T.K. Khan, M. Ravikanth / Tetrahedron 67 (2011) 5816e5824
5823
(100 MHz, CDCl3,
d
in ppm): 55.74, 77.3, 94.28, 99.93, 114.29, 116.31,
b
a
m,
-Py), 7.07 (2H, d, J¼8.7 Hz, BDP-Ar), 7.55e7.58 (8H, m), 8.03 (1H, s,
-Py), 8.05e8.11 (8H, m, Ar), 8.24 (2H, d, J¼8.2 Hz), 8.94e9.00 (8H,
118.74, 124.08, 126.15, 126.67, 127.17, 127.68, 128.87, 129.03, 129.90,
130.92, 131.09, 131.33, 132.64, 133.70, 136.46, 137.30, 144.01, 162.14.
b
-py). 13C NMR (100 MHz, CDCl3,
d
in ppm): 21.69, 55.75, 65.73,
19F NMR (282.2 MHz, CDCl3,
d
in ppm): ꢁ145.49 (q, JBeF¼56.5 Hz).
102.00, 113.97, 114.27, 118.89, 120.52, 120.70,121.85, 123.49, 126.55,
127.32, 127.60, 128.90, 129.60, 130.71, 130.90, 131.09, 131.25, 131.70,
132.21, 132.50, 132.64, 134.21, 134.34, 134.67, 134.86, 135.72, 136.20,
137.09, 137.56, 139.35, 139.42, 141.91, 143.89, 144.32, 145.20, 162.18.
11B NMR (96.3 MHz, CDCl3,
d
in ppm): 0.991 (t, JBeF¼30.5 Hz). HR-MS
calcd for (C32H21BF2N2O): 499.1793 found: 499.1813.
4.4.2. BODIPYeBODIPY conjugate 2. Alumina column (petroleum
ether/dichloromethane 75:25) Rf (25% pet. ether/CH2Cl2) 0.30; 40%
yield; IR (KBr, cmꢁ1) 769, 754, 849, 928, 1021, 1081, 1119, 1218, 1527,
1604, 1672, 1965, 2400, 2855, 2927, 3020; 1H NMR (400 MHz,
19F NMR (282.2 MHz, CDCl3,
11B NMR (96.3 MHz, CDCl3,
d
in ppm): ꢁ145.92 (q, JBeF¼56.4 Hz).
d
in ppm): 0.69 (t, JBeF¼28.92 Hz). HR-
MS calcd for (C65H46BF2N6OZn) m/z 1041.3164 observed 1040.3192.
CDCl3): 3.94 (3H, s, OMe), 6.59 (2H, m,
(1H, m, -Py), 6.97 (2H, m,
-Py), 7.07 (2H, d, J¼8.2 Hz, Ar), 7.56 (2H,
d, J¼8.24 Hz, Ar), 7.61 (2H, d, J¼8.24 Hz, Ar), 7.72 (2H, m, -Py), 7.83
(2H, d, J¼7.9 Hz, Ar), 7.98 (2H, s, -Py), 8.02 (1H, s,
-Py). 13C NMR
(100 MHz, CDCl3, in ppm): 55.75, 65.73, 85.0, 100.0, 114.32, 18.98,
b
-Py), 6.63 (1H, s,
b
-Py), 6.79
4.4.6. BODIPYe21,23-dithiaporphyrin conjugate 6. Silica column
(petroleum ether/dichloromethane 50:50) Rf (50% pet. ether/
CH2Cl2) 0.30; 38% yield; IR (KBr, cmꢁ1) 669, 770, 849, 928, 1018,
1122, 1217, 1423, 1526, 1603, 1965, 2400, 2927, 3019, 3272; 1H NMR
(400 MHz, CDCl3): 2.71 (9H, s), 3.93 (3H, s, OMe), 6.59 (1H, s, BDP-
b
b
b
a
a
d
119.33, 123.32, 129.00, 130.74, 131.08, 131.57, 132.23, 132.46, 132.66,
b
-Py), 6.85 (1H, d, J¼3.3 Hz, BDP-
(2H, d, J¼8.2 Hz, BDP-Ar), 7.57 (2H, d, J¼8.5 Hz, BDP-Ar), 7.61e7.63
(8H, m), 8.04 (1H, s,
d, J¼8.2 Hz), 8.68e8.73 (4H, m,
b-Py), 7.01 (2H, m, BDP-b-Py), 7.07
134.88, 144.60, 144.96, 149.0, 162.0, 166.0, 167.89. 19F NMR
(282.2 MHz, CDCl3,
d
in ppm): ꢁ145.12 (q, JBeF¼56.4 Hz), ꢁ146.08
a
-py), 8.12e8.14 (6H, d, J¼7.02 Hz, Ar), 8.27 (2H,
(q, JBeF¼56.4 Hz). 11B NMR (96.3 MHz, CDCl3,
d
in ppm): 0.753 (m).
b
-py), 9.66e9.73 (4H, m,
b
-Th). 19
F
ES-MS calcd for (C33H22B2F4N4O): 588.19 found: 569.26 [Mꢁ19]þ.
