MONO-, BIS- AND TETRAHYDROXY PHTHALOCYANINES AS BUILDING BLOCKS
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The product 16 was obtained as a dark green solid with
quantitative yield (57 mg). H NMR (300 MHz; CDCl3;
product 20 was collected as first green fraction (Rf =
0.85 in CHCl3/EtOH 18:1) and crystallized on a watch
glass. After washing with n-pentane, the compound 20
was obtained as a dark green solid (25 mg, 55%). UV-
vis (CHCl3): λmax, nm (ε, M-1.cm-1) 335 (73731), 734
1
Me4Si): δH, ppm 9.30 (1H, d, J = 8.3 Hz, 25-phthalo-H),
8.91 (1H, d, J = 2.1 Hz, 22-phthalo-H), 7.82 (1H, dd,
J1 = 8.3 Hz, J2 = 2.1 Hz, 24-phthalo-H), 7.69–7.12 (10H,
m, phthalo-H, Ar-H), 5.22 (2H, s, ArCH2O), 4.91–4.82
(8H, m, 4,8,11,15-OCH2C3H7), 4.70 (2H, t, J = 6.4 Hz,
1-OCH2C3H7), 4.61 (2H, t, J = 6.4 Hz, 18-OCH2C3H7),
2.70–2.53 (4H, m, COC2H4CO), 2.51–2.40 (2H, m,
1-OCH2CH2C2H5), 2.30–2.17 (10H, m, 4,8,11,15,18-
OCH2CH2C2H5), 2.15–2.03 (2H, m, 1-OC2H4CH2CH3),
1.99–1.76 (2H, m, 18-OC2H4CH2CH3), 1.74–1.60 (8H,
m, 4,8,11,15-OC2H4CH2CH3), 1.40 (9H, s, OC(CH3)3),
1.28 (3H, t, J = 7.4 Hz, 1-OC3H6CH3), 1.14–1.05 (15H,
m, 4,8,11,15,18-OC3H6CH3), 0.10 (2H, s, NH). MS (ESI-
TOF; CHCl3/MeOH 1:1): m/z 1225.6375 [M + H]+ (calcd.
for C71H84N8O11 1225.6338).
1
(136634), 760 (154889). H NMR (300 MHz; CDCl3;
Me4Si): δH, ppm 9.30 (1H, d, J = 8.3 Hz, 25-phthalo-H),
8.91 (1H, d, J = 2.1 Hz, 22-phthalo-H), 7.83 (1H, dd,
J1 = 8.3 Hz, J2 = 2.1 Hz, 24-phthalo-H), 7.69–7.12 (10H,
m, phthalo-H, Ar-H), 5.23 (2H, s, ArCH2O), 4.91–4.82
(8H, m, 4,8,11,15-OCH2C3H7), 4.70 (2H, t, J = 6.4 Hz,
1-OCH2C3H7), 4.61 (2H, t, J = 6.4 Hz, 18-OCH2C3H7),
2.97–2.91 (2H, m, COC2H4CO), 2.84–2.78 (2H, m,
COC2H4CO), 2.51–2.40(2H, m, 1-OCH2CH2C2H5), 2.30–
2.18 (10H, m, 4,8,11,15,18-OCH2CH2C2H5), 2.15–2.03
(2H, m, 1-OC2H4CH2CH3), 1.95–1.81 (2H, m, 18-OC2H4-
CH2CH3), 1.74–1.60 (8H, m, 4,8,11,15-OC2H4CH2CH3),
1.29 (3H, t, J = 7.4 Hz, 1-OC3H6CH3), 1.12–1.05 (15H,
m, 4,8,11,15,18-OC3H6CH3), 0.09 (2H, s, NH). MS (ESI-
TOF; MeOH/CHCl3 10:1): m/z 1335.5555 [M + H]+
(calcd. for C73H75N8O11F5 1335.5554).
1,4-di[hydroxypropyloxy]-9(10),16(17),23(24)-
tri[tert-butyl]phthalocyanine (6). Lithium (80 mg,
12 mmol) was dissolved in 1-pentanol (40 mL) under
argon atmosphere. 3,6-di(hydroxypropyloxy)phthalonit-
rile(4)(160mg, 0.58mmol)and4-tert-butylphthalonitrile
(5) (641 mg, 3.48 mmol) were added and the reaction
mixture was heated at reflux for 2.5 h under argon atmo-
sphere. The solution was cooled to room temperature
and the solvent was evaporated under reduced pressure
(bath temperature 80 °C). The product was dissolved in
CHCl3, the organic layer was washed with water (2 × 100
mL) and the solvent was evaporated under reduced pres-
sure. The crude product was purified by column chro-
matography on Silica 100, eluting the first fraction with
CHCl3 and the second fraction with CHCl3/EtOH 20:1.
