PAPER
Synthesis of Octaglycosylated Zinc(II) Phthalocyanines
3101
H-3¢), 3.85–3.72 (m, 6 H, H-4, H-5, H-5¢), 2.09, 2.08, 2.04, 2.01,
1.98, 1.90, 1.87 (7 s, 7 × 6 H, CH3).
13C NMR (100 MHz, CDCl3): d = 20.7, 20.8, 20.9, 21.0, 21.1, 21.2,
61.2, 67.0, 69.2, 69.3, 69.4, 69.9, 70.8, 71.1, 71.2, 76.4, 95.9, 101.5,
111.0, 115.3, 119.9, 150.1, 168.9, 169.1, 169.4, 169.9, 170.3, 170.7,
171.5.
and concentrated in vacuo. The obtained syrup purified by column
chromatography over silica gel using toluene–acetone (5:1) as sol-
vent to afford 3b as a white solid; yield: 5.54 g (65%); mp 226–
230 °C; [a]D20 –79.2 (c 0.5, CHCl3).
1H NMR (400 MHz, CDCl3): d = 7.87 (s, 2 Harom), 5.24 (t, J4,3 = J4,5
=
9.9 Hz, 2 H, H-4), 5.07 (dd, J2,3 = 10.2 Hz, J3,4 = 9.9 Hz, 4 H, H-2,
H-3), 4.81 (d, J1,2 = 10.2 Hz, 2 H, H-1), 4.16 (d, J = 4.3 Hz, 4 H, H-
6a,b), 3.84–3.79 (m, 2 H, H-5), 2.13, 2.06, 2.02, 1.98 (4 s, 4 × 6 H,
CH3).
HRMS (FT-ICR): m/z [M + Na]+ calcd for C60H72N2O36 + Na:
1419.3763; found: 1419.37678.
Anal. Calcd for C60H72N2O36: C, 51.58; H, 5.19; N, 2.00. Found: C,
51.62; H, 5.10; N, 1.95.
13C NMR (100 MHz, CDCl3): d = 20.9, 21.0, 21.2, 62.5, 68.2, 69.7,
73.7, 76.7, 84.1, 114.6, 115.3, 134.4, 142.9, 169.6, 169.7, 170.3,
171.0.
4,5-Di(2,3,6,2¢,3¢,4¢,6¢-hepta-O-acetyl-a-D-cellobiose)phthalo-
nitrile (3g)
HRMS (FT-ICR): m/z [M + Na]+ calcd for C36H40N2O18S2 + Na:
Prepared from 2,3,6,2¢,3¢,4¢,6¢-hepta-O-acetyl-a-D-cellobiose (1g,
2.54 g, 4 mmol) as described for compound 3a. Purification was
carried out by column chromatography using hexane–EtOAc (2:5)
to afford the product as a white solid; yield: 2.92 g (74%); mp 150–
155 °C; [a]D20 +97.6 (c 0.5, CHCl3).
1H NMR (400 MHz, CDCl3): d = 7.47 (s, 2 Harom), 5.65 (d, J1,2 = 3.3
Hz, 2 H, H-1), 5.51 (t, J3,2 = J3,4 = 10.2 Hz, 2 H, H-3), 5.07 (t,
875.1615; found: 875.16136.
Anal. Calcd for C36H40N2O18S2: C, 50.70; H, 4.73; N, 3.28. Found:
C, 50.75; H, 4.69; N, 3.41.
4,5-Di(2,3,4,6-tetra-O-acetyl-1-thio-b-D-galactopyrano-
syl)phthalonitrile (3d)
Prepared from 2,3,4,6-tetra-O-acetyl-1-thio-b-D-galactopyranose
(1d, 1.46 g, 4 mmol) as described for compound 3b. Column chro-
matography was carried out by using hexane–EtOAc (1:1) to afford
J3¢,2¢ = 9.2 Hz, 4 H, H-4¢, H-3¢), 4.98 (dd, J2,3 = 10.2 Hz, J2,1 = 3.3
Hz, 2 H, H-2), 4.77 (t, J4,5 = 9.2 Hz, 2 H, H-4), 4.39 (br d, J1¢,2¢ = 8.1
Hz, 2 H, H-1¢), 4.36–4.32 (m, 4 H, H-2¢, H-6b¢), 4.08–3.97 (m, 4 H,
H-6a, H-6a¢), 3.72–3.60 (m, 6 H, H-6b, H-5, H-5¢), 2.10, 2.06, 2.04,
1.96, 1.95, 1.90, 1.89 (7 s, 7 × 6 H, CH3).
