Tetrahedron 62 (2006) 8484–8488
Distyryl-boradiazaindacenes: facile synthesis of novel
near IR emitting fluorophores
Zeynep Dost, Serdar Atilgan and Engin U. Akkaya*
Department of Chemistry, Middle East Technical University, TR-06531 Ankara, Turkey
Received 22 March 2006; revised 9 June 2006; accepted 22 June 2006
Available online 13 July 2006
Abstract—Boradiazaindacenes with methyl substituents at 3 and 5 positions were for the first time shown to undergo efficient double
condensation reactions with an aromatic aldehyde yielding a series of extended conjugation dyes. These new fluorophores have absorption
maxima in the range of 650–660 nm. The dyes reported here have large quantum yields with 20 nm Stokes’ shifted emission peaks. The
straightforward synthesis of such red shifted BODIPY derivatives is important in relation to the synthesis of novel and useful fluorescent
chemosensors. In addition, this facile transformation may make these new fluorophores’ building blocks in the construction of large functional
supramolecular systems.
Ó 2006 Elsevier Ltd. All rights reserved.
1. Introduction starting from 3,5-dimethylboradiazaindacene derivatives.
The condensation reactions seem not to be limited to
Boradiazaindacenes (a.k.a., BODIPY dyes, BDPs, difluoro- dialkylamino substituted aromatic aldehydes, which is an
bora-dipyrromethenes, etc.) are well known1 fluorescent important finding for the broader applicability of the deriva-
dyes with many applications, such as fluorescent labeling tization reaction. The novel alkoxystyryl derivatives have
of biomolecules,2 ion sensing, and signaling,3 energy trans- large quantum yields in polar solvents, thus partly demon-
fer cassettes,4 light harvesting systems,5 and fluorescent strating their potential as fluorescent labels.
stains.6 The parent dye absorbs near 480 nm and emits
around 490 nm. While this is satisfactory for many applica-
tions, longer wavelength excitability and emission would be 2. Results and discussion
highly valuable considering Rayleigh scattering and pig-
mentation problems in many biological samples.7 Thus, The synthesis of the dyes 11, 13, and 15 starts with the prepa-
there have been many attempts4b,8 to move the peak absorp- ration of the standard BODIPY dyes 5, 8, and 9 (Scheme 1).
tion wavelength to the red end of the visible spectrum, with 8-Phenyl- and 8-tert-butyloxycarbonylmethoxyphenyl de-
varying degrees of success. The use of benzo- or naphtho- rivatives were synthesized using appropriate aldehydes and
pyrroles leading to fused BODIPY’s may hamper the solu- purified by a standard work-up. These dyes were then treated
bility to a significant extent. In recent years we and others with aldehyde 2 under reflux with azeotropic removal of
have shown3g,9 that the absorption and emission characteris- water. In the other compounds, additional bromine substitu-
tics of boradiazaindacenes can be altered to a great extent by ents were placed as auxochromic groups. The reaction with
simple condensation reactions of 3,5-dimethylboradiaza- the aldehyde produced both single and double condensation
indacenes with p-dialkylamino substituted aromatic alde- products, which can be separated by silica gel column chro-
hydes. However, only one of the slightly acidic methyl matography. The presence of tert-butyl groups improved or-
groups was reported to condense to yield monostyryl deriva- ganic solubility to a great extent as expected. The absorption
tives. The dyes obtained showed strong charge transfer char- spectra of the dyes 10–15 were obtained in a polar protic sol-
acteristics with reduced emission quantum yields in polar vent, isopropanol. The spectra are shown in Figure 1. The
solvents. Here, we are reporting the first synthesis of doubly second styryl group causes a bathochromic shift of about
styryl substituted boradiazaindacenes (DS-BODIPY’s), 100 nm. The bromine substitution at the pyrrolic positions
results in an additional 11 nm of shift toward the red end
of the visible spectrum. These dyes show remarkable red
Keywords: DS-BODIPY; BODIPY derivatives; Near IR emitting dyes;
Fluorophores; Chromophores.