The product 6 was obtained from the second fraction
(Rf = 0.40 in CHCl3/EtOH 18:1). Second fraction was
repurified on Silica 60, eluting as before. The collected
product 6 was crystallized on a watch glass, washed with
acetonitrile, and obtained as a dark green powder (99 mg,
20%) after drying. UV-vis (CHCl3/EtOH 1:1): λmax, nm
(ε, M-1.cm-1) 340 (59122), 693 (89631), 719 (84165).
1H NMR (300 MHz; CDCl3/CD3OD 10:1; Me4Si): δH,
ppm 9.50–8.45 (6H, m, phthalo-H), 8.28–8.07 (3H, m,
phthalo-H), 6.88–6.07 (2H, m, 2,3-phthalo-H), 4.65–4.24
(8H, m, OCH2CH2CH2OH), 2.51–2.23 (4H, m, OCH2-
CH2CH2OH), 1.91–1.68 (27H, m, C(CH3)3), -2.40–2.97
(2H, m, NH), CH2OH were not resolved. MS (ESI-TOF;
CHCl3/MeOH 1:1): m/z 831.4359 [M + H]+ (calcd. for
C50H54N8O4 831.4346).
1,4,8,11,15,18-hexabutoxy-23-[3-(succinatoxy-
methyl)phenoxy]phthalocyanine (18). The product 16
(57 mg, 46.5 µmol) was dissolved in dry CH2Cl2 (2 mL),
TFA (2 mL) was added, and the solution was stirred at
room temperature for 3 h. More CH2Cl2 was added and
the organic phase was washed with water (3 × 50 mL).
After evaporating the solvent under reduced pressure, the
product was crystallized on a watch glass and washed
with n-pentane. The product 18 (Rf = 0.30 in CHCl3/EtOH
9:1) was obtained as dark green solid (50 mg, 93%).
UV-vis (CHCl3): λmax, nm (ε, M-1.cm-1) 335 (43472),
1
734 (85217), 761 (98005). H NMR (300 MHz; CDCl3;
Me4Si): δH, ppm 9.30 (1H, d, J = 8.3 Hz, 25-phthalo-H),
8.85 (1H, d, J = 2.0 Hz, 22-phthalo-H), 7.84 (1H, dd, J1
= 8.3 Hz, J2 = 2.1 Hz, 24-phthalo-H), 7.69–7.12 (10H,
m, phthalo-H, Ar-H), 5.21 (2H, s, ArCH2O), 4.90–4.81
(8H, m, 4,8,11,15-OCH2C3H7), 4.69 (2H, t, J = 6.4 Hz,
1-OCH2C3H7), 4.59 (2H, t, J = 6.4 Hz, 18-OCH2C3H7),
2.67–2.52 (4H, m, COC2H4CO), 2.50–2.39 (2H, m,
1-OCH2CH2C2H5), 2.30–2.18 (10H, m, 4,8,11,15,18-
OCH2CH2C2H5), 2.16–2.03 (2H, m, 1-OC2H4CH2CH3),
1.97–1.77 (2H, m, 18-OC2H4CH2CH3), 1.74–1.59 (8H,
m, 4,8,11,15-OC2H4CH2CH3), 1.28 (3H, t, J = 7.4 Hz,
1-OC3H6CH3), 1.12–1.05 (15H, m, 4,8,11,15,18-
OC3H6CH3), 0.09 (2H, s, NH), COOH was not resolved.
MS (ESI-TOF; MeOH/CHCl3 10:1): m/z 1169.5627 [M
+ H]+ (calcd. for C67H76N8O11 1169.5712).
1,4,8,11,15,18-hexabutoxy-23-[3-((pentafluoro-
phenoxy)succinatoxymethyl)phenoxy]phthalocya-
nine(20). DCC(14mg, 68.4µmol)andpentafluorophenol
(13 mg, 68.4 µmol) were added to a solution of the com-
pound 18 (40 mg, 34.2 µmol) in EtOAc (10 mL). The
mixture of compounds was stirred at room temperature.
After one day of stirring, DCC (14 mg) and pentafluo-
rophenol (13 mg) were added more. After five days the
solvent was evaporated under reduced pressure and the
product was dissolved in a few milliliters of CH2Cl2
and filtered through a cotton plug. Purification was car-
ried out twice by column chromatography on Silica 100
and on Silica 60, eluting both times with CHCl3. The
1,4-di[(3-bromopropanoate)propyloxy]-9(10),-
16(17),23(24)-tri[tert-butyl]phthalocyanine(11).Phthalo-
cyanine 6 (20 mg, 24 µmol) was dissolved in CH2Cl2
(5 mL) and 3-bromopropionyl chloride (9) (1.64 M solu-
tion in CH2Cl2, 0.176 mL, 288 µmol) was added to the
sealed vial. The reaction mixture was stirred at room
Copyright © 2010 World Scientific Publishing Company
J. Porphyrins Phthalocyanines 2010; 14: 407–411