20
3d as a white solid; yield: 1.36 g (80%); mp 108–112 °C; [a]D
–18.8 (c 0.5, CHCl3).
1H NMR (400 MHz, CDCl3): d = 7.99 (s, 2 Harom), 5.46 (d, J4,3 = 3.1
Hz, 2 H, H-4), 5.29 (t, J2,1 = J2,3 = 9.9 Hz, 2 H, H-2), 5.08 (dd,
J3,2 = 9.9 Hz, J3,4 = 3.1 Hz, 2 H, H-3), 4.78 (d, J1,2 = 9.9 Hz, 2 H, H-
1), 4.17–4.00 (m, 6 H, H-5, H-6a,b), 2.19, 2.08, 2.06, 1.96 (4 s, 4 × 6
H, CH3).
13C NMR (100 MHz, CDCl3): d = 20.9, 21.0, 21.1, 21.4, 62.5, 66.6,
67.5, 71.9, 75.8, 84.5, 114.2, 115.5, 134.5, 142.8, 169.8, 170.2,
170.4, 170.9.
13C NMR (100 MHz, CDCl3): d = 20.7, 20.8, 20.9, 21.0, 21.1, 21.2,
61.8, 62.0, 68.1, 68.9, 69.7, 70.6, 70.9, 71.7, 72.3, 73.2, 95.9, 101.2,
111.0, 115.3, 119.4, 150.4, 169.0, 169.4, 169.9, 170.5, 170.7, 171.6.
HRMS (FT-ICR): m/z [M + Na]+ calcd for C60H72N2O36 + Na:
1419.3763; found: 1419.37746.
Anal. Calcd for C60H72N2O36: C, 51.58; H, 5.19; N, 2.00. Found: C,
51.46; H, 5.29; N, 1.89.
HRMS (FT-ICR): m/z [M + Na]+ calcd for C36H40N2O18S2 + Na:
4,5-Di(2,3,6,2¢,3¢,4¢,6¢-hepta-O-acetyl-a-D-maltose)phthalo-
nitrile (3i)
875.1615; found: 875.16055.
Anal. Calcd for C36H40N2O18S2: C, 50.70; H, 4.73; N, 3.28. Found:
C, 50.43; H, 4.47; N, 3.13.
Prepared from 2,3,6,2¢,3¢,4¢,6¢-hepta-O-acetyl-a-D-maltose (1i;
2.54 g, 4 mmol) as described for compound 3a. Purification was
carried out by column chromatography using hexane–EtOAc (2:5)
to afford the product as a white solid; yield: 1.86 g (62%); mp 128–
131 °C; [a]D20 +213.8 (c 0.8, CHCl3).
1H NMR (400 MHz, CDCl3): d = 7.62 (s, 2 Harom), 5.79 (d, J1,2 = 3.8
Hz, 2 H, H-1), 5.61 (t, J3¢,4¢ = 9.9 Hz, 2 H, H-3¢), 5.32 (d, J1¢,2¢ = 4.0
Hz, 2 H, H-1¢), 5.26 (t, J3,2 = J3,4 = 10.2 Hz, 2 H, H-3), 5.05–5.01
(m, 4 H, H-2¢, H-4¢), 4.86 (dd, J2,3 = 10.2 Hz, J2,1 = 3.8 Hz, 2 H, H-
2), 4.43 (br d, J = 10.7 Hz, 2 H, H-6a), 4.23–4.19 (m, 4 H, H-5¢, H-
6b), 4.05–3.94 (m, 8 H, H-4, H-5, H-6a¢,6b¢), 2.11, 2.08, 2.07, 2.04,
2.01, 1.98, 1.96 (7 s, 7 × 6 H, CH3).