fluorescence even under ambient light. The fluorescence
* Corresponding author. Tel.: +90 312 210 51526; fax: +90 312 210 1280; spectra were also obtained in isopropanol. The novel fluoro-
e-mail:
[email protected] phores had relatively small Stokes’ shifts of 15 nm, with
0040–4020/$ - see front matter Ó 2006 Elsevier Ltd. All rights reserved.
doi:10.1016/j.tet.2006.06.082
Z. Dost et al. / Tetrahedron 62 (2006) 8484–8488 8485
R1 10,12 11,13
1
S1
S2 a) TFA, CH2Cl2 , 6 hrs 14 15
b) DDQ
c) NEt3, BF3.OEt2 Me Me
0.8
N (20-80%)
H R2 R2
O H N N
B
Absorbance
S2= H (3) or Et (4) Me F F Me 0.6
S1= H (1) or
OCH2COO-tBu (2) 5, 6 or 7
R1
0.4
NBS, AlBN, CCl4 Me Me
5 or 6 0.2
∆
Br Br
N N
B
Me F F Me
0
500 550 600 650 700
8 or 9
Wavelength (nm)
7, 8 or 9
2 Figure 1. Normalized absorption spectra of extended conjugation BODIPY
Piperidine dyes in isopropanol. Compounds 10, 12, and 14 are monostyryl derivatives,
AcOH
Toluene whereas, 11, 13, and 15 are distyryl compounds.
R1 Dean-Stark, ∆ R1
15
100 10,12
14 11,13
Me Me Me Me
R2 R2 R2 R2
N N N N
B B 80
F F Me F F
Rel. Emission Intensity
60
R3 R3 R3
10, 12 or 14 11, 13 or 15
(13-20%) (18-32%)
R1 R2 R3 40
5 H H -
8 H Br -
10 H Br OCH2COO-tBu
11 H Br OCH2COO-tBu 20
7 OCH2COO-t Bu Et -
14 OCH2COO-t Bu Et OCH2COO-tBu
15 OCH2COO-t Bu Et OCH2COO-tBu
6 OCH2COO-t Bu H -
9 OCH2COO-t Bu Br - 0
12 OCH2COO-t Bu Br OCH2COO-tBu 570 620 670 720 770
13 OCH2COO-t Bu Br OCH2COO-tBu Wavelength (nm)
Scheme 1. Synthesis of monostyryl- and distyryl-boradiazaindacene dyes. Figure 2. Normalized emission spectra of extended conjugation BODIPY
dyes in isopropanol. Compounds 10, 12, and 14 are monostyryl derivatives,
whereas, 11, 13, and 15 are distyryl compounds. The excitation wavelength
was 530 nm for the monostyryl dyes and 610 nm for the distyryl dyes. Slit
sharp emission peaks (Fig. 2). Compound 11 had the most widths were 5 nm.
red shifted emission peak at 679 nm. More importantly how-
ever, the fluorophores had only very little internal charge
transfer characteristics; the emission peak position was well transform these dyes into building blocks in functional
only slightly moved bathochromically on changing the sol- supramolecular systems. We are at present investigating such
vent from toluene to DMSO (Fig. 3). The quantum yield paths for further development.
of emission for the dyes 11, 13, and 15 was determined using
bis[4-(dimethylamino)-2-hydroxyphenyl]squaraine as a ref-
erence10 (Table 1). The extinction coefficients were also 3. Conclusion
very large (log 3 4.94–5.00), thus the brightness factor
(Ff3) for these novel fluorophores is in fact larger than We have synthesized and characterized near IR emitting
fluorescein. This straightforward derivatization of parent boradiazaindacene dyes in a very straightforward reaction.
