Synthesis and optical properties of difluorobora-s-diazaindacene dyes with trifluoromethyl meso-substituents

Article abstract of DOI:10.1002/ejoc.201300212

A series of meso-CF₃-4,4-difluoro-4-bora-3a,4a-diaza-s-indacene (BODIPY) dyes with aryl and hetaryl substituents at the C-3 and C-5 positions, both symmetric and asymmetric, have been synthesized in 36-90 % yields by a new strategy involving as the key step the condensation of 2,2,2-trifluoro-1-(5- arylpyrrol-2-yl)-1-ethanols with diverse 2-arylpyrroles. The starting 2,2,2-trifluoro-1-(5-arylpyrrol-2-yl)-1-ethanols are easily prepared by reduction of the available 2-trifluoroacetyl-5-arylpyrroles. The synthesized dyes fluoresce in a longer wavelength region (626-698 nm) with high quantum yield (0.84-0.99). A new strategy for the synthesis of highly efficient symmetric and asymmetric BODIPY fluorophores that combine trifluoromethyl and 3,5-aryl substituents has been developed. The key step is the P ₂O₅-promoted condensation of 2,2,2-trifluoro-1-(5- arylpyrrol-2-yl)-1-ethanols with diverse 2-arylpyrroles. Copyright

Full text of DOI:10.1002/ejoc.201300212

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FULL PAPER
Synthetic Dyes
L. N. Sobenina, O. V. Petrova,
K. B. Petrushenko, I. A. Ushakov,
A. I. Mikhaleva, R. Meallet-Renault,
B. A. Trofimov* .............................. 1–13
Synthesis and Optical Properties of Di-
fluorobora-s-diazaindacene Dyes with Tri-
fluoromethyl meso-Substituents
Keywords: Synthetic methods / Dyes/pig-
ments / Nitrogen heterocycles / Fluor-
escence
A new strategy for the synthesis of highly
efficient symmetric and asymmetric
BODIPY fluorophores that combine tri-
fluoromethyl and 3,5-aryl substituents has
been developed. The key step is the P2O5-
promoted condensation of 2,2,2-trifluoro-
1-(5-arylpyrrol-2-yl)-1-ethanols with di-
verse 2-arylpyrroles.
0000, 0–0
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B. A. Trofimov et al.
FULL PAPER
DOI: 10.1002/ejoc.201300212
1
Synthesis and Optical Properties of Difluorobora-s-diazaindacene Dyes with
Trifluoromethyl meso-Substituents
Lyubov N. Sobenina,[a] Olga V. Petrova,[a] Konstantin B. Petrushenko,[a] Igor A. Ushakov,[a]
Albina I. Mikhaleva,[a] Rachel Meallet-Renault,[b] and Boris A. Trofimov*[a]
Keywords: Synthetic methods / Dyes/pigments / Nitrogen heterocycles / Fluorescence
6
A series of meso-CF3-4,4-difluoro-4-bora-3a,4a-diaza-s-ind-
acene (BODIPY) dyes with aryl and hetaryl substituents at
the C-3 and C-5 positions, both symmetric and asymmetric,
have been synthesized in 36–90% yields by a new strategy
involving as the key step the condensation of 2,2,2-trifluoro-
1-(5-arylpyrrol-2-yl)-1-ethanols with diverse 2-arylpyrroles.
The starting 2,2,2-trifluoro-1-(5-arylpyrrol-2-yl)-1-ethanols
are easily prepared