 3.60 (s, 24H,
CO2Me), 3.82 (t, J ) 6.5 Hz, 16H, CH2), 4.07 (s, 12H, CO2Me), 7.63
(s, 8H, phenyl-H), 8.66 (s, 8H, â-pyrrole); UV-vis (CH2Cl2) λmax (log
ꢀ) 424 (5.63), 551 (4.26), 592 (3.45); HRMS (FAB) calcd for
5,10,15,20-Tetrakis(4-methoxycarbonyl-3,5-bis(methoxycarbon-
ylmethoxy)phenyl)porphyrin (8a). This compound was prepared from
7a (680 mg, 2 mmol) in a manner similar to that described for 8c:
C
148H212N4O32Zn (M+) 2621.4374, found 2621.4663.
1
yield 15% (120 mg); H NMR (CDCl3, 500 MHz) δ -2.62 (s, 2H,
[5,10,15,20-Tetrakis(4-carboxy-3,5-bis(carboxymethoxy)phenyl)-
NH), 3.42 (s, 24H, CO2Me), 4.05 (s, 12H, CO2Me), 4.34 (s, 16H, CH2),
7.57 (s, 8H, phenyl-H), 8.78 (s, 8H, â-pyrrole); UV-vis (CH2Cl2) λmax
(log ꢀ) 419 (5.66), 512 (4.43), 544 (3.83), 587 (4.00). Anal. Calcd for
C76H70N4O32: C, 58.84; H, 4.55; N, 3.61. Found: C, 58.15; H, 4.52;
N, 3.29.
porphyrinato]zinc(II) Potassium Salt (1). This compound was
prepared from 9a (87 mg, 54 µmol) in a manner similar to that described
for 3: yield 89% (92 mg); 1H NMR (deuterated Borax buffer, pD 8.6,
I ) 0.1 M) δ 4.27 (s, 16H, CH2), 7.53 (s, 8H, phenyl-H), 9.07 (s, 8H,
â-pyrrole); UV-vis (Borax buffer, pH 9.0, I ) 0.1 M) λmax (log ꢀ)
423 (5.41), 555 (3.98), 592 (3.18).
5,10,15,20-Tetrakis(4-methoxycarbonyl-3,5-bis(4-methoxycar-
bonylbutoxy)phenyl)porphyrin (8b). This compound was prepared
from 7b (2.122 g, 5 mmol) in a manner similar to that described for
8c: yield 22% (527 mg); 1H NMR (CDCl3) δ -2.62 (s, 2H, NH), 0.83
(quintet, J ) 7.5 Hz, 16H, CH2), 0.98 (quintet, J ) 7.5 Hz, 16H, CH2),
1.51 (t, J ) 7.0 Hz, 16H, CH2), 3.06 (s, 24H, CO2Me), 3.88 (t, J ) 6.5
Hz, 16H, CH2), 4.07 (s, 12H, CO2Me), 7.63 (s, 8H, phenyl-H), 8.58
(s, 8H, â-pyrrole); UV-vis (CH2Cl2) λmax (log ꢀ) 422 (5.62), 515
(4.38), 548 (3.95), 590 (4.00); HRMS (FAB) calcd for C100H118N4O32
(M+) 1886.7728, found 1886.7751. Anal. Calcd for C100H118N4O32: C,
63.62; H, 6.30; N, 2.97. Found: C, 63.37; H, 6.32; N, 2.92.
[5,10,15,20-Tetrakis(4-carboxy-3,5-bis(4-carboxybutoxy)phenyl)-
porphyrinato]zinc(II) Potassium Salt (2). This compound was
prepared from 9b (51 mg, 26 µmol) in a manner similar to that described
for 3: yield 84% (49 mg); 1H NMR (deuterated Borax buffer, pD 8.6,
I ) 0.1 M) δ 0.89 (quintet, J ) 7.5 Hz, 16H, CH2), 1.19 (quintet, J )
7.5 Hz, 16H, CH2), 1.66 (t, J ) 7.5 Hz, 16H, CH2), 3.99 (t, J ) 7.0
Hz, 16H, CH2), 7.76 (s, 8H, phenyl-H), 8.91 (s, 8H, â-pyrrole); UV-
vis (Borax buffer, pH 9.0, I ) 0.1 M) λmax (log ꢀ) 426 (5.42), 557
(4.03), 596 (3.38).
