Chemistry of Materials
fluxed for 1 day under irradiation of light from a 180-W sunlamp.
Page 2 of 12
(d) Preparation of 5-(5’-bromo-2’-formylphenyl)-10,15,20-
trispentafluoro- phenylporphyrin (compound 5, Figure 1).
Compound 4 (1.5 g, 0.02 mol) was dissolved into dry CH Cl (200
mL) then an excess amount of activated MnO (~5 g) was added.
The solution was stirred under N for 2 hours. The TLC showed
complete conversion of the compound to 5. The MnO was isolat-
ed by filtration. The solvent was removed in vacuo and the residue
was purified with Silica-gel column using CH Cl as eluent to give a
pure violet powder (1.4 g, 93.5 % yield). H NMR (CDCl , 400
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
After cooling the reaction mixture, the solid succinimide was re-
moved by filtration, and the filtrate was evaporated in vacuo. The
resulting pale yellow powder was mixed with water:acetone:THF
(4:1:1, 600 mL). The mixture was refluxed for 1 day to give a clear
colorless solution. On cooling, 23 g of a 5-bromo-2-formylbenzoic
acid was produced that is isolated by filtration and washed with
distilled water. The acid was then converted to the corresponding
methyl ester by refluxing with MeOH (500 mL) in the presence of
2
2
2
2
2
2
2
1
3
anhydrous InCl
and after addition of water, white solid residue was extracted with
CHCl from water. The CHCl layer containing the desired com-
pound was dried over anhydrous Na SO and the solvent was evap-
orated to give 24 g of 2 as a white powder in 84.4% yield. H NMR
CDCl ): δ 10.46 (s, 1H, CHO), 7.87 (d, 1H, Ar-H), 7.75 (d, 1H,
3
(2.0 g) for about 18 h. The solvent was removed
MHz): δ 9.39 (s, 1H, -CHO), 8.92 (s, 4H, por-β-pyrrole H), 8.86
(d, 2H, por-β-pyrrole H), 8.80 (d, 2H, por-β-pyrrole H), 8.43 (d,
1H, Ar-H), 8.30 (d, 1H, Ar-H), 8.15 (dd, 1H, Ar-H), -2.82 (s, 2H,
por-pyrrole H). MALDI-TOF-MS m/z = 990.0 (found), 991.5
(calcd.).
(e) Preparation of 5-bromo-1,2-bis[5,10,15-tris pentafluoro-
phenyl porphyrinyl]benzene (compound 6, Figure 1). A 1-L
three-necked flask was charged with compound 5 (1.8 g, 0.02 mol),
pyrrole (1 g, 0.015 mol), pentafluoro-benzaldehyde (2.1 g, 0.01
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
3
3
2
4
1
(
3
Ar-H), 7.65 (dd, 1H, Ar-H), and 3.88 (s, 3H, OCH ). MALDI-
3
TOF-MS m/z = 242.5 (found), 243.0 (calcd.).
(
b) Preparation of 5-(5’-bromo-2’-methoxycarbonylphenyl)-
1
0,15,20- trispentafluorophenylporphyrin (compound 3, Fig-
mol), and dry CH
temperature for 20 min under N
2
Cl
2
(500 mL). The solution was stirred at room
. Then, BF •Et O (4 mL) was
ure 1). A 2-L three-neck round-bottomed flask was charged with
2
3
2
compound 2 (11 g, 0.045 mol), pentafluorobenz-aldehyde (26.6 g,
added. After 4−h stirring, DDQ solution (5 g in 100 mL benzene)
was added and the stirring was continued for additional 2−h. A
pure violet powder of compound 6 was isolated (0.4 g, 12.4 %
0
.136 mol), freshly distilled pyrrole (12.1 g, 0.180 mol), and CHCl
3
(
1300 mL). The colorless solution was purged with nitrogen for
about 15 min. Then, boron trifluoride diethyl ether complex
BF •Et O, 15 mL) was added via s syringe. The color changed
1
yield) after column chromatographic separation. H NMR
(
3
2
(CDCl ): δ 9.31 (dd, 4H, pyrrole β-H), 9.01 (d, 1H, Ar-H), 8.70
3
slowly to dark red. The mixture was stirred at room temperature
under nitrogen and TLC monitored the progress of the reaction.
After 10 h, excess DDQ (DDQ = 2,3-dichloro-5,6-dicyano-p-
benzoquinone) solution (20 g/150 ml benzene, 0.088 mol) was
added to the reaction mixture, where the color changed to dark
green. The mixture was stirred at room temperature for further 4 h.
The solvent was removed, the residue was dissolved in a small
(d, 1H, Ar-H), 8.49 (dd, 1H, Ar-H), ) 8.38 (d, 12H, pyrrole β-H), -
4.15 (s, 4H, pyrrole NH). MALDI-TOF-MS: m/z = 1770.4
(found), 1769.9 (calcd.).