13C NMR (100 MHz, CDCl3): d = 20.8, 20.9, 21.0, 21.1, 21.2, 61.8,
63.0, 68.3, 69.1, 69.4, 70.3, 70.4, 71.9, 74.1, 77.1, 95.9, 96.8, 111.0,
115.3, 119.9, 150.1, 168.9, 169.1, 169.4, 169.9, 170.3, 170.7, 171.5.
HRMS (FT-ICR): m/z [M + Na]+ calcd for C60H72N2O36 + Na:
1419.3763; found: 1419.37527.
4,5-Di(2,3,6,2¢,3¢,4¢,6¢-hepta-O-acetyl-1-thio-b-D-lactose)phtha-
lonitrile (3f)
Prepared from 2,3,6,2¢,3¢,4¢,6¢-hepta-O-acetyl-1-thio-b-D-lactose
(1f, 2.60 g, 4 mmol) as described for compound 3b. Purification was
carried out by column chromatography using hexane–EtOAc (1:2)
to afford 3f as a white solid; yield: 1.57 g (55%); mp 140–145 °C;
[a]D20 –47.2 (c 0.8, CHCl3).
1H NMR (400 MHz, CDCl3): d = 7.83 (s, 2 Harom), 5.33 (d,
J4¢,3¢ = 3.6 Hz, 2 H, H-4¢), 5.21 (t, J3,2 = J3,4 = 8.9 Hz, 2 H, H-3), 5.07
(dd, J2,1 = 10.2, J2,3 = 8.9 Hz, 2 H, H-2), 4.92 (m, 4 H, H-2¢, H-3¢),
4.75 (d, J1,2 = 10.2, Hz, 2 H, H-1), 4.50 (br d, J6b,6a = 11.9 Hz, 2 H,
H-6b), 4.47 (d, J1¢,2¢ = 7.9 Hz, 2 H, H-1¢), 4.09–4.05 (m, 6 H, H-6a,
H-6a¢,b¢), 3.86 (t, J5¢,6a¢ = 6.6 Hz, 2 H, H-5¢), 3.78–3.71 (m, 4 H, H-
4, H-5), 2.15, 2.11, 2.04, 2.03, 2.01, 1.93 (6 s, 42 H, CH3).
13C NMR (100 MHz, CDCl3): d = 20.8, 20.9, 21.0, 21.1, 21.2, 61.2,
62.5, 69.4, 69.9, 70.8, 71.2, 71.3, 73.6, 76.1, 77.1, 83.9, 101.5,
114.5, 115.3, 134.4, 142.8, 169.4, 169.8, 169.9, 170.4, 170.7, 170.8.
Anal. Calcd for C60H72N2O36: C, 51.58; H, 5.19; N 2.00. Found: C,
51.73; H, 5.01; N, 2.04.
HRMS (FT-ICR): m/z [M + Na]+ calcd for C60H72N2O34S2 + Na:
Phthalonitriles 3b,d,f,h; 4,5-Di(2,3,4,6-tetra-O-acetyl-1-thio-b-
D-glucopyranosyl)phthalonitrile (3b); Typical Procedure
Bu4NOH (14 mL, 20 mmol) was added to a mixture of 4,5-difluo-
rophthalonitrile (2b; 1.64 g, 10 mmol) and 2,3,4,6-tetra-O-acetyl-1-
thio-b-D-glucopyranose (1b; 7.29 g, 20 mmol) in CH2Cl2 (20 mL).
The reaction mixture was stirred at r.t. for 48 h, diluted with H2O
(200 mL) and extracted with CH2Cl2 (2 × 100 mL). The combined
organic phases were washed with H2O (200 mL), dried (MgSO4),
1451.3306; found: 1451.32976.
Anal. Calcd for C60H72N2O34S2: C, 50.42; H, 5.08; N, 1.96. Found:
C, 50.41; H, 5.12; N, 1.85.
4,5-Di(2,3,6,2¢,3¢,4¢,6¢-hepta-O-acetyl-1-thio-b-D-cello-
biose)phthalonitrile (3h)
Prepared from 2,3,6,2¢,3¢,4¢,6¢-hepta-O-acetyl-1-thio-b-D-cello-
biose (1h, 2.60 g, 4 mmol) as described for compound 3b. Purifica-
Synthesis 2010, No. 18, 3097–3104 © Thieme Stuttgart · New York