A.N. Volov et al.
Polyhedron 206 (2021) 115331
+
(
M , 100%).
3
3.5. A B-type mono-glycosylated platinum(II) phthalocyanine (5)
3
.2. 1,2,3,4,5,6-penta-O-acetyl-β-galactopyranose (2)
Glycophthalonitrile (4) (1.0 g, 0,0018 mol) and tert-butylph-
thalonitrile (2.6 g, 0,0144 mol) was added in argon flow to Schlenk flask
Sodium acetate (1.0 g, 12 mmol) was added in acetic anhydride (20
containing Pt(PhCN)
2
Cl
2
(0.85 g, 0,0018 mol) in anhydrous benzonitrile
◦
◦
mL) was heated to 100 C for 30 min, then β-D-galactopyranose (2.0 g,
at 190 C. Resulting solution was stirred for 10 h and it was controlled by
TLC (DCM-MeOH 9:1). The volatiles were then evaporated in vacuo and
the residue was purified by silica-gel chromatography using
dichloromethane-methanol (changing gradually from v/v 1:0 to 9:1) as
1
1 mmol) was added in the solution under stirring. After 1 h of the re-
◦
action at 100 C, the mixture was cooled and poured into cold water. The
formed precipitate was separated by filtration, washed by water, hexane
and dried under vacuum that yielded pure product (6) as white powder
1
the eluent. The product 5 was isolated as a blue solid (0.15 g, 24%). H
Ar
(
4.2 g, 96%).
M.P. 142–143 C; H NMR (CDCl
NMR (CDCl
3
, 600 MHz,) δ 8.71–8.84 (m, 8H, α-H ), 7.75–7.90 (m, 4H,
◦
1
Ar
, 600 MHz,) δ 5.71 (d, J = 8.31 Hz,
β-H ), 7.94 (s, 1H, triazole), 5.87 (d, J = 9.2 Hz, 1H, H-1), 5.59 (dd, J =
),
3
1
3
H, H-1), 5.43 (m, 1H, H-4), 5.33 (t, J = 8.31 Hz, 1H, H-2), 5.09 (dd, J =
1.0 and 3.3 Hz, 1H, H-4), 5.48 (t, J = 9.2 Hz, 1H, H-2), 5.36 (s, 2H, CH
2
.42, 10.39 Hz, 1H, H-3), 4.1 – 4.19 (m, 2H, H-6a and H-6b), 4.04 – 4.08
5.29 (dd, J = 3.3 and 9.2 Hz, 1H, H-3), 4.28 (t, J = 6.3, 1H, H-5), 4.18
(
m, 1H, H-5), 2.16 (s, 3H, OAc), 2.12 (s, 3H, OAc), 2.04 (s, 6H, OAc),
(ddd, J = 6.9, 6.3 and 1.0 Hz, 2H, H-6), 2.30 (s, 3H, OAc), 2.09 (s, 3H,
ꢀ
1
195
1
1
9
.99 (s, 3H, OAc); FT-IR
ν
(cm ): 3299, 1715, 1643, 1600, 1580, 1525,
OAc), 2.01 (s, 3H, OAc), 1.90 (s, 3H, OAc).;
3
Pt NMR (CDCl , 129
488, 1438, 1402, 1380, 1291, 1253, 1156, 1092, 1039, 1024, 1001,
MHz) δ ꢀ 3210.79. UV–Vis (CHCl
3
), λmax nm (log
ε): 345 (4.56), 629
+
27, 806, 769, 726. GC/MS (EI, 70 eV): 390 (M , 100%).
(4.54), 667 (4.44), 693 (5.31); HRMS (ESI-TOF): Calcd for
+
C
69
H
81
N
7
O
10Pt [M + H] : 1299.4513. Found: 1299.4524.
3
.3. 1-Azido-1-deoxy-2,3,4,6-tetra-O-acetyl-β-galactopyranose (3)
4
. Conclusion
To a solution of galactosyl peracetate (5.0 g, 12.82 mmol) in anhy-
drous dichloromethane was added trimethylsilyl azide (2.21 mL, 16.66
mmol), followed by 1.0 M solution of stannic chloride (0.75 mL, 6.41
mmol). The resulting solution was stirred at room temperature for 12 h
under inert atmosphere. After the completion of the reaction (on TLC),
the reaction mixture was diluted with dichloromethane, washed with
saturated aqueous solution of sodium bicarbonate, water, dried over
In this paper we have demonstrated the synthesis of new glycosy-
lated phthalonitriles with galactose moieties with 1,2,3-triazole spacer
via Cu(II)-catalysed click reaction. It was found that click reaction be-
tween azide derivatives of galactose and propynyloxy-substituted
phthalonitrile proceed regioselectively and lead to formation of 1,4-
regioisomer of 1,2,3-trizole, that is confirmed by NMR spectroscopy.
1
MgSO
4
, filtered and concentrated in vacuo to give the crude product,
The structure of new glycosylated phthalonitrile was confirmed by H
NMR, 13C NMR spectroscopy, FT-IR spectroscopy, high resolution mass-
spectrometry. Platinum(II) glycoconjugated phthalocyanine was syn-
thetized by Pt(PhCN) Cl -promoted mixed cyclisation with tert-butyl-
which was purified by recrystallization (hexane/dichloromethane) to
give the title compound (7) (4.3 g, 89%) as a white solid.
