4
42
A.B. Ormond, H.S. Freeman / Dyes and Pigments 96 (2013) 440e448
reflux in pyridine (55 mL) for 1 h, cooled to room temperature, and
water bath, and then with an ice-water bath. The reaction was
slowly quenched with concentrated NH OH (40 mL). After 30 min
of stirring, the green solution was poured into 5% NaOH (70 mL),
and stirred for 1 h. The solid was collected, washed twice with
water, and dried. The purple solid was extracted with THF
ꢁ
the solution was stored at ꢂ4 C over night. The mixture was
4
filtered and the solid washed with acetone until the washings were
colorless. The purple product was dried in vacuo at room temper-
ature to give 2.87 g (30%) H
soluble in common organic solvents.
A mixture of porphyrin H (p-NO
HCl (12 M, 140 mL) was deaerated with Ar for 20 min. A solution of
SnCl $2H O (13.04 g, 58 mmol) in concentrated HCl (28 mL), also
2 2
(p-NO )TPP. The product was not
(4 ꢀ 100 mL), and the solvent was evaporated to give 0.58 g (98%) 5:
1
2
2
)TPP (2.87 g, 3.61 mmol) and
R
f
¼ 0.42 (1:2 hexane:acetone); H NMR
d e 2.96 (s, 2H), 5.46
(s, 8H), 7.00 (d, J ¼ 8.8 Hz), 7.35e7.45 (m, 12H), 8.91 (s, 8H); Q-TOF
þ
2
2
obsd 675.2986 (M þ H) , calcd 674. 2906 (M ¼ C44
34 8
H N ).
deaerated with Ar, was added to the porphyrin mixture and the
ꢁ
reaction mixture was heated using a water bath at 75e80 C for
2.1.5. 5,10,15,20-Tetrakis(meta-methanesulfonamidophenyl)
porphyrin (6)
Porphyrin 5 (0.35 g, 0.52 mmol) was combined with THF
(100 mL), methanesulfonyl chloride (0.80 mL, 10 mmol), and trie-
thylamine (1.81 mL, 13 mmol), and stirred at room temperature for
30 min. THF was evaporated and the product was stirred for 30 min
3
0 min. The hot-water bath was removed and replaced with a cold-
water bath, and then with an ice-water bath. The reaction was
slowly quenched with concentrated NH OH (180 mL) under Ar,
4
then opened to the atmosphere and stirred for 1 h. The product was
collected by filtration, added to 2% NaOH (280 mL), and stirred
vigorously for 30 min. The solid was collected, washed twice with
water, dried, Soxhlet extracted with acetone (250 mL), and
3
with saturated aqueous NaHCO (100 mL) and 5% NaOH (20 mL).
The solid was collected by filtration, washed with H
2
O (3 ꢀ 20 mL),
the solvent was evaporated to give 1.80 g (74%) 1: R
f
¼ 0.34 (1:2
and dried. The crude product was purified via column chroma-
tography on a silica gel column (2.5 ꢀ 24 cm), eluting with 4:1 to
2:3 hexane:acetone. The product fractions were combined and
hexane:acetone); 1H NMR
d
e 2.74 (s, 2H) 5.57 (s, 8H), 6.99
(
6
d, J ¼ 7.5 Hz, 8H), 7.84 (d, J ¼ 7.5 Hz, 8H), 8.87 (s, 8H); ESI-MS obsd
þ
75.2991 (M þ H) , calcd 674. 2906 (M ¼ C44
H
34
N
8
).
concentrated to give 0.35 g (69%) 6: R
f
¼ 0.22 (1:1 hexane:acetone);
1
H NMR
d e 2.94 (s, 2H), 3.64 (s, 12H), 7.70e7.82 (m, 4H), 7.98
2
.1.2. 5,10,15,20-Tetrakis(para-methanesulfonamidophenyl)
(d, J ¼ 7.7 Hz, 4H), 8.04 (m, 4H), 8.39e8.47 (m, 4H), 8.93 (br s, 8H),
þ
porphyrin (2)
10.17 (s, 4H); Q-TOF obsd 987.2082 (M þ H) , calcd 986.2008
Porphyrin 1 (0.50 g, 0.74 mmol) was combined withTHF(150mL),
methanesulfonyl chloride (1.15 mL, 15 mmol), and triethylamine
(M ¼ C48
42 8 8 4
H N O S ).
(
2.58 mL,19 mmol), and stirred at room temperature for 1 h. THF was
evaporated and the product mixture was neutralized with 5% NaOH
250 mL). The purple solid was collected by filtration, washed with
O, and dried to give 0.57 g (81%) 2: R
¼ 0.65 (1:2 hexane:acetone);
2.1.6. 5,10,15,20-Tetrakis(meta-trifluoroacetamidophenyl)
porphyrin (7)
(
2 2
Porphyrin 5 (0.35 g, 0.52 mmol) was combined with CH Cl
H
2
f
(250 mL) and pyridine (4.10 mL, 51 mmol), and then trifluoroacetic
anhydride (2.73 mL, 20 mmol) was added slowly. The reaction
mixture was stirred at room temperature for 30 min and the
solvent was evaporated to 125 mL. The mixture was poured into
1
H NMR
d
e 2.92 (s, 2H), 3.77 (s, 3H), 7.65 (d, J ¼ 8.5 Hz, 8H), 8.18
(
(
d, J ¼ 8.5 Hz, 8H), 8.88 (s, 8H), 10.28 (s, 4H); Q-TOF obsd 987.2077
þ
M þ H) , calcd 986.2008 (M ¼ C48
42 8 8 4
H N O S ).
saturated aqueous NaHCO
The organic phase was washed with H
anhydrous MgSO , and concentrated. The crude product was
3
(250 mL) and the layers were separated.
