Molecules 2017, 22, 845
9 of 13
3
.2.3. Acetyl-Protected Counterpart (6a)
To a mixture of compound (0.15 g, 0.20 mmol) and 4a (0.10 g, 0.24 mmol) in CHCl /EtOH/H O
7 mL, v/v/v = 12:1:1) were added CuSO4 5H O (10 mg, 0.040 mmol) and ascorbate sodium (16 mg,
2
3
3
2
(
·
0.081 mmol). The mixture was stirred at room temperature for 24 h. Then H O (30 mL) was added to
2
the reaction mixture and the solution was extracted with CHCl (3
extracts were washed by saturated brine, and dried over anhydrous Na SO . The crude product was
×
30 mL). The combined organic
3
2
4
purified by silica gel chromatography (CHCl /MeOH = 5:1, v/v) to afford blue-green solid 6a (0.13 g,
3
1
5
6%). H-NMR (400 MHz, DMSO-d ):
δ
8.93–9.18 (m, 6H, Pc-H
α
), 8.71 (br s, 1H, Pc-H
α
), 8.26 (br s,
6
1
H, Pc-H
J = 9.6 Hz, 1H, CH), 4.90 (t, J = 9.6 Hz, 1H, CH), 4.73–4.83 (m, 2H, CH ), 4.49–4.61 (m, 6H, CH ), 4.16
α
), 8.02–8.16 (m, 6H, Pc-H ), 7.97 (s, 1H, triazole-H), 7.47 (d, J = 8.4 Hz, 1H, Pc-H ), 5.23 (t,
β
β
2
2
(
dd, J = 4.8 Hz, 12.4 Hz, 1H, CH), 3.91–4.12 (m, 6H, 2CH , 2CH), 3.86 (vt, J = 4.8 Hz, 2H, CH ), 3.74 (t,
2 2
J = 4.8 Hz, 2H, CH ), 3.64–3.69 (m, 4H, CH ), 2.01 (s, 3H, CH ), 1.97 (s, 3H, CH ), 1.92 (s, 6H, CH );
2
2
3
3
3
+
HRMS (ESI): m/z calcd. for C H N NaO Zn [M + Na] : 1202.2963, found 1202.2934.
57
53 11
14
3
.2.4. Acetyl-Protected Counterpart (6b)
According to the procedure described for 6a, compound
3
(0.15 g, 0.20 mmol) was treated with 4b
(
0.12 g, 0.24 mmol), CuSO4
·
5H O (10 mg, 0.040 mmol) and ascorbate sodium (16 mg, 0.081 mmol) to
2
1
give 6b as a blue-green solid (0.16 g, 63%). H-NMR (400 MHz, DMSO-d ): 8.87–9.13 (m, 6H, Pc-H
α
),
6
8
.68 (br s, 1H, Pc-H
α
), 7.98–8.23 (m, 8H, 1 triazole-H, 1 Pc-H
α
, 6 Pc-H ), 7.46 (br s, 1H, Pc-H ), 5.25
β
β
(
t, J = 9.6 Hz, CH), 4.90 (t, J = 9.6 Hz, CH), 4.73–4.82 (m, 2H, CH ), 4.53–4.60 (m, 4H, CH ), 4.50 (t,
2
2
J = 4.8 Hz, 2H, CH ), 4.17 (dd, J = 4.8 Hz, 12.4 Hz, 1H, CH), 4.06–4.12 (m, 2H, CH ), 3.98–4.04 (m, 1H,
2
2
CH), 3.93–3.98 (m, 1H, CH), 3.85 (t, J = 4.8 Hz, 2H, CH ), 3.79 (t, J = 5.2 Hz, 2H, CH ), 3.74 (t, J = 5.2 Hz,
2
2
2
H, CH ), 3.63–3.72 (m, 4H, CH ), 3.52–3.59 (m, 2H, CH ), 3.41–3.49 (m, 6H, CH ), 2.01 (s, 3H, CH ),
2 2 2 2 3
1
.97 (s, 3H, CH ), 1.96 (s, 3H, CH ), 1.93 (s, 3H, CH ). HRMS (ESI): m/z calcd. for C H N O Zn
3 3 3 61 63 11 16
2+
+
[M + 2H] : 634.6867, found 634.6856; m/z calcd. for C H N O Zn [M + H] : 1268.3667, found
61 62 11 16
1
268.3629.
