1.5 equiv.). Green oily derivative; Rf 0.50 (25 : 1 CH2Cl2–
EtOH). 1H NMR (CDCl3): d 8.10–7.10 (m, 35H, 7 C6H5),
5.85 (dd, 1H, J2,3 9.8, J3,4 9.1 Hz, H-3), 5.72 (m, 2H, H-20,
H-5, H-6b), 4.00–3.70 (m, 12H, 6OCH2), 3.60–3.10 (m, 12H,
6SCH2), 2.14, 2.11, 2.03, 1.98 (4s, 12H, 4CH3COO), 2.10–1.95
(m, 12H, 6SCH2CH2), 1.85–1.72 (m, 12H, 6 SCH2CH2CH2),
1.60–1.45 (m, 24 H, 12CH2 alkyl chains), 1.10–0.97 (m, 18H,
6CH3 alkyl chains). 13C NMR (CDCl3): d 170.75, 170.08,
169.93, 169.77 (CQO), 124.23 (NCHQC), 96.89 (C-1), 71.09,
70.79, 70.72, 70.29, 69.57 (OCH2), 69.54 (C-2), 69.14 (C-3),
68.76 (C-5), 66.14 (C-4), 62.43 (C-6), 61.01 (CH2OCQ), 33.89,
31.98, 29.32, 29.28, 22.89, 22.85 (CH2 alkyl chains), 20.95,
20.86, 20.77, 20.75 (CH3COO), 14.36 (CH3 alkyl chains).
HRMS (ESI) calc. for C93H125N11NiO14S6,1869.7085; found
1869.7066.
H-40), 5.48 (dd, 1H, J1,2 7.9 Hz, H-2), 5.37 (dd, 1H, J2 ,3 10.3,
0
0
0
0
0
0
0
J3 ,4 3.0 Hz, H-3 ), 4.88 (d, 1H, H-1), 4.82 (d, 1H, J1 ,2 7.9 Hz,
H-10), 4.65–4.50 (m, 3H, H-6a, CH2OC6H3), 4.49 (dd, 1H,
J5,6b 3.8, J6a,6b 11.8 Hz, H-6b), 4.25 (dd, 1H, J4,5 10.0 Hz,
H-4), 4.22–4.15 (m, 2H, C-1OCH2), 3.98–3.45 (m, 16H,
6OCH2, H-5, H-50, H-60a, H-60b), 3.40–3.05 (m, 12H,
6SCH2), 2.12–1.92 (m, 12H, 6SCH2CH2), 1.85–1.67 (m, 12H,
6SCH2CH2CH2), 1.60–1.40 (m, 24H, 12CH2 alkyl chains),
1.10–0.97 (m, 18H, 6CH3 alkyl chains). 13C NMR (CDCl3):
d 165.91, 165.63, 165.48, 165.31, 165.29, 165.24 (COC6H5),
133.62, 133.47, 128.71–128.32 (C6H5), 101.40 (C-1), 101.10
(C-10), 76.13 (C-4), 73.12 (C-3), 72.99 (C-5), 71.86 ( Cꢂ2, C-30),
71.47 (C-50), 69.98 (C-20), 67.60 (C-40), 70.97, 70.78, 70.66,
70.33, 70.20, 69.55 (OCH2), 67.96 (CH2OC6H3), 62.49 (C-6),
61.13 (C-60), 33.91, 31.96, 29.90, 29.33, 28.88, 22.36 (CH2 alkyl
chains), 14.37 (CH3 alkyl chains). MS (Maldi) calc. for
[2,3,9,10,16,17-Hexa-(1-hexylthio)-23-((1-(1,4,7,10-tetra-
oxadodecyl)-1H-1,2,3-triazol-4-yl)methyl 2,3,4,6-tetra-O-acetyl-
b-D-galactopyranoside)] phthalocyaninato nickel (18). Obtained
in 95% yield, following method 2, from propargyl 2,3,4,6-
tetra-O-acetyl-b-D-galactopyranoside (14) (16 mg, 41 mmol)
and phthalocyanine 5 (52 mg, 35 mmol). 62 mg; green oily
derivative; Rf 0.34 (20 : 1 CH2Cl2–EtOH). HRMS (ESI) calc.
C
132H152N8Ni1O22S6, 2510.87; found 2510.90.