boradiazaindacene structures to yield near IR emitting This is the first report of the double condensation reaction
dyes is not only important for the development of new with 3,5-dimethylboradiazaindacenes. The use of Dean–
biologically relevant fluorescent labels, but also may very Stark apparatus seems to be critical in removing any water
8486 Z. Dost et al. / Tetrahedron 62 (2006) 8484–8488
solvents were distilled over CaCl2 before use. tert-Butyl
100
2-(4-formylphenoxy)acetate was synthesized according to
literature.11 All chemicals were obtained from Aldrich,
unless noted otherwise. Merck Silica Gel 60 F254 TLC Alu-
toluene
80 minum Sheets were used in monitoring reactions by thin
relative emission intensity
isopropanol layer chromatography. Merck Silica Gel 60 (particle size
chloroform 0.040–0.0963 mm, 230–400 mesh ASTM) was used in
60 column chromatography.
EtOH
4.2. Synthesis
40
DMSO
4.2.1. 2,6-Dibromo-1,3,5,7-tetramethyl-8-phenyl-4,40 -
difluoroboradiazaindacene (8). 8-Phenyl-BODIPY (5,
20 0.33 g, 1.02 mmol), AIBN (0.335 g, 2.04 mmol), and NBS
(0.363 g, 2.04 mmol) were refluxed for 30 min in CCl4
(15 mL). Crude product was then concentrated under vac-
0
uum, and purified by silica gel column chromatography
630 650 670 690 710 730 750 770 790 (hexane–EtOAc, 3:1). The red colored fraction was col-
wavelength (nm) lected and the solvent was removed under reduced pressure
to yield the desired compound (5) (393.3 mg, 80%).
Figure 3. Normalized emission spectra of distyryl-BODIPY dye 13 in sol-
vents of varying polarities. Excitation was at 610 nm with 5 nm slit widths. 1
H NMR (400 MHz, CDCl3): 1.37 (s, 6H, CH3), 2.56 (s, 6H,
CH3), 7.15–7.2 (m, 2H, Ar–H), 7.42–7.48 (m, 3H, Ar–H).
Table 1. Selected spectral data of distyryl-BODIPY compounds 11, 13, 13
and 15
C NMR (100 MHz, CDCl3): 153.9, 142.1, 140.6, 134.4,
130.5, 129.5, 129.4, 129.2, 127.8, 28.0, 13.6. Elemental
Distyryl-BODIPY 11 13 15 analysis: Found: C, 47.45; H, 3.62; N, 5.99.
lmax (abs, nm) 657 646 656 C19H17BBr2F2N2 requires: C, 47.35; H, 3.56; N, 5.81. ESI-
lmax (em, nm) 679 668 678 MS (m/z): 482 [M+].
fwhm (nm) 41 36 43
3 (M1 cm1) 1.01105 8.85104 8.79104 4.2.2. Monostyryl- and distyryl-BODIPY dyes (10 and
Fem 0.42 0.44 0.40
11). Compound 8 (500 mg, 1.037 mmol) and tert-butyl
2-(4-formylphenoxy)acetate (2, 0.245 g, 1.037 mmol) were
refluxed in a mixture of toluene (50 mL), glacial acetic
formed in the reaction and thus shifting the equilibrium to acid (0.77 mL), and piperidine (0.94 mL). Any water formed
the double condensation products, which are the distyrl- during the reaction was removed azeotropically by heating
BODIPY dyes. The simplicity of the modification would overnight in a Dean–Stark apparatus. Crude product was
allow facile synthesis of many other BODIPY dyes with then concentrated under vacuum, and purified by silica gel
desired functional groups. The synthesis has a modular column chromatography (EtOAc–hexane, 1:4). The blue
character. The dyes display only a small degree of solvato- colored fraction was collected and the solvent was removed
chromism, this is most likely due to alkoxy group being a under reduced pressure to yield the bright red fluorescent
weakly electron donor substituent compared to dialkylamino compound 10 (145 mg, 20%).
group found in many strong ICT-character chromophores.
