J Po lue ran sae l od fo Mn aot te rai ad l jsu Cs th em mai rs gt ri ny sB
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obtained in the solid (KBr disk) on a NEXUS-870 (Nicolet) δ (ppm): 8.28 (s, 1H), 8.06 (d, J= 9.1 Hz, 4H), 7.67 (d, J= 8.91 Hz, 1H),
-
1
DOI: 10.1039/C9TB00421A
spectrophotometer in the 400 4000 cm . Mass spectra were 6.41(dd, J= 2.23, 9.15 Hz, 1H), 6.21 (s, 1H), 3.48(q, J= 7.15 Hz, 4H),
13
performed on a Micromass GCT-MS (ESI source). Absorption spectra 1.19(t, J= 7.41 Hz, 6H). C NMR (100 MHz, CDCl
3
) δ (ppm): 162.52,
were recorded on a UV-3100 spectrophotometer. Emission spectra 157.32, 152.49, 146.68, 139.21, 134.58, 126.34, 124.97, 113.38,
were obtained on an F-2500 fluorescence spectrophotometer.
107.75, 97.71, 45.43, 13.38. ESI-MS: m/z, cal: 361.14, found:
+
-1
3
3
1
1
7
62.1477 [M+1] . FT-IR (KBr, cm ): 3481.73(m), 3361.58(m),
219.96(w), 2923.51(m), 2853.06(w), 1629.50(s), 1583.27(s),
505.28(m), 1479.95(m), 1446.04(w), 1333.96(s), 1300.21(s),
216.36(m), 1146.02(w), 1112.38(m), 1036.80(m), 841.30(m),
52.77(m), 631.90(m).
Synthesis of 03B
(0.87 g, 2.0 mmol) was added mixture solution of
03
ethyldiisopropylamine (DIEA)(0.5 mL)and dichloromethane (10
mL), it was stirred at the room temperature for 30 minutes under
the nitrogen protection. Then BF ·OEt (2.52 mL, 20 mmol)was
3 2
added by using injector. The reaction at room temperature for 18 h.
EtOH was added when the reaction was finished. The rude
production was collected by filtration; the product was separated
by column chromatography (using silica gel). Yield:0.52 g (53.8 %).
Scheme 1 The synthetic routes of BODIPY analogues.
Synthesis
1
H NMR (400 MHz, CDCl
3
) δ (ppm): 8.03 (s, 1H), 7.36 (d, J= 8.59 Hz,
2
3
d
H), 7.25 (m, 5H), 7.07 (m, 7H), 6.36 (d, J= 9.02 Hz, 1H), 6.25 (s, 1H),
Synthesis of 01B
13
.44 (q, J= 7.02 Hz, 4H), 1.25 (t, J=7.1 Hz, 6H). C NMR (100 MHz,
-DMSO) δ (ppm):161.60, 157.39, 147.36, 137.50, 133.61, 129.38,
The BODIPY analogues were prepared according to the similar
6
17-19
procedures with previous work.
in freshly distilled CH Cl
(15 mL) and was heated to dissolution. found: 484.2401[M+1] . FT-IR (KBr, cm ): 3036.53(w), 2924.37(m),
Then BF3·OEt
(0.47 mL 3.75 mmol)was added by using injector, 2851.73(w), 1636.72(s), 1596.89(s), 1508.10(s), 1492.48(s),
01 (0.4 g, 1.5 mmol) was added 124.67,123.49, 106.52, 45.18, 13.39. ESI-MS: m/z, cal: 483.23,
+
-1
2
2
2
waiting for a minute, DIEA (0.65 mL 3.75 mmol) was added, the 1461.05(w), 1414.55(w), 1355.51(m), 1327.68(m), 1276.60(m),
solution was heated to reflux for 2 h, cooled the room temperature 1213.79(m), 1145.70(m), 1033.43(m), 971.51(m), 826.80(m),
and poured into saturation solution of NaHCO
aqueous layer was extracted with dichloromethane and the organic
phases were dried (anhydrous Na SO ). The solvent removed and
3
(50 mL), the 745.65(m), 695.34(m), 616.91(m).
Synthesis of 04B
2
4
the residue separated by column chromatograph (using silica gel)
The same procedure as described synthesis of 02B, except 01 was
1
1
giving a yield of 0.32 g (64.6 ); H NMR (400 MHz, CDCl
3
) (ppm): replaced by 04. Yield: 0.44 g (80.1 %). H NMR (400 MHz, CDCl
3
)
8
6
.02 (s, 1H), 7.38 (d, J = 8.20 Hz, 2H ), 7.23 ( t, J = 12.43 Hz, 3H ), δ(ppm): 7.90 (m, 4H), 7.52 (m, 4H), 7.18 (d, J = 8.99 Hz, 1H), 6.37
.34 ( dd, J = 2.27 Hz, 9.03 Hz, 2H ), 6.23 ( s, 1H ), 3.44 ( q, J = 7.12 (dd, J = 2.07, 9.00 Hz, 2H), 6.32 (s, 1H), 3.47 (q, J = 7.13, 7.13, 7.15
13
13
Hz, 4H ), 2.37 (s, 3H), 1.25 ( t, J = 7.40 Hz, 6H ). C NMR (100 MHz, Hz, 4H), 1.24 (t, J = 0.40 Hz, 6H). C NMR (100 MHz, CDCl
CDCl
) (ppm): 161.76, 158.09, 156.08, 140.79, 137.61, 133.74, 161.94, 156.05, 139.17, 133.94, 128.32, 124.85, 123.14,105.05,
29.92, 122.98, 106.47, 98.17, 45.12, 29.69, 21.00, 12.64. ESI-MS: 97.42, 45.19, 30.11, 12.65. ESI-MS: m/z, cal: 366.17, found:
3
) δ(ppm):
3
1
+
-1
+
-1
m/z, cal: 330.17, found: 331.17 M+1 . FT−IR (KBr, cm ): 2978.98 ( 367.1783[M+1] . FT-IR (KBr, cm ): 2922.83(m), 1623.20(s),
w ), 2925.81 (w), 1626.26 (s), 1591.59 (s), 1507.52 (s), 1447.44 1591.17(s), 1506.85(s), 1450.51(s), 1411.46(m), 1344.58(s),
(
(
w),1354.83 (m), 1277.87 (w), 1205.94 (s), 1143.80 (m), 1074.12 1216.58(m), 1077.74(m), 964.78(m), 824.68(m), 787.31(m),
w), 1038.38 (m), 972.61 (m),901.32 (w), 822.92 (w), 795.56 (w), 678.28(m).
4
93.77 (w).
X-ray crystallography and structure solution
Synthesis of 02B
X-ray diffraction data of single crystals were collected by Siemens
Smart 1000 CCD diffractometer, and the determination of unit cell
The synthesis of 02B was similar to that of 01B, except 01 was
replaced by 02. Yield: 0.42 g (75.7 ); H-NMR (400 MHz, CDCl
1
3
)
parameters and data collections were performed with MoK
radiation ( = 0.71073 Å). Unit cell dimensions were collected with
least-squares refinements and all structures were solved by direct
methods using SHELXS-97. The other non-hydrogen atoms were
located in successive difference Fourier syntheses. The final
refinement was performed by full-matrix least-squares methods
2
with anisotropic thermal parameters for non-hydrogen atoms on F .
The hydrogen atoms were added theoretically and riding on the
concerned atoms.
Fig. 1 Structures of BODIPY analogues.
2
| J. Name., 2012, 00, 1-3
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