◦
1
M.P. 90–91 C; H NMR (CDCl , 600 MHz,) δ 5.43 (dd, J = 1.0 and
3
2
2
3
3
6
4
3
3
1
.3 Hz, 1H, H-4), 5.17 (dd, J = 8.6 and 10.2 Hz, 1H, H-2), 5.04 (dd, J =
.3 and 10.2 Hz, 1H, H-3), 4.61 (d, J = 8.6 Hz, 1H, H-1), 4.19 (dd, J =
.9 and 12.3 Hz, 1H, H-6a), 4.14 (dd, J = 6.3 and 12.3 Hz, 1H, H-6b),
.02 (ddd, J = 6.9, 6.3 and 1.0 Hz, 1H, H-5), 2.18 (s, 3H, OAc), 2.10 (s,
substituted phthalonitrile. We have investigated photophysical proper-
ties of platinum complex and it was established that new platinum(II)
glycosylated phthalocyanine efficiently generate singlet oxygen and can
be used for PDT as photosensitizer.
ꢀ
1
H, OAc), 2.07 (s, 3H, OAc), 1.99 (s, 3H, OAc). FT-IR
ν
(cm ): 3210,
+
100, 3063, 2127, 1747, 1304, 1123.. GC/MS (EI, 70 eV): 373 (M ,
00%).
CRediT authorship contribution statement
Alexander N. Volov: Conceptualization, Investigation, Methodol-
ogy, Supervision, Writing - original draft, Conceptualization, Investi-
gation, Methodology, Supervision, Writing - original draft. Nikolai A.
Volov: Formal analysis, Investigation. Ivan D. Burtsev: Data curation,
Investigation.
′
′′ ′′ ′′ ′′
′
′
3
1
.4. 1-[{1 -(2 ,3 ,4 ,6 -tetra-O-acetyl-β-D-galactopyranosyl)-1 H-
′
′
′
,2 ,3 -triazol-4 -yl}- hydroxymethyl]phthalonitrile (4)
4
-(Propyn-3-yloxy)phthalonitrile (1) (1 mmol) and azido sugar (3)
(
1 mmol) were suspended in a mixture of 1:1 tert-butanol/ water (10 mL)
and kept for stirring at room temperature. To the stirring reaction
mixture freshly prepared solution of sodium ascorbate (20 mol %) in 10
Declaration of Competing Interest
mL and freshly prepared solution of CuSO
4
⋅5H
2
O (10 mol %) in 20 mL
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
water were sequentially added. The reaction mixture was stirred at
ambient temperature for 24 h. After completion of reaction (TLC), the
reaction mixture was extracted with EtOAc and water. The organic layer
4
was dried over anhydrous MgSO and evaporated under reduced pres-
Acknowledgements.
sure to give a crude mass. The latter was purified by silica gel column
chromatography using chloroform/methanol (9:1) as eluants to give the
1
The work was supported by a grant from the Russian Science Foun-
dation (RSF Grant No. 18-73-00216).
◦
cycloaddition products detailed below. Yield 79%. M.P. 171–172 C; H
NMR (CDCl
, 600 MHz,) δ 7.92 (s, 1H, triazole), 7.70 (d, J = 8.7 Hz, 1H,
3
Har.), 7.38 (d, J = 2.4 Hz, 1H, Har.), 7.34 (dd, J = 2.4, 8.7 Hz, 1H, Har.),
Appendix A. Supplementary data
5
5
.85 (d, J = 9.2 Hz, 1H, H-1), 5.55 (dd, J = 1.0 and 3.3 Hz, 1H, H-4),
.46 (t, J = 9.2 Hz, 1H, H-2), 5.31 (s, 2H, CH ), 5.26 (dd, J = 3.3 and 9.2
2
Hz, 1H, H-3), 4.25 (t, J = 6.3, 1H, H-5), 4.15 (ddd, J = 6.9, 6.3 and 1.0
Hz, 2H, H-6), 2.19 (s, 3H, OAc), 2.02 (s, 3H, OAc), 1.99 (s, 3H, OAc),
1
6
1
2
.85 (s, 3H, OAc). 13C NMR (CDCl
3
, 150 MHz) δ 20.4, 20.5, 20.5, 20.6,
References
1.1, 66.8, 68.0, 70.3, 74.0, 86.3, 107.8, 115.1, 115.5, 117.3, 119.8,
ꢀ
1
20.2, 125.7, 142.6, 161.0, 169.0, 169.6, 169.7, 170.2. FT-IR
ν
(cm ):
[
1] L.B. Josefsen, R.W. Boyle, Unique Diagnostic and Therapeutic Roles of Porphyrins
+
231. GC/MS (EI, 70 eV): 555 (M , 100%). HRMS (ESI-TOF): Calcd for
+
C
25
H
25
5
N O
10 [M + H] : 556.1701. Found: 556.1718.
5