With the well known advantages of working with red or Rf 0.65. 1H NMR (400 MHz, CDCl3, d ppm): 1.29 (s, 3H,
near IR emitting fluorophores, we have no doubt that this CH3), 1.32 (s, 3H, CH3), 1.42 (s, 9H, C(CH3)3), 2.56 (s,
series of boradiazaindacenes will be attractive candidates 3H, CH3), 4.5 (s, 2H, OCH2), 6.84 (d, J¼8.7 Hz, 2H,
for practical applications. C]CH), 7.16–7.22 (m, 2H, Ar–H), 7.42–7.54 (m, 6H,
Ar–H), 8.00 (d, J¼16.6 Hz, 1H, C]CH).
13
4. Experimental C NMR (100 MHz, CDCl3): 167.1, 159.0, 154.0, 148.5,
141.5, 140.6, 140.1, 138.5, 134.6, 131.3, 131.0, 130.5,
4.1. General 129.5, 129.4, 129.1, 128.0, 118.2, 116.3, 115.0, 110.1,
109.7, 82.5, 65.7, 28.0, 13.8, 13.6, 10.6. Elemental analysis:
The compounds were characterized and analyzed by Nuclear Found: C, 54.71; H, 4.58; N, 3.93. C32H31BBr2F2N2O3
Magnetic Resonance spectroscopy (NMR), UV–vis spec- requires: C, 54.89; H, 4.46; N, 4.00. ESI-MS (m/z): 707 [M+].
troscopy, and fluorescence spectroscopy. 1H and 13C Nuclear
Magnetic Resonance spectra of all compounds were re- The green colored fraction was collected and the solvent was
corded in CDCl3 with Bruker Gmbh DPX-400, 400 MHz removed under reduced pressure to yield the distyryl dye 11
High Performance Digital FTNMR Spectrometer. UV–vis (300 mg, 32%).
spectra were recorded by Varian Bio 100 UV–vis Spectro-
photometer. Fluorescence spectra were recorded using Rf 0.47. 1H NMR (400 MHz, CDCl3, d ppm): 1.37 (s, 6H,
Varian Cary Eclipse Fluorescence Spectrophotometer. All CH3), 1.42 (s, 18H, C(CH3)3), 4.5 (s, 4H, OCH2), 6.88
Z. Dost et al. / Tetrahedron 62 (2006) 8484–8488 8487
(d, J¼8.8 Hz, 4H, C]CH), 7.23 (dd, J¼2.1 Hz, J¼5.8 Hz, 7.01; N, 3.95. C42H51BF2N2O6 requires: C, 69.23; H, 7.05;
2H, Ar–H), 7.42–7.47 (m, 3H, Ar–H), 7.51–7.58 (m, 6H, N, 3.84. ESI-MS (m/z): 728 [M+].
Ar–H), 8.01 (d, J¼16.6 Hz, 2H, C]CH).
The green colored fraction was collected and then the
13
C NMR (100 MHz, CDCl3): 168.6, 159.8, 149.3, 141.9, solvent was removed under reduced pressure to yield the
139.9, 139.5, 135.7, 132.9, 131.4, 130.4, 130.3, 130.2, distyryl compound 15 (90 mg, 18%).