(f) Preparation of 5-bromo-1,2-bis[5,10,15-trispentafluoro-
phenylporp-hyrinate zinc]benzene (compound 7, Figure 1). A
solution of 6 (0.2 g, 0.001 mol) in CHCl
was refluxed overnight with excess Zn(OAc)
mol). The solvent was then removed, the desired compound was
extracted with CHCl /water two times, and the organic layer was
dried over anhydrous sodium sulfate. The compound was further
purified with a silica-gel column using CH Cl as an eluent. The
reddish orange band was collected to give a reddish violet powder
(0.2 g, 95.9 % yield). MALDI-TOF-MS: m/z = 1896.2 (found),
1896.7 (calcd.).
3
/MeOH (50 mL, 1:1)
•4H O (0.3 g, 0.014
2
2
amount of CHCl
column and the reaction mixture was eluted with CHCl
3
, the solution was loaded into an activated Al
2
O
3
3
. The first
3
broad reddish violet band was collected. The TLC chromatography
of this band showed the presence of light red band on the top fol-
lowed by green band, strong reddish violet band then green and
black bands on the bottom. The reddish violet band was collected,
the solvent was removed, and the residue was further purified with
2
2
silica-gel column eluted with n-hexane:CH
2
Cl
2
(1:1) to give 5.0 g
(g) Preparation of 5-diethylphosphonyl-1,2-bis(5,10,15-tris-
pentafluoro-phenylporphyrinate zinc)benzene (compound 8,
Figure 1). Following reported procedures,
flask was charged with 7 (200 mg, 0.11 mmol), Pd(OAc)
mg, 0.11 mmol), triphenylphosphine (83.0 mg, 0.32 mmol), tri-
ethylamine (50 mg, 0.49 mmol), diethylphosphite, and dry
THF/EtOH (50 mL, 1:1). The whole mixture was refluxed under
of the pure compound (3) in 10.8 % isolated yield based on the
1
42,43
amount of compound 2. H NMR (CDCl
pyrrole H), 8.33 (m, 2H, Ar-H), 8.09 (dd, 1H, Ar-H), 2.86 (s, 3H,
OCH ), and −2.78 (s, 2H, por-pyrrole H). MALDI-TOF-MS: m/z
1023.0 (found), 1021.5 (calcd.).
c) Preparation of 5-(5’-bromo-2’-hydroxymethylphenyl)-
0,15,20-tris pentafluorophenylporphyrin (compound 4, Fig-
3
): δ 8.85 (d, 8H, por-β-
a 100-mL 2-necked
, (23.7
2
3
=
(
1
N
2
for 5 days. A standard workup including chromatography (sili-
ure 1). A 500-mL flask was charged with 3 (2.0 g, 0.02 mol) and dry
THF (50 mL). The solution was cooled to 0 C, then LDBBA (30
ca-gel, CH Cl /MeOH, 98:2 v/v) afforded reddish violet solid
(195 mg, 90.7 % yield). MALDI-TOF-MS: m/z = 1953.9 (found),
1953.9 (calcd.).
(h) Preparation of 5-diethylphosphonato-1,2-bis[5,10,15-tris-
pentafluoro-phenylporphyrin]benzene (compound 9, Figure
2
2
o
mL, 0.33 M solution) was added dropwise. The reaction mixture
o
was stirred for 4 h at 0 C under N
2
atmosphere, while the progress
of the reaction was monitored with TLC. After completed, the
reaction was quenched by 2 N HCl and the product was extracted
1). A CH Cl solution (50 mL) of 8 (195 mg, 0.10 mmol) was
3
with CH
2
Cl
2
. The solvent was removed and the residue was puri-
Cl as an eluent to give 4
1.94 g, 99 % yield) as a pure violet powder. H NMR (CDCl
stirred with 6M HCl solution (50 mL) for 2−h. The organic layer
fied with a silica-gel column using CH
2
2
was separated from the acidic aqueous layer, washed with aq. Na-
1
(
8
7
−
(
3
): δ
.85 (d, 8H, pyrrole β-H), 8.24 (t, 1H, Ar-H), 8.02 (dd, 1H, Ar-H),
.87 (d, 1H, Ar-H), 4.27 (s, 2H, -CH OH), 2.17 (t, 1H, -OH), and
2.87 (s, 2H, por-pyrrole H). MALDI-TOF-MS: m/z = 994.1
found), 993.5 (calcd.).
HCO
The solvent was removed and the residue was purified with a silica-
gel column using CH1Cl :MeOH (98:2) as an eluent to afford 190
mg of 9 in 98% yield. H NMR (CDCl ): δ 9.29 (dd, 6H, pyrrole β-
H), 9.02 (m, 1H, Ar-H), 8.88 (d, 1H, Ar-H), 8.82 (d, 1H, Ar-H)),
8.44 (d, 10H, pyrrole β-H), 4.60 (q, 4H, Et-CH ), 1.63 (t, 6H, Et-
3
, then with water, and then dried over anhydrous Na
2
SO
4
.
2
2
2
3
2
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