1
for C93H125N11NiO14S6,1869.7085; found, 1869.7067. H NMR
[2,3,9,10,16,17-Hexa-(1-hexylthio)-23-((1-(1,4,7,10-tetra-
(CDCl3): d 7.73 (s, 1H, QCH), 5.39 (dd, 1H, J3,4 3.4, J4,5
0.5 Hz, H-4), 5.28 (dd, 1H, J1,2 7.9, J2,3 10.4 Hz, H-2), 5.01
(dd, 1H, H-3), 4.97 and 4.82 (2d, 2H, J 12.5 Hz, OCH2CQ),
4.67 (d, 1H, H-1), 4.63–4.53 (m, 2H, CH2N), 4.30–4.20 (m,
2H, C6H3OCH2), 4.16 (d, 2H, J5,6a 6.4, J5,6b 6.4 Hz, H-6a,
H-6b), 4.00–3.65 (m, 13H, H-5, 6OCH2), 3.50–3.05 (m, 12H,
6SCH2) 2.15, 2.05, 1.99, 1.97 (4s, 12H, 4CH3COO), 2.10–1.95
(m, 12H, 6SCH2CH2), 1.85–1.68 (m, 12H, 6SCH2CH2CH2),
1.60–1.45 (m, 24H, 12CH2 alkyl chains), 1.10–0.97 (m, 18H,
6CH3 alkyl chains). 13C NMR (CDCl3): d 170.53, 170.33,
170.176, 169.51 (CH3COO), 144.09 (C = quat), 124.09
(NCHQC), 100.53 (C-1), 70.97 (C-3), 70.92 (C-5), 71.13,
70.88, 70.81, 70.77, 69.62 (OCH2), 68.89 (C-2), 67.17 (C-4),
62.91 (CH2CQ), 61.35 (C-6), 50.50 (CH2N), 33.96, 32.02,
31.98, 29.82, 29.46, 29.37, 29.04, 28.95, 22.94, 22.89 (CH2
alkyl chains), 20.87, 20.82, 20.79, 20.69 (CH3CO), 14.56 (CH3
alkyl chains).
oxadodecyl)-1H-1,2,3-triazol-4-yl)methyl 2,3,4,6-tetra-O-acetyl-
b-D-glucopyranoside)]phthalocyaninato nickel (16). Obtained
in 95% yield, following method 2, from propargyl 2,3,4,6-
tetra-O-acetyl-b-D-glucopyranoside (12) (27.6 mg, 72 mmol)
and phthalocyanine 5 (88 mg, 60 mmol). 105 mg; green oily
1
derivative; Rf 0.34 (20 : 1 CH2Cl2–EtOH). H NMR (CDCl3):
d 7.76 (s, 1H,QCH), 5.19 (dd, 1H, J2,3 9.6, J3,4 9.1 Hz, H-3),
5.09 (dd, 1H, J4,5 9.9 Hz, H-4), 5.01 (dd, 1H, J1,2 7.9 Hz H-2),
4.95 and 4.83 (2d, 2H, J 12.5 Hz, OCH2CQ), 4.70 (d, 1H,
H-1), 4.61–4.55 (m, 2H, CH2N), 4.27 (dd, 1H, J5,6a 4.6, J6a,6b
12.3 Hz, H-6a), 4.26–4.20 (m, 2H, C6H3OCH2), 4.14 (d, 1H,
J5,6b 1.8 Hz, H-6b), 4.00–3.65 (m, 13H, H-5, 6OCH2),
3.60–3.00 (m, 12H, 6SCH2), 2.09, 2.01, 1.99, 1.99 (4s, 12H,
4CH3COO), 2.10–1.95 (m, 12H, 6SCH2CH2), 1.85–1.72 (m,
12H, 6SCH2CH2CH2), 1.60–1.45 (m, 24H, 12CH2 alkyl
chains), 1.10–0.97 (m, 18H, 6CH3 alkyl chains). 13C NMR
(CDCl3): d 170.73, 170.25, 169.51, 169.43 (COCH3), 124.09
(QCH), 99.84 (C-1), 72.87 (C-3), 71.97 (C-5), 71.29 (C-2),
71.09, 70.83, 70.76, 70.71, 70.28, 69.59 (CH2O), 68.39
(C-4), 62.90 (CH2CQ), 61.91 (C-6), 50.40 (CH2N), 33.91,
31.98, 29.43, 29.33, 29.01, 28.90, 28.76, 22.89, 22.85
(CH2 alkyl chains), 20.84, 20.72, 20.68, 20.68 (CH3COO),
14.36 (CH3 alkyl chains). HRMS (ESI) calc. for
C93H125N11NiO14S6,1869.7085; found 1869.7014.