2
.1.3. 5,10,15,20-Tetrakis(para-trifluoroacetamidophenyl)
porphyrin (3)
Porphyrin 1 (0.50 g, 0.74 mmol) was combined with CH
300 mL) and pyridine (5.85 mL, 73 mmol), and then trifluoroacetic
2
O (2 ꢀ 150 mL), dried over
4
2
Cl
2
purified via column chromatography on a silica gel column
(2.5 ꢀ 24 cm), eluting with 4:1 to 3:2 hexane:ethyl acetate. The
(
anhydride (3.90 mL, 28 mmol) was added slowly. After stirring at
room temperature for 1 h, the solvent was reduced to 150 mL. The
combined product fractions were concentrated to give 0.25 g (47%)
1
7: R
f
¼ 0.54 (1:1 hexane:ethyl acetate); H NMR
d e 2.95 (s, 2H),
mixture was poured into 10% NaHCO
separated, and the product was extracted into CH
The organic layers were combined, washed with H
dried over anhydrous MgSO , and the solvent was evaporated to
give 0.70 g (89%) 3: R
¼ 0.61 (1:1 hexane:acetone); H NMR
s, 2H), 8.16 (d, J ¼ 8.4 Hz, 8H), 8.27 (d, J ¼ 8.4 Hz, 8H), 8.87 (s, 8H),
3
(300 mL), the layers were
Cl
(2 ꢀ 100 mL).
O (2 ꢀ 250 mL),
7.88 (t, J ¼ 7.9 Hz, 4H), 8.11 (m, 4H), 8.19 (d, J ¼ 8.5 Hz, 4H), 8.58 (m,
þ
2
2
4H), 8.92 (s, 8H); Q-TOF obsd 1059.2288 (M þ H) , calcd 1058.2198
2
(M ¼ C52
30 12 8 4
H F N O ).
4
1
f
d
e 2.93
2.1.7. 5,10,15,20-Tetrakis(para-hydroxyphenyl) porphyrin (4)
(
1
A solution of p-acetoxybenzaldehyde (2.26 g, 14 mmol) in pro-
pionic acid (50 mL) was brought to a reflux, and pyrrole (0.95 mL,
14 mmol) was added. After stirring for 30 min, the reaction mixture
was cooled to room temperature, and the product was collected by
filtration. The purple precipitate was washed with propionic acid
(25 mL) until the washings were colorless, and dried to give 0.56 g
þ
1.72 (s, 4H); Q-TOF obsd 1059.2276 (M þ H) , calcd 1058.2198
(
M ¼ C52 ).
30 12 8 4
H F N O
2
.1.4. 5,10,15,20-Tetrakis(meta-aminophenyl) porphyrin (5)
A solution of m-nitrobenzaldehyde (7.62 g, 50 mmol) in pro-
pionic acid (200 mL) was brought to a reflux. Pyrrole (3.39 mL,
(19%) H
Porphyrin H
with EtOH (1 mL), H
stirred at reflux for 1 h. After cooling to room temperature, the
mixture was diluted with H O (25 mL), neutralized with 5% NaOH
until the color of the green solution turned dark red and pH was 7.5.
The mixture was stirred vigorously for 1 h, ethyl acetate was added,
and the mixture stirred for 1 h. The organic layer was separated,
2
(p-OCOMe)TPP: R
(p-OCOMe)TPP (0.50 g, 0.59 mmol) was combined
O (3 mL), and concentrated HCl (1 mL), and
f
¼ 0.63 (2:1 toluene:ethyl acetate).
5
3
0 mmol) was added to the mixture and the reaction was stirred for
0 min. The reaction mixture was cooled to room temperature,
2
2
filtered, and the solid was washed with H
until the washings were colorless. The dark product was dried,
finely powdered, and 1 g portions were dissolved in CH Cl , and
passed through a silica gel column (2.8 ꢀ 9 cm) eluting with CH Cl
The collected product fractions were combined and the solvent was
evaporated to give 0.70 g (7%) H (m-NO )TPP: R Cl ).
)TPP (0.70 g, 0.88 mmol) in HCl (12 M,
2
O and then with MeOH
2
2
2
2
2
.
2
2
f
¼ 0.77 (CH
2
2
washed twice with water, dried over anhydrous MgSO
4
, and
To porphyrin H
2
(m-NO
2
concentrated to give 0.40 g (100%) 4: R
f
¼ 0.31 (2:1 toluene:ethyl
1
3
7
1
5 mL), a solution of SnCl
mL) was added, and the reaction mixture was stirred at 70 C for
h. The hot-water bath was removed and replaced with a cold-
2
$2H
2
O (3.18 g, 14 mmol) in HCl (12 M,
acetate); H NMR
(d, J ¼ 8.4 Hz, 8H), 8.86 (s, 8H), 9.96 (s, 4H); Q-TOF obsd 679.2388
d
e 2.89 (s, 2H), 7.20 (d, J ¼ 8.4 Hz, 8H), 8.00
ꢁ
þ
(M þ H) , calcd 678.2267 (M ¼ C44
30 4 4
H N O ).