5,10,15,20-Tetrakis(4-methoxycarbonyl-3,5-bis(10-methoxycar-
bonyldecyloxy)phenyl)porphyrin (8c). Aldehyde 7c (1.78 g, 3 mmol)
and pyrrole (208 µL, 3 mmol) were dissolved in CH2Cl2 (300 mL)
under N2 and then BF3‚OEt2 (125 µL, 0.99 mmol) was added. After
the reaction mixture was stirred at room temperature for 100 min, 2,3-
dichloro-5,6-dicyanobenzoquinone (510 mg, 2.2 mmol) was added and
the mixture was refluxed for 2 h. The solution was then neutralized by
addition of triethylamine (138 µL, 1 mmol) and evaporated. The mixture
was separated by column chromatography (SiO2, CHCl3/AcOEt ) 100/
1-10/1) and crude product was washed with methanol thoroughly to
afford a purple solid of 8c (296 mg, yield 16%): 1H NMR (CDCl3) δ
-2.64 (s, 2H, NH), 0.61 (quintet, J ) 7.5 Hz, 16H, CH2), 0.76 (m,
32H, CH2), 0.88 (quintet, J ) 7.5 Hz, 16H, CH2), 0.94 (quintet, J )
7.5 Hz, 16H, CH2), 0.97 (quintet, J ) 7.5 Hz, 16H, CH2), 1.06 (quintet,
J ) 7.5 Hz, 16H, CH2), 1.45 (quintet, J ) 7.5 Hz, 16H, CH2), 2.17 (t,
J ) 7.5 Hz, 16H, CH2), 3.60 (s, 24H, CO2Me), 3.82 (t, J ) 6.5 Hz,
16H, CH2), 4.07 (s, 12H, CO2Me), 7.62 (s, 8H, phenyl-H), 8.57 (s,
8H, â-pyrrole); UV-vis (CH2Cl2) λmax (log ꢀ) 422 (5.61), 515 (4.36),
549 (3.93), 584 (4.01); HRMS (FAB) calcd for C148H214N4O32 (M+)
2559.5239, found 2559.6562. Anal. Calcd for C148H214N4O32: C, 69.40;
H, 8.42; N, 2.19. Found: C, 69.28; H, 8.32; N, 2.15.
[5,10,15,20-Tetrakis(4-carboxy-3,5-bis(10-carboxydecyloxy)phe-
nyl)porphyrinato]zinc(II) Potassium Salt (3). Zinc porphyrin 9c (48
mg, 19 µmol) was dissolved in a solution prepared by mixing THF
(36 mL), methanol (15 mL), and 0.5 M KOH (16 mL). After being
stirred at room temperature for 24 h, the solution was concentrated
and passed through Sephadex G-15 followed by lyophilization to afford
3 (43 mg, yield 79%): 1H NMR (deuterated Borax buffer, pD 8.6, I )
0.1 M) δ 0.38 (quintet, J ) 7.5 Hz, 16H, CH2), 0.51 (quintet, J ) 7.5
Hz, 16H, CH2), 0.62 (quintet, J ) 7.5 Hz, 16H, CH2), 0.71 (quintet, J
) 7.5 Hz, 16H, CH2), 0.86 (quintet, J ) 7.5 Hz, 16H, CH2), 1.00
(quintet, J ) 7.5 Hz, 16H, CH2), 1.08 (quintet, J ) 7.5 Hz, 16H, CH2),
1.40 (quintet, J ) 7.5 Hz, 16H, CH2), 2.10 (t, J ) 7.5 Hz, 16H, CH2),
3.93 (t, J ) 7.0 Hz, 16H, CH2), 7.76 (s, 8H, phenyl-H), 8.84 (s, 8H,
â-pyrrole); UV-vis (Borax buffer, pH 9.0, I ) 0.1 M) λmax (log ꢀ)
426 (5.37), 555 (3.98), 593 (2.75).
Acknowledgment. We thank K. Akiyoshi for his help in
dynamic light scattering studies. The kind help of T. Kobatake
in mass spectroscopic studies is also acknowledged. This work
was supported by a Grant-in Aid for Scientific Research on
Priority Areas No. 11132233 from the Ministry of Education,
Science, Sports and Culture, Japan.
[5,10,15,20-Tetrakis(4-methoxycarbonyl-3,5-bis(methoxycarbo-
nylmethoxy)phenyl)porphyrinato]zinc(II) (9a). This compound was
prepared from 8a (100 mg, 65 µmol) in a manner similar to that
1
described for 9c: yield 84% (87 mg); H NMR (CDCl3) δ 3.38 (s,
JA9922126