J Fluoresc
BODIPY, can be used for copper (II) ion in the half-water
medium. The sensitivity and selectivity studies were support-
ed by bio-imaging of yeast cells.
[100 MHz, CDCl3]: δ (ppm); 154.03, 139.49, 138.66,
135.88, 136.11, 133.02, 130.77, 128.99, 128.38, 45.66,
16.98, 14.66, 12.54, 11.66. Analytical Cal. for (%)
C24H28N2F2ClB: H, 6.58; C, 67.22; N, 6.53; Found: H,
6.97; C, 66.98; N, 6.13. MS for C24H28N2F2ClB: 428 [M +
H]+.
Experimental Section
Materials, Methods, and Instruments
The Synthesis of Compound 4 (8-{4-(Azidomethyl)
Phenyl}-2,6-Diethyl-4,4-Difluoro-1,3,5,7-Tetra
Methyl-4-Bora-3a,4a-Diaza-S-Indacene)
All chemicals were analytical grade and they were used as
received without any further purification. Elemental analyses
and melting points of compounds were carried out by using a
Compound 1 (0.44 mmol) and NaN3 (0.344 g, 0.53 mol) were
dissolved in N,N-dimethylformamide (20 mL) and mixed for
24 h at room temperature under inert atmosphere. The residue
was extracted with water/chloroform. The organic phases
were collected, dried with Na2SO4. Following evaporation
of chloroform, raw product was purified in column (only di-
chloromethane) (0.56 g, 96%). Caution: Compound 4 must be
handled with special care due to its explosive character,
Gallenkamp and a TruSpec, respectively. H and 13C-NMR
1
spectral measurements were taken in CDCl3 on a Varian
400 MHz spectrometer at room temperature. The FT-IR data
were carried out on a Bruker Vertex 70 spectrophotometer.
The emission and absorption spectra were taken on a
PerkinElmer LS 55 and Shimadzu 1280 apparatus, respective-
ly (the emission slits were set as 5 nm in the fixed excitation).
The dried dichloromethane was used for the synthesis of
Bodipy including chlorine terminal. Merck plates (silica gel
60 F254 on aluminum) were used for TLC (thin layer chro-
matography) observations. The spectroscopic measurements
were carried out by metal chloride in half aqueous medium.
For all the microscope images, an Olympus (BX51/BX2-
FLB3–000) microscope was used. Microscope images were
collected using a CCD camera (DP70 12.5 million-pixel res-
olution). The microscope has a different magnification lens:
4×, 10×, 20×, 50× and 100×. The capture of images is possible
with software: DP Manager. For the fluorescence light, an
FTIC filter was used, otherwise, for all the other images, a
transmitted light was used.
1
Melting point: 140 °C. H-NMR [400 MHz, CDCl3]: 7.45
(PhH, d, 2H), 7.33 (PhH, d, 2H,) 4.48 (CH2, s, 2H,), 2.57
(CH3, s, 6H) 2.32 (CH2, q, 4H), 1.28 (CH3, s, 6H,), 0.99
(CH3, t, 6H). 13C NMR [100 MHz, CDCl3]: δ (ppm);
154.04, 138.99, 138.03, 135.98, 135.62, 132.95, 130.81,
128.29, 129.03, 55.34, 17.44, 15.02, 12.32, 11.99.
Analytical Cal. for (%) C24H28BF2N5: H, 6.48; C, 66.22; N,
16.09; Found: H, 6.67; C, 66.38; N, 16.15.
The Synthesis of Compound 7 (N1,N3-di(Prop-2-Ynyl)
Isophthalamide) (Compound 7)
0.5 mL of triethylamine was added to a solution of
isophthaloyl dichloride (167.0 mg, 1 mmol) in dichlorometh-
ane at −5 °C (salt-ice). Then, 0.4 mL of propargylamine
(Compound 6) was added dropwise to this solution at room
temperature and stirred for 48 h. The mixture was extracted in
a DCM-water mixture (v/v ratio: 1/3) and the crude product
was extracted into the organic phase. The organic phase was
dried with MgSO4 and the solvent was evaporated in vacuo.
The crude product was purified by column (Petroleum ether
40–60% / EtOAc; 1: 1). A white solid was obtained. Yield:
81%. m.p. 177 °C.
The Preparing of Compounds
The Synthesis of Compound 3
8-{4-(chloromethyl)phenyl}-2,6-diethyl-4,4-difluoro-1,3,5,7-
tetramethyl-4-bora-3a,4a-diaza-s-indacene was prepared just
as the synthesis procedure in our previous papers [31].
p-(chloromethyl)benzoyl chloride (7.5 g, 0.04 mol) was bitten
by bit added to a solution (in DCM, 200 mL) of Kryptopyrrole
(10.8 mL, 0.08 mol) in Ar atmosphere at room temperature.
Then, the stirring of the solution was allowed for 4 h.
Following cooling of the solution, 10 mL of triethylamine
was added to the mixture, it was stirred at r. t. for half-hour
and boron trifluoride diethyl etherate (8 mL) was injected by
syringe. The mixture was heated to 65 °C for 3 h and the
residue was purified by a solution of ethylacetate-
cyclohexane in 1:8 ratio (3.47 g, Yield 40%). Melting point:
189 °C. 1H NMR [400 MHz, CDCl3]: 7.42 (PhH, d, 2H), 7.20
(PhH, d, 2H), 4.65 (CH2, s, 2H), 2.46 (CH3, s, 6H) 2.23 (CH2,
q, 4H) 1.29 (CH3, s, 6H) 0.91 (CH3, t, 6H). 13C NMR
1H-NMR [400 MHz,CDCl3]: 9.08 (NH, t, 2H), 8.35 (PhH,
t, 1H), 8.02–7.95 (PhH, m, 2H), 7.56 (PhH, t, 1H), 4.10–4.08
(CH2, m, 4H), 3.15 (CH, t, 2H); 13C NMR [100 MHz,
CDCl3]:d(ppm); 165.7, 133.9, 129.8, 128.2, 126.2, 80.8,
72.5, 28.1.
The Synthesis of d-BODIPY
0.870 g of Compound 4 and 0.240 g of Compound 7 were
a d d e d t o
a m i x t u r e s o l v e n t i n c l u d i n g
chloroform:methanol:water in a ratio of 10: 1: 1, respectively.