NMR (282.2 MHz, CDCl3,
NMR (96.3 MHz, CDCl3,
calcd for (C65H45BF2N4OS2): calculated 1011.2994 found: 1011.3018.
d
in ppm): ꢁ146.07 (q, JBeF¼56.4 Hz). 11
B
HR-MS calcd for (C33H22B2F3N4O): 569.1932 found 569.1945.
d
in ppm):0.896 (t, JBeF¼27.4 Hz). HR-MS
4.4.3. BODIPYeterpyridine conjugate 3. Alumina column (petro-
leum ether/dichloromethane 40:60) Rf (60% pet. ether/CH2Cl2)
0.45; 50% yield; IR (KBr, cmꢁ1) 710, 758, 887, 983, 1023, 1081, 1121,
1216, 1527, 1604, 1965, 2201, 2855, 2926, 3018; 1H NMR (400 MHz,
4.4.7. BODIPYethiasapphyrin conjugate 7. Alumina column (pe-
troleum ether/dichloromethane 40:60) Rf (60% pet. ether/CH2Cl2)
0.60; 53% yield; IR (KBr, cmꢁ1) 710, 799, 856, 945, 1076, 1081, 1261,
1553, 2123, 2921, 2852, 3322; 1H NMR (400 MHz, CDCl3): ꢁ0.84
CDCl3): 3.94 (3H, s, OMe), 6.59 (1H, m,
-Py), 6.95 (2H, m,
-Py), 7.33e7.39 (4H, m, pyridylþBDP-Ar), 7.47
(2H,d, J¼7.9 Hz, BDP-Ar), 7.69 (2H, d, J¼8.2 Hz, Tpy-Ar), 7.80 (2H, d,
b-Py), 6.75 (1H, d, J¼3.97 Hz,
b
b
(2H, s,
(1H, s, BDP-
m, BDP[
-PyþAr]), 7.60 (10H, m, Ar[BDPþsap]), 8.06 (1H, s, BDP-
Py), 8.12e8.21 (4H, m, Ar), 8.27 (2H, d, J¼7.3 Hz, Ar), 8.35 (2H, d,
J¼8.2 Hz, Ar), 8.59e8.71 (4H, m, -Py sap), 9.8 (2H, d, J¼8.54 Hz,
b-Th), 2.64 (6H, s, tol), 2.74 (3H, s, tol), 3.93 (3H, s, OMe), 6.62
b
-Py), 6.87 (1H, d, J¼4.27 Hz, BDP-
b-Py), 7.02e7.18 (4H,
J¼7.6 Hz, Tpy-Ar), 7.88e7.96 (2H, m, pyridyl), 8.0 (1H, s,
a
-Py), 8.67
b
a-
(2H, d, J¼7.63 Hz, pyridyl), 8.75 (4H, d, J¼3.97 Hz, pyridyl). 13C NMR
(100 MHz, CDCl3,
d
in ppm): 55.56, 114.10, 118.76, 121.42, 123.40,
b
123.95, 127.36, 130.63, 132.47, 132.79, 136.94, 145.00, 149.18, 156.11.
19F NMR (282.2 MHz, CDCl3,
in ppm): ꢁ146.17 (q, JBeF¼56.4 Hz).
11B NMR (96.3 MHz, CDCl3,
b-Th-bth), 10.25e10.28 (2H, m, b
-Th-bth). 19F NMR (282.2 MHz,
d
CDCl3,
CDCl3,
d
in ppm): ꢁ146.04 (q, JBeF¼56.0 Hz). 11B NMR (96.3 MHz,
d
in ppm): 0.769 (t, JBeF¼25.9 Hz). HR-
d
in ppm): 0.912 (t, JBeF¼28.9 Hz). HR-MS calcd for
MS calcd for (C39H27BF2N5O): 631.2355 found: 631.2367.
(C69H47BF2N4OS3): 1093.3047 found: 1093.3051.
4.4.4. BODIPYeporphyrin conjugate 4. Silica column (petroleum
ether/dichloromethane 60:40) Rf (40% pet. ether/CH2Cl2) 0.55; 40%
yield; IR (KBr, cmꢁ1) 710, 758, 888, 983, 1023, 1081, 1121, 1216, 1286,
1507, 1604, 1965, 2201, 2855, 2926, 3018, 3320; 1H NMR (400 MHz,
Acknowledgements
M.R. thanks Department of Atomic Energy (DAE-BRNS) and
Department of Science and Technology for financial support. T.K.K.
thanks Indian Institute of Technology, Bombay for fellowship.