129.9, 129.2, 117.3, 115.8, 83.5, 66.5, 29.0, 14.6. Elemental
analysis: Found: C, 58.82; H, 5.01; N, 2.98. Rf 0.29. 1H NMR (400 MHz, CDCl3): 1.08 (t, J¼7.3 Hz, 6H,
C45H45BBr2F2N2O6 requires: C, 58.85; H, 4.94; N, 3.05. CH3), 1.30 (s, 6H), 1.42 (s, 27H, C(CH3)3), 2.48–2.58 (q,
ESI-MS (m/z): 918 [M+]. J¼7.3 Hz, 4H, CH2), 4.49 (s, 4H, OCH2), 4.52 (s, 2H,
OCH2), 6.86 (d, J¼8.6 Hz, 2H, Ar–H), 6.95 (d, J¼8.5 Hz,
4.2.3. 2,6-Diethyl-1,3,5,7-tetramethyl-8-(4-tert-butoxy- 2H, Ar–H), 7.09–7.2 (m, 4H, Ar–H), 7.49 (d, J¼8.6 Hz,
carbonyl-methyloxyphenyl)-4,40 -difluoroboradiazainda- 4H, Ar–H), 7.59 (d, J¼16.7 Hz, 2H, C]CH).
cene (7). 2,4-Dimethyl-3-ethylpyrrole (4, 0.81 g,
13
6.55 mmol) and tert-butyl 2-(4-formylphenoxy)acetate (2, C NMR (100 MHz, CDCl3): 166.8, 166.7, 157.5, 157.4,
0.75 g, 3.18 mmol) were dissolved in absolute CH2Cl2 149.4, 137.8, 134.1, 132.6, 132.3, 130.1, 128.9, 128.1,
(200 mL) under N2 atmosphere, one drop of TFA was added 127.7, 117.6, 114.3, 113.9, 111.3, 81.6, 81.5, 64.9, 64.8,
and the solution was stirred at rt until TLC analysis showed 27.1, 27.0, 17.4, 13.1, 10.7. Elemental analysis: Found: C,
complete consumption of the aldehyde. At this point, a solu- 69.88; H, 6.98; N, 2.99. C55H65BF2N2O9 requires: C,
tion of tetrachlorobenzoquinone (0.81 g, 3.18 mmol) in 69.76; H, 6.92; N, 2.96. ESI-MS (m/z): 946 [M+].
CH2Cl2 (150 mL) was added, stirring was continued for
15 min. Then, Et3N (10.0 mL) and BF3$OEt2 (10.0 mL) 4.2.5. 1,3,5,7-Tetramethyl-8-(4-tert-butoxycarbonyl-
were added. After stirring for another 12 h, crude product methyloxyphenyl)-4,40 -difluoroboradiazaindacene (6). A
was washed three times with water, dried over Na2SO4, procedure very similar to the synthesis of compound 7 was
and evaporated to dryness. The residue was chromato- applied in the synthesis of this BODIPY dye. Thus, tert-
graphed on silica gel (CHCl3–MeOH, 96:4) to afford butyl 2-(4-formylphenoxy)acetate (2, 1.5 g, 6.35 mmol),
324 mg (yield: 20%) of 7 in the form of orange needles. 2,4-dimethylpyrrole (3, 1.25 g, 13.1 mmol), Et3N (10.0 mL),
BF3$OEt2 (10.0 mL), and 1.62 g of DDQ were used in this
1
H NMR (400 MHz, CDCl3): 0.90 (t, J¼7.5 Hz, 6H, CH3), reaction. The residue was chromatographed on silica gel
1.25 (s, 6H, CH3), 1.42 (s, 9H, C(CH3)3), 2.13–2.26 (q, (CHCl3–MeOH, 95:5) to afford 0.784 g of compound 6 in
J¼7.5 Hz, 4H, CH2), 4.50 (s, 2H, OCH2), 6.94 (d, the form of orange needles. Yield: 27%.
J¼8.5 Hz, 2H, Ar–H), 7.1 (d, J¼8.5 Hz, 2H, Ar–H).
1
H NMR (400 MHz, CDCl3): 1.35 (s, 6H, CH3), 1.42 (s, 9H,
13
C NMR (100 MHz, CDCl3): 165.9, 156.6, 151.8, 138.2, C(CH3)3), 2.48 (s, 6H, CH3), 4.55 (s, 2H, OCH2), 5.88 (s,
136.6, 130.9, 129.3, 127.87, 127.0, 113.4, 80.7, 64.1, 26.2, 2H, Pyr–H), 6.94 (d, J¼8.5 Hz, 2H, Ar–H), 7.10 (d,
15.2, 12.8, 10.7, 10.0. Elemental analysis: Found: C, J¼8.5 Hz, 2H, Ar–H).
