10
M. MALACHOWSKA ET AL.
followed by addition of TFA (46 ml, 0.48 mmol). The
reaction mixture was stirred overnight at rt, shielded from
light and then it was quenched by the addition of a saturated
6b. 5 (163 mg: 0.138 mmol) and 2,4,6-trifluro-
benzaldehyde (22 mg; 0.138 mmol), TFA (13 ml; 0.138
mmol), Et N (19.2 ml; 0.138 mmol), DDQ (66 mg; 0.29
3
aqueous solution of NaHCO (10 mL). The mixture
mmol). Yield 34 mg; 18.7% of the violet-red amorphous
3
1
was extracted with dichloromethane, organics dried
solid 6b. H NMR (CDCl ): d, ppm 9.98 (br, 4H), 9.02
3
with MgSO and concentrated under reduced pressure.
(br, 4H), 8.40 (d, 4H, J = 6.0 Hz), 8.25 (d, 4H, J = 6.0 Hz),
7.84–7.81 (m, 5H), 7.74–7.66 (m, 14H), 7.59–7.28 (m,
25H), 7.25–7.16 (m, 10H), 6.81 (t, 2H, J = 9.0 Hz), 6.52
(d, 2H, J = 3.0 Hz), 6.45–6.36 (m, 8H), 5.77 (m, 4H),
5.62 (dd, 2H, J = 3.5 Hz), 5.02 (m, 4H), 4.5 (dd, 2H, J =
3.0 Hz), 4.34 (dd, 2H, J = 3.0 Hz). For C H F N O
4
The residue was purified by column chromatography
(
hexane:ethyl acetate 7:2) to afford 0.47 g (82.6%) of as
1
amorphous solid 5. H NMR (CDCl ): d, ppm 9.23 (br,
3
2H), 8.77 (br, 2H), 8.12–7.99 (m, 6H), 7.98–7.91 (m, 3H),
7.88–7.76 (m, 10H), 7.61–7.27 (m, 12H) 7.26–7.16 (m,
4H), 6.71–6.69 (m, 1H), 6.47–6.44 (m, 1H), 6.18–6.03
1
52 108
6
4
34
+
calcd. monoisotopic mass: 2646.67; found MS-ESI : m/z
+
(
5
4
m, 4H), 6.04–5.79 (m, 6H), 5.4 (dd, 1H, J = 3.5 Hz),
2648.72 [M + 2H] .
.16–5.11 (m, 1H) 4.77–4.71 (m, 4H), 4.57–4.53 (m, 2H),
.27–4.22 (m, 1H). For C H N O calcd. monoisotopic
6c. 5 (132 mg: 0.111 mmol) and 4-flurobenzaldehyde
(14 mg; 0.111 mmol), TFA (13 ml; 0.111 mmol), Et N
69
56
+
2
17
3
+
mass: 1184.35, found MS-ESI : m/z 1207.35 [M + Na] .
(15.4 ml; 0.111 mmol), DDQ (53 mg; 0.24 mmol). Yield
1
Synthesis of porphyrin-sucrose derivatives (6a–
36 mg; 25.1% of the violet-red amorphous solid 6c. H
6
h). To the solution of 5 (1 equiv.) in anhydrous dichloro-
NMR (CDCl ): d, ppm 9.94 (br, 4H), 8.96 (br, 1H), 8.39
3
methane was added the relevant aldehyde (1 equiv.) and
Ar was bubbled through the mixture for 10 min. Then
TFA (1 equiv.) was added and the reaction was stirred
overnight at rt, shielded from light under an inert Ar
atmosphere. Then triethylamine (1 equiv.) and DDQ
(d, 4H, J = 6.0 Hz), 8.25 (d, 4H, J = 6.0 Hz), 8.3–7.93
(m, 5H), 7.87–7.84 (m, 5H), 7.76–7.73 (m, 5H), 7.59–
7.53 (m, 12H), 7.47–7.34 (m, 15H), 7.34–7.28 (m, 12H),
7.26–7.16 (m, 7H), 7.08–7.02 (m, 5H), 6.98–6.93 (t, 4H,
J = 9.0 Hz), 6.90 (t, 4H, J = 9.0 Hz), 6.79 (t, 4H, J =
9.0 Hz), 6.49 (m, 3H), 6.41 (m, 2–3H), 5.72 (m, 4H),
5.56 (dd, 2H, J = 3.5 Hz), 5.12–5.05 (m, 2H), 5.01–4.97
(m, 4H), 4.42–4.35 (m, 2H), 4.19–4.09 (m, 2H). For
C H F N O calcd. monoisotopic mass: 2574.71
(
2.1 equiv.) were added and the stirring was continued
for an additional 2 h. After this time, Na CO and silica
2
3
gel was added and the solvent was evaporated under
reduced pressure. The resulting solid was loaded onto
the top of the chromatographic column and eluted with
hexane:ethyl acetate to afford as a red-violet amorphous
solid. All porphyrin derivatives were purified using the
same eluent: gradient starting from hexane: ethyl acetate
1
52 112
2
4
34
+
+
found MS-ESI : m/z 2576.72 [M + 2H] .