CDCl3): ꢁ2.7 (1H, s), 2.70 (9H, s), 3.9 (3H, s), 6.59 (1H, s, BDP-
6.84 (1H, d, J¼3.9 Hz, BDP- -Py), 6.99e7.02 (2H, m, BDP- -Py), 7.04
(2H, d, J¼8.7 Hz, BDP-Ar), 7.54e7.58 (8H, m), 8.03 (1H, s, -Py),
8.05e8.10 (8H, m, Ar), 8.24 (2H, d, J¼8.2 Hz), 8.86e8.89 (8H, m,
-py). 13C NMR (100 MHz, CDCl3,
in ppm): 21.69, 55.69, 65.76,
b-Py),
b
b
a
Supplementary material
Complete characterization data of compounds, 1H and 13C NMR
and 19F spectra. Supplementary data associated with this article can
b
d
70.74, 84.09, 102.00, 113.97, 114.28, 118.89, 120.55, 120.70, 121.85,
123.49, 126.55, 127.32, 127.62, 128.90, 129.60, 130.73, 130.90, 131.09,
131.25, 131.70, 132.21, 132.50, 132.64, 134.21, 134.40, 134.68, 134.87,
135.72, 136.20, 137.09, 137.57, 139.37, 139.42, 141.91, 143.89, 144.32,
References and notes
144.32, 145.20, 162.19. 19F NMR (282.2 MHz, CDCl3,
d
in ppm):
ꢁ145.85 (q, JBeF¼56.4 Hz). 11B NMR (96.3 MHz, CDCl3,
d in ppm):
1. (a) Loudet, A.; Burgess, K. Chem. Rev. 2007, 107, 4891e4932; (b) ziessel, R.;
Ulrich, G.; Harriman, A. New J. Chem. 2007, 31, 496e501; (c) Ulrich, G.; Ziessel,
R.; Harriman, A. Angew. Chem., Int. Ed. 2008, 47, 1184e1201.
2. (a) Li, F.; Yang, S. I.; Ciringh, Y.; Seth, J.; Martin, C. H., III; Singh, D. L.; Kim, D.;
Birge, R. R.; Bocian, D. F.; Holten, D.; Lindsey, J. S. J. Am. Chem. Soc. 1998, 120,
10001e10017; (b) Lammi, R. K.; Amboise, A.; Balasubramanian, T.; Wagner, R.
W.; Bocian, D. F.; Holten, D.; Lindsey, J. S. J. Am. Chem. Soc. 2000, 122,
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0.912 (t, JBeF¼28.99 Hz). HR-MS calcd for (C65H48BF2N6O): calcu-
lated 977.3951 found: 977.3906.
4.4.5. BODIPYeZn(II)porphyrin conjugate 5. A solution of 4 (20 mg,
0.02 mmol) and Zn(OAc)2 (64.5 mg, 1.33 mmol) in dichloro-
methane/methanol (3:1, 20 mL) was stirred at room temperature
for 2 h. The crude compound was purified by silica gel column
chromatography using petroleum ether/dichloromethane (60:40)
as eluent, and the desired porphyrin 5 was collected as a violet solid
in 85% yield; Rf (40% pet. ether/CH2Cl2) 0.30; IR (KBr, cmꢁ1) 669,
770, 849, 928, 1018, 1122, 1423, 1526, 1603, 1965, 2400, 2854, 2927,
3019, 3272; 1H NMR (400 MHz, CDCl3): 2.70 (9H, s), 3.9 (3H, s), 6.60
3. Haugland, R. P. In Handbook of Molecular Probes and Research Products Molecular
Probes: Eugene, OR, 2002.
4. Golovkova, T. A.; Kozlov, D. V.; Neckers, D. C. J. Org. Chem. 2005, 70, 5545e5549.
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2000, 122, 968e969; (b) Baki, C. N.; Akkaya, E. U. J. Org. Chem. 2001, 66,
1512e1513; (c) Rurack, K.; Kollmannsberger, M.; Daub, J. Angew. Chem., Int. Ed.
2001, 40, 385e387; (d) Turfan, B.; Akkaya, E. U. Org. Lett. 2002, 4, 2857e2859;
(e) Baruah, M.; Qin, W.; Vallee, R. A. L.; Belijonne, D.; Rohand, T.; Dehaen, W.;
Boens, N. Org. Lett. 2005, 7, 4377e4380; (f) Baruah, M.; Qin, W.; Basaric, N.;
(1H, s, BDP-b-Py), 6.86 (1H, s, BDP-b-Py), 6.99e7.02 (2H, m, BDP-