68.35; H, 7.39; N, 5.40. C29H37BF2N2O3 requires: C,
68.24; H, 7.31; N, 5.49. ESI-MS (m/z): 510 [M+]. 13
C NMR (100 MHz, CDCl3): 167.6, 158.5, 155.3, 143.1,
141.5, 131.8, 129.3, 127.9, 121.2, 115.3, 82.6, 65.8, 61.7,
4.2.4. Monostyryl- and distyryl-BODIPY dyes (14 and 28.0, 14.5. Elemental analysis: Found: C, 66.17; H, 6.55;
15). A similar procedure was followed in the synthesis of N, 6.11. C25H29BF2N2O3 requires: C, 66.09; H, 6.43; N,
these monostyryl and distyryl dyes; thus, the BODIPY 6.17. FABMS (m/z): 454 [M+].
dye 7 (0.2662 g, 0.5215 mmol) and the aldehyde 2
(0.246 g, 1.043 mmol), piperidine (0.47 mL) and acetic 4.2.6. 2,6-Dibromo-1,3,5,7-tetramethyl-8-(4-tert-butoxy-
acid (0.39 mL) were used in this reaction. The desired carbonyl-methyloxyphenyl)-4,40 -difluoroboradiazainda-
compounds were purified by silica gel column chromato- cene (9). Compound 6 (0.784 g, 1.73 mmol), AIBN (0.57 g,
graphy (CHCl3–hexane, 5:1). The blue colored fraction 3.46 mmol), and NBS (0.616 g, 3.46 mmol) were refluxed
was collected and the solvent was removed under reduced for 40 min in CCl4 (40 mL). Crude product was concentrated
pressure to yield the monostyryl compound 14 (50 mg, under reduced pressure and purified by silica gel column
13%). chromatography (CHCl3). The red colored fraction was col-
lected and the solvent was removed under reduced pressure
Rf 0.35. 1H NMR (400 MHz, CDCl3): 0.92 (t, J¼7.3 Hz, 3H, to yield the desired compound (9) (761 mg, 72%).
CH3), 1.04–1.09 (t, J¼7.3 Hz, 3H, CH3), 2.26 (q, 7.5 Hz,
1
2H, CH3), 2.50 (s+q, 5H, CH3+CH2), 4.46 (s, 2H, OCH2), H NMR (400 MHz, CDCl3): 1.34 (s, 6H, CH3), 1.42 (s, 9H,
4.52 (s, 2H, OCH2), 6.84 (d, J¼8.5 Hz, 1H, C]CH), 6.94 C(CH3)3), 2.52 (s, 6H, CH3), 4.52 (s, 2H, OCH2), 6.96 (d,
(d, J¼9.6 Hz, 2H, Ar–H), 7.03–7.22 (m, 3H, Ar–H), 7.34 J¼8.5 Hz, 2H, Ar–H), 7.08 (d, J¼8.5 Hz, 2H, Ar–H).
(d, J¼6.7 Hz, 1H, Ar–H), 7.48 (d, J¼9.6 Hz, 2H, Ar–H).
13
C NMR (100 MHz, CDCl3): 167.5, 158.9, 153.9, 143.0,
13
C NMR (100 MHz, CDCl3): 167.8, 167.7, 158.5, 158.3, 140.6, 130.7, 129.2, 127.2, 115.6, 111.7, 82.7, 82.7, 82.6,
155.0, 149.2, 139.1, 138.7, 138.5, 134.5, 133.5, 132.8, 68.0, 65.8, 28.0, 13.8. Elemental analysis: Found: C,
132.1, 131.2, 129.7, 128.9, 128.5, 118.4, 115.2, 114.9, 49.02; H, 4.49; N, 4.49. C25H27BBr2F2N2O3 requires: C,
82.5, 82.4, 65.9, 65.8, 28.1, 28.0, 18.3, 17.1, 14.5, 14.1, 49.05; H, 4.45; N, 4.58; O, 7.84. FABMS (m/z): 612
12.7, 11.9, 11.5. Elemental analysis: Found: C, 69.34; H, [M+].
