Paper
NJC
The mixture was stirred vigorously for 48 h then poured into References
water. The mixture was filtered. The residue was purified by
1
S. Z. Topal, U¨ . ˙I s-ci, U. Kumru, D. Atilla, A. G. G u¨ rek, C. Hirel,
M. Durmus-, J.-B. Tommasino, D. Luneau, S. Berber, F. Dumoulin
and V. Ahsen, Dalton Trans., 2014, 43, 6897.
T. Nyokong, Coord. Chem. Rev., 2007, 251, 1707.
Y. Arslano ˘g lu, A. M. Sevim, E. Hamuryudan and A. G u¨ l, Dyes
Pigm., 2005, 68, 129.
column chromatography using first dichloromethane as the
eluent, then dichloromethane/ethanol (100/1). The fraction con-
taining the desired phthalonitrile 3 was chromatographed on a
second silica gel column using a hexane/ethyl acetate mixture as
2
3
the eluent. Yield 18% (1.40 g). C20
solid. m.p:89–91 1C. FT-IR nmax (cm ) 3533, 2927, 2857, 2228,
H
28
N
2
OS
2 W
, M 376.58. White
ꢁ1
¨
˙
4
5
D. Topkaya, F. Dumoulin, V. Ahsen and U. Is-ci, Dalton
Trans., 2014, 43, 2032.
1
6
563, 1459, 1395, 1347, 1285, 1227, 1119, 1049, 1001, 933, 752,
89. HRMS m/z: 399.153 [M + Na] . H NMR (500 MHz, CDCl )
3
+
1
N. Kobayashi, H. Ogata, N. Nonaka and E. A. Luk’yanets,
Chem. – Eur. J., 2003, 9, 5123.
6 D. Aydın Tekdas-, R. Garifullin, B. -Sent u¨ rk, Y. Zorlu,
U. Gundogdu, E. Atalar, A. B. Tekinay, A. A. Chernonosov,
Y. Yerli, F. Dumoulin, M. O. Guler, V. Ahsen and
A. G. G u¨ rek, Photochem. Photobiol., 2014, 90, 1376.
S. Tuncel, A. Trivella, D. Atilla, K. Bennis, H. Savoie,
F. Albrieux, L. Delort, H. Billard, V. Dubois, V. Ahsen,
F. Caldefie-Ch ´e zet, C. Richard, R. W. Boyle, S. Ducki and
F. Dumoulin, Mol. Pharmaceutics, 2013, 10, 3706.
ppm: 7.42 (2H, s, ArCH), 3.67–3.65 (3H, m, CH O, OH), 3.04–3.00
2
(
4H, q, CH –S), 1.79–1.33 (16H, m, CH ), 0.92–0.90 (3H, t, CH ).
2 2 3
1
3
C NMR (125 MHz, CDCl ) ppm: 144.28, 144.03 (ArC–S), 128.12,
3
128.07 (ArCH), 115.66, 115.65 (CN), 111.04–110.96 (ArC–C), 62.65
(
2
C
CH
2
–O), 32.69, 32.57, 32.40, 31.20, 28.63, 28.62, 28.53, 27.98,
2.43 (CH ), 25.27, 25.25 (CH S), 13.95 (CH ). Anal. calc. for
OS (376.57): C: 63.79; H: 7.49; N: 7.44; found: C: 63.89;
H: 7.40; N: 7.43.
2
2
3
7
20
H
N
28 2
2
Preparation of phthalocyanine 1. To a mixture of phthalo-
nitrile 3 (200 mg, 0.53 mmol) and phthalonitrile 4 (1.5 g,
8
9
W. Duan, K. Smith, H. Savoie, J. Greenman and R. W. Boyle,
Org. Biomol. Chem., 2005, 3, 2384.
D. Lafont, Y. Zorlu, H. Savoie, F. Albrieux, V. Ahsen,
R. W. Boyle and F. Dumoulin, Photodiagn. Photodyn. Ther.,
4
.16 mmol) in n-pentanol (4 mL) were added DBU (0.4 mL)
and anhydrous zinc acetate (580 mg, 3.16 mmol). The reaction
mixture was refluxed at 140 1C for 6 h and then the green
product was poured into a water/ethanol mixture and filtered.
The residue was purified using column chromatography using
first dichloromethane, and then the polarity of the eluent
was gradually increased up to that of dichloromethane/ethanol
2
013, 10, 252.