3
.2.5. Glucosylated Zinc(II)-phthalocyanine (7a)
According to the procedure described for 6a, compound
3
(0.15 g, 0.20 mmol) was treated with the
deprotected glucose 5a (0.10 g, 0.40 mmol), CuSO4
·
5H O (10 mg, 0.040 mmol) and ascorbate sodium
2
1
(16 mg, 0.081 mmol) to give 7a as a blue-green solid (0.11 g, 56%). H-NMR (400 MHz, DMSO-d ):
6
δ
9.37–9.48 (m, 6H, Pc-H
α
), 9.27 (d, J = 8.0 Hz, 1H, Pc-H
α
), 8.91 (s, 1H, Pc-H
α
), 8.20–8.28 (m, 6H,
Pc-H ), 8.18 (s, 1H, triazole-H), 7.79 (d, J = 8.0 Hz, 1H, Pc-H ), 5.13–5.18 (m, 1H, CH), 5.06–5.10 (m,
β
β
1
H, CH), 5.02–5.06 (m, 1H, CH), 4.67–4.72 (m, 2H, CH ), 4.53–4.62 (m, 6H, CH ), 4.23–4.28 (m, 2H,
2 2
CH ), 4.03–4.10 (m , 3H, CH, CH ), 3.86–3.93 (m, 1H, CH), 3.74–3.81 (m, 2H, CH ), 3.67 (t, J = 4.4 Hz,
2
2
2
2
H, CH ), 3.61–3.65 (m, 4H, CH ), 3.53–3.58 (m, 2H, CH ), 3.02–3.18 (m, 3H, OH), 2.93–3.00 (m, 1H,
2 2 2
+
OH); HRMS (ESI): m/z calcd. for C H N O Zn [M + H] : 1012.2715, found 1012.2705.
49
46 11 10
3
.2.6. Glucosylated Zinc(II)-phthalocyanine (7b)
According to the procedure described for 6a, compound 3 (0.15 g, 0.20 mmol) was treated with
deprotected glucose 5b (0.14 g, 0.42 mmol), CuSO ·5H O (10 mg, 0.040 mmol) and ascorbate sodium
4
2
1
(
16 mg, 0.081 mmol) to give 7b as a blue-green solid (0.13 g, 59%). H-NMR (400 MHz, DMSO-d ):
6
9
.12–9.35 (m, 6H, Pc-H
α
), 8.96 (br s, 1H, Pc-H
α
), 8.55 (br s, 1H, Pc-H ), 8.09–8.26 (m, 6H, Pc-H ), 8.06
β
β
(
s, 1H, triazole-H), 7.61 (br s, 1H, Pc-H ), 4.95–5.00 (m, 1H, CH), 4.86–4.94 (m, 2H, CH), 4.59–4.68 (m,
β
2
H, CH ), 4.58 (br s, 2H, CH ), 4.45–4.54 (m, 3H, CH, CH ), 4.12–4.17 (m, 1H, CH), 4.03–4.09 (m, 2H,
2 2 2
CH ), 3.76–3.85 (m, 4H, CH ), 3.68–3.73 (m, 2H, CH ), 3.61–3.67 (m, 4H, CH ), 3.47–3.58 (m, 10H, CH ),
2
2
2
2
2
+
3
.01–3.17 (m, 3H, OH), 2.92–3.00 (m, 1H, OH); HRMS (ESI): m/z calcd. for C H N O Zn [M + H] :
53 54 11 12
1
100.3239, found 1100.3223.