8488 Z. Dost et al. / Tetrahedron 62 (2006) 8484–8488
4.2.7. Monostyryl- and distyryl-BODIPY dyes (12 and References and notes
13). The applied procedure was very similar to the synthesis
of other styryl dyes in this study. The dibromo compound 9 1. Handbook of Fluorescent Probes and Research Products, 9th
(0.761 g, 1.24 mmol), 2 (0.587 g, 2.49 mmol), piperidine ed.; Haugland, R. P., Ed.; Molecular Probes: Eugene, OR,
(11.2 mL), and acetic acid (0.93 mL) were used in this 2003.
reaction. Following the usual work-up, the reaction mix- 2. (a) Yee, M.; Fas, S. C.; Stohlmeyer, M. M.; Wandless, T. J.;
ture was purified by silica gel column chromatography Cimprich, K. A. J. Biol. Chem. 2005, 280, 29053–29059;
(CHCl3–hexane, 5:1). The blue colored fraction was col- (b) Tan, K.; Jaquinod, L.; Paolesse, R.; Nardis, S.;
lected and the solvent was removed under reduced pressure Di Natale, C.; Di Carlo, A.; Prodi, L.; Montalti, M.;
to yield the desired compound 12 (0.154 g, 15%). Zaccheroni, N.; Smith, K. M. Tetrahedron 2004, 60, 1099–
1106.
Rf 0.39. 1H NMR (400 MHz, CDCl3): 1.35 (s, 3H, CH3), 3. Recent examples: (a) Turfan, B.; Akkaya, E. U. Org. Lett. 2002,
1.38 (s, 3H, CH3), 1.47 (s, 18H, C(CH3)3), 2.58 (s, 3H, 4, 2857–2859; (b) Ulrich, G.; Ziessel, R. J. Org. Chem. 2004,
CH3), 4.47 (s, 2H, OCH2), 4.53 (s, 2H, OCH2), 6.83 (d, 69, 2070–2083; (c) Gabe, Y.; Urano, Y.; Kikuchi, K.; Kojima,
J¼8.7 Hz, 2H, Ar–H), 6.98 (d, J¼8.5 Hz, 2H, Ar–H), 7.12 H.; Nagano, T. J. Am. Chem. Soc. 2004, 126, 3357–3367; (d)
(d, J¼8.5 Hz, 2H, Ar–H), 7.54–7.45 (m, 3H), 8.1 (d, Rurack, K.; Kollmannsberger, M.; Resch-Genger, U.; Daub,
J¼15.5 Hz, 1H, C]CH). J. J. Am. Chem. Soc. 2000, 122, 968–969; (e) Coskun, A.;
Baytekin, B. T.; Akkaya, E. U. Tetrahedron Lett. 2003, 44,
13
C NMR (100 MHz, CDCl3): 167.6, 166.5, 159.1, 158.3, 5649–5651; (f) Coskun, A.; Akkaya, E. U. Tetrahedron Lett.
156.2, 148.6, 143.0, 141.5, 138.3, 132.9, 129.5, 128.3, 2004, 45, 4947–4949; (g) Coskun, A.; Akkaya, E. U. J. Am.
126.9, 121.0, 115.5, 114.9, 82.7, 80.3, 65.8, 61.5, 39.3, Chem. Soc. 2005, 127, 10464–10465.