6d. 5 (176 mg: 0.149 mmol) and benzaldehyde (16 mg;
0.149 mmol), TFA (14 ml; 0.149 mmol), Et N (15 ml;
3
0.149 mmol), DDQ (71 mg; 0.314 mmol). Yield 41 mg;
1
8
:1 increasing slowly polarity ending on 7:2 (v/v).
21.7% of the violet-red amorphous solid 6d. H NMR
Typical procedure — synthesis of porphyrin (6a).
(CDCl ): d, ppm 9.9 (br, 4H), 8.97 (br, 4H), 8.43 (d, 4H,
3
Ar was bubbled through the solution of 5 (174 mg; 0.147
mmol; 1 equiv.) in anhydrous dichloromethane (5 mL)
and pentafluorobenzaldehyde (29 mg; 0.147 mmol, 1
equiv.) for 10 min. The reaction mixture was shielded
from light and TFA (15 ml: 0.147 mmol) was added. The
stirring was continued overnight at rt. The disappearance
of the starting material was monitored by TLC (hexane:
ethyl acetate 7:4), then triethylamine (20 ml: 0.147
mmol) and DDQ (70 mg; 0.31 mmol, 2.1. equiv.) were
added. The reaction was stirred at rt for 2 h, followed by
addition of Na CO (15.6 mg: 0.147 mmol) and silica gel
J = 6.0 Hz), 8.27 (d, 4H, J = 6.0 Hz), 8.08 (d, 5H, J =
6.0 Hz), 7.85–7.83 (m, 5H), 7.77–7.67 (m, 10H), 7.64–
7.32 (m, 35H), 7.32–7.28 (m, 5H), 7.24–7.08 (m, 7H),
6.66 (m, 4H), 6.51 (m, 2H), 6.43–6.39 (m, 1H), 6.37 (d,
2H, J = 3.0 Hz), 5.72–5.63 (m, 4H), 5.53 (dd, 2H, J =
3.5 Hz), 5.08–5.04 (m, 2H), 4.98–4.93 (m, 2H), 4.39–
4.34 (m, 2H), 4.21–4.16 (m, 2H). For C H N O
1
52 114
4
34
+
calcd. monoisotopic mass: 2538.73; found MS-ESI : m/z
+
2540.77 [M + 2H] .
6e. 5 (110 mg; 0.093 mmol), propionaldehyde (7 ml;
0.093 mmol), TFA (10 ml, 0.085 mmol), Et N (13 ml,
2
3
3
(
1 g). The solid was put on the top of the short column
0.093 mmol), DDQ (44 mg, 0.02 mmol). Purification by
column chromatography with hexane:ethyl acetate (7:2).
and chromatographed in hexane:ethyl acetate 8:1 to 7:2
to obtain 57 mg (28.5%) of the violet-red amorphous
Yield 17 mg; 15% of the violet-red amorphous solid 6e.
1
1
solid 6a. H NMR (CDCl ): d, ppm 10.06 (br, 4H),
H NMR (CDCl ): d, ppm 9.99 (br, 4H), 9.96 (br, 4H),
3
3
9
6
7
6
.04 (br, 4H), 8.38 (d, 4H, J = 6.0 Hz), 8.21 (d, 4H, J =
.0 Hz), 7.86 (d, 4H, J = 6.0 Hz), 7.78–7.67 (m, 15H),
.6–7.38 (m, 24H), 7.33–7.19 (m, 14H), 7.14 (t, 4H, J =
.0 Hz), 7.04–6.96 (m, 4H), 6.71 (t, 4H, J = 6.0 Hz), 6.5
8.44 (d, 4H, J = 6.0 Hz), 8.28 (d, 4H, J = 6.0 Hz), 7.94 (d,
5H, J = 6.0 Hz), 7.78–7.71 (m, 6H), 7.62–7.49 (m, 20H),
7.49–7.39 (m, 12H), 7.34–7.30 (m, 5H), 7.25–7.22 (m,
4H), 7.16–7.05 (m, 10H), 6.90–6.85 (m, 4H), 6.82–6.77
(m, 4H), 6.63–6.56 (m, 2H), 6.51 (d, 2H, J = 3.0 Hz), 6.43
(d, 2H, J = 6.0 Hz), 5.78 (t, 2H, J = 9 Hz), 6.66–6.62 (m,
2H), 5.59 (dd, 2H, J = 3.5 Hz), 5.19–5.14 (m, 2H), 5.10
(dt, 2H, J = 3.0 Hz), 4.94–4.87 (m, 4H), 4.44 (dd, 2H,
J = 3.0 Hz), 4.19 (m, 1H), 2.06–2.01 (m, 6H), 1.17–1.13
(
9
d, 2H, J = 3.0 Hz), 6.42–6.35 (m, 4H), 5.84 (t, 2H, J =
.0 Hz), 5.04–4.94 (m, 4H), 4.73 (dd, 2H, J = 3.5 Hz). For
C H F N O calcd. monoisotopic mass: 2718.63;
1
52 104 10
4
34
+
+
found MS-ESI : m/z 2718.63 [M + H] , 2758.64 [M +
H + K] .
+
Copyright © 2016 World Scientific Publishing Company
J. Porphyrins Phthalocyanines 2016; 20: 10–12