0 I. R. Vlahov and C. P. Leamon, Bioconjugate Chem., 2012,
3, 1357.
1
2
1
1
1 N. B. McKeown, J. Mater. Chem., 2000, 10, 1979.
2 F. Giuntini, F. Dumoulin, R. Daly, V. Ahsen, E. M. Scanlan,
A. Lavado, J. W. Aylott, G. Rosser, A. Beeby and R. W. Boyle,
Nanoscale, 2012, 4, 2034.
(
20/1). 1 was fully purified using preparative silica thin layer
chromatography using dichloromethane/ethanol (200/1). Yield
3% (110 mg). C80 OS Zn, M 1523.73. Deep green wax.
FT-IR nmax (cm ) 2954, 2924, 2854, 2572, 1592, 1483, 1457,
1
H
112
N
8
8
W
ꢁ
1
¨
˙
¨
1
3 S. Alpugan, U. Is-ci, F. Albrieux, C. Hirel, A. G. Gurek,
Y. Bretonni `e re, V. Ahsen and F. Dumoulin, Chem. Commun.,
2014, 50, 7466.
1
6
404, 1369, 1335, 1281, 1260, 1085, 1066, 943, 897, 778, 741,
+
98. MALDI-TOF-MS (matrix DHB): m/z 1524.514 [M + H] .
3
UV-Vis (CHCl ) lmax (log e) 370 (4.93), 710 (5.41).
Preparation of phthalocyanine–biotine conjugate 5. Biotine 14 M. Kandaz, A. T. Bilgicli and A. Altindal, Synth. Met., 2010,
0
(
146 mg, 0.6 mmol), N,N -dimethylaminopyridine (1 equiv.,
160, 52.
7
3 mg) and dicyclohexylcarbodiimide (1 equiv., 124 mg) 15 Y. Zorlu, D. Topkaya Tas-kıran, D. K. Tarakçı, U. Kumru,
¨
˙
were stirred two hours in DMF (2 mL), then phthalocyanine 1
45 mg, 0.3 mmol) was added. Stirring of the reaction mixture
S. Alpugan, U. Is-ci, F. Dumoulin and V. Ahsen, J. Chem.
Crystallogr., 2014, 44, 337.
(
at room temperature was continued overnight. After TLC 16 V. N. Nemykin, S. V. Dudkin, F. Dumoulin, C. Hirel,
control of the completion of the reaction, water was added to
A. G. G u¨ rek and V. Ahsen, ARKIVOC, 2014, i, 142.
the reaction mixture which was filtered and thoroughly washed 17 A. Wang, L. Long and C. Zhang, Tetrahedron, 2012, 68, 2433.
with a water/ethanol mixture (1/1). Phthalocyanine–biotine 18 J. Mack and N. Kobayashi, Chem. Rev., 2011, 111, 281.
conjugate 5 was purified using preparative silica gel thin 19 G. de la Torre and T. Torres, J. Porphyrins Phthalocyanines,
layer chromatography, eluent dichloromethane/ethanol (10/1).
Yield 79% (41 mg). C90 Zn, M
1749.99. Deep green 20 R. Jones and O. Gunnarsson, Rev. Mod. Phys., 1989, 61, 689.
wax. MALDI-TOF-MS (matrix DHB): m/z 1751.18 [M + H]
2002, 6, 274.
H
126
N
10
O
3
S
9
W
+
21 M.-R. Ke, S.-L. Yeung, D. K. P. Ng, W.-P. Fong and P.-C. Lo,
J. Med. Chem., 2013, 56, 8475.
22 S. Wang, J. Wang and J.-Y. Chen, J. Mater. Chem. B, 2014,
+
and 1773.02 [M + Na] . UV-Vis (CHCl
00 (3.88).
3
) lmax (log e) 365 (3.51),
7
2
, 1594.
3 J. Kim, C.-H. Tung and Y. Choi, Chem. Commun., 2014,
0, 10600.
4 D. Jung, S. Maiti, J. H. Lee, J. H. Lee and J. S. Kim, Chem.
Commun., 2014, 50, 3044.
2
2
5
Acknowledgements
The Scientific and Technological Research Council of Turkey
(
TUBITAK) is gratefully acknowledged (project 112T670 coupled 25 J. Garcia, S. Barluenga, K. Gorska, F. Sasse and N. Winssinger,
to the COST Action CM1105).
Bioorg. Med. Chem., 2012, 20, 672.
3934 | New J. Chem., 2015, 39, 3929--3935
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