28.0, 23.2, 13.3. Elemental analysis: Found: C, 54.86; H, 4. (a) Burghart, A.; Thoresen, L. H.; Chen, J.; Burgess, K.;
4.88; N, 3.43. C38H41BBr2F2N2O6 requires: C, 54.97; H, Bergstr€
om, F.; Johansson, L. B.-Å. Chem. Commun. 2000,
4.98; N, 3.37. ESI-MS (m/z): 830 [M+]. 2203–2204; (b) Wan, C.-W.; Burghart, A.; Chen, J.;
Bergstr€
om, F.; Johansson, L. B.-Å.; Wolford, M. F.; Kim,
The green colored fraction was collected and then the sol- T. G.; Topp, M. R.; Hochstrasser, R. M.; Burgess, K.
vent was removed under reduced pressure to yield the de- Chem.—Eur. J. 2003, 9, 4430–4441; (c) Ulrich, G.; Goze, C.;
sired compound 13 (0.248 g, 20%). Guardigli, M.; Roda, A.; Ziessel, R. Angew. Chem., Int. Ed.
2005, 44, 3694–3698.
Rf 0.29. 1H NMR (400 MHz, CDCl3): 1.39 (s, 6H, CH3), 5. Maas, H.; Calzaferri, G. Angew. Chem., Int. Ed. 2002, 41,
1.43 (s, 18H, OC(CH3)3), 1.50 (s, 9H, OC(CH3)3), 4.49 (s, 2284–2288.
4H, OCH2), 4.54 (s, 2H, OCH2), 6.85 (d, J¼8.6 Hz, 4H, 6. Dahim, D.; Mizuno, N. K.; Li, X.-M.; Momsen, W. E.;
Ar–H), 6.96 (d, J¼8.5 Hz, 2H, Ar–H), 7.11 (d, J¼8.6 Hz, Momsen, M. M.; Brockman, H. L. Biophys. J. 2002, 83,
2H, Ar–H), 7.5 (m, 6H), 8.0 (d, J¼16.6 Hz, 2H, C]CH). 1511–1524.
7. Cullander, C. J. Microsc. 1994, 176, 281–286.
13
C NMR (100 MHz, CDCl3): 166.7, 166.5, 157.9, 157.8, 8. (a) See Ref. 4a; (b) Shen, Z.; Rohr, H.; Rurack, K.; Uno, H.;
147.3, 139.9, 137.6, 131.3, 129.5, 128.6, 128.3, 126.7, Spieles, M.; Schulz, B.; Reck, G.; Ono, N. Chem.—Eur. J.
115.4, 115.4, 114.5, 113.9, 109.1, 81.7, 81.6, 64.7, 64.6, 2004, 10, 4853–4871.
27.0, 27.0, 12.9. Elemental analysis: Found: C, 58.46; H, 9. (a) Haugland, R. P.; Kang, H. C. Molecular Probes, US Patent
5.35; N, 2.68. C51H55BBr2F2N2O9 requires: C, 58.42; H, 4,774,339, 1988; (b) Rurack, K.; Kollmannsberger, M.; Daub,
5.29; N, 2.67. ESI-MS (m/z): 1048 [M+]. J. Angew. Chem., Int. Ed. 2001, 40, 385–387; (c) Coskun, A.;
Deniz, E.; Akkaya, E. U. Org. Lett. 2005, 7, 5187–5189.
10. Law, K.-Y. J. Phys. Chem. 1987, 91, 5184–5193.
Acknowledgements 11. Mehrotra, M. M.; Heath, J. A.; Rose, J. W.; Smyth, M. S.;
Seroogy, J.; Volkots, D. L.; Ruhter, G.; Schotten, T.; Alaimo,
The authors gratefully acknowledge support from TUBITAK L.; Park, G.; Pandeya, A.; Scarborough, R. M. Bioorg. Med.
(TBAG 104T350) and Turkish Academy of Sciences. Chem. Lett. 2002, 12, 1103–1107.