[2,3,9,10,16,17-Hexa-(1-hexylthio)-23-((1-(1,4,7,10-tetra-
oxadodecyl)-1H-1,2,3-triazol-4-yl)methyl
4-O-(2,3,4,6-tetra-
O-acetyl-b-D-galactopyranosyl)-2,3,6-tri-O-acetyl-b-D-gluco-
pyranoside]phthalocyaninato nickel (19). Obtained in 93%
yield, following method 2, from propargyl 4-O-(2,3,4,6-tetra-
O-acetyl-b-D-galactopyranosyl)-2,3,6-tri-O-acetyl-b-D-gluco-
pyranoside (15) (28.3 mg, 72 mmol) and phthalocyanine 5
(50 mg, 35 mmol). 68 mg; green oily derivative; Rf 0.34 (20 : 1
CH2Cl2–EtOH). HRMS (ESI) calc. for C105H141N11NiO22S6,
[2,3,9,10,16,17-Hexa-(1-hexylthio)-23-((1-(1,4,7,10-tetra-
oxadodecyl)-1H-1,3-triazol-4-yl)methyl 2,3,4,6-tetra-O-acetyl-
a-D-mannopyranoside)] phthalocyaninato nickel (17). Obtained
in 94% yield, following method 2, from propargyl 2,3,4,6-
tetra-O-acetyl-a-D-mannopyranoside (13) (25 mg, 65 mmol)
and phthalocyanine 5 (80 mg, 54 mmol). 97 mg; green oily
1
2157.7930; found 2157.7904. H NMR: (CDCl3): d 5.34 (dd,
0
0
0
0
0
1H, J3 ,4 3.4, J4 ,5 0.5 Hz, H-4 ), 5.22 (dd, 1H, J2,3 9.3, J3,4 9.2 Hz,
H-3), 5.11 (dd, 1H, J1 ,2 7.9, J2 ,3 10.4 Hz, H-20), 4.95 (dd,
1H, H-30), 4.93–4.88 (m, 2H, H-2, 0.5CH2CQ), 4.80 (d, 1H, J
12.6 Hz, 0.5CH2CQ), 4.65 (d, 1H, J1,2 7.9 Hz, H-1), 4.60–4.54
(m, 2H, CH2N), 4.51 (dd, 1H, J5,6a 1.5, J6a,6b 11.9 Hz, H-6a),
4.48 (d, 1H, H-10), 4.28–4.20 (m, 2 H, C6H3OCH2), 4.17–4.08
(m, 3H, H-6b, H-60a, H-60b), 4.00–3.70 (m, 14H, H-4, H-50,
6OCH2), 3.65 (ddd, 1H, J4,5 9.9, J5,6b 4.5 Hz, H-5), 3.60–3.00
(m, 12 H, 6SCH2CH2), 2.15, 2.13, 2.05, 2.05, 2.03, 2.00, 1.96
(7s, 21H, 4CH3COO), 2.10–1.95 (m, 12H, 6SCH2CH2),
0
0
0
0
1
derivative; Rf 0.34 (20 : 1 CH2Cl2–EtOH). H NMR (CDCl3):
d 7.79 (s, 1H, QCH), 5.33 (dd, 1 H, J2,3 3.5 Hz, J3,4 9.8 Hz,
H-3), 5.31–5.29 (m, 1 H, H-4), 5.26 (dd, 1H, J1,2 1.9, H-2), 4.98
(d, 1H, H-1), 4.85 and 4.69 (2d, 2 H, J 12.2 Hz, OCH2CQ),
4.61–4.57 (m, 2H, CH2N), 4.31 (dd, 1H, J5,6a 5.2, J6a,6b 12.6 Hz,
H-6a), 4.28–4.22 (m, 2H, C6H3OCH2), 4.14–4.07 (m, 2H,
ꢀc
This journal is The Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2010
1160 | New J. Chem., 2010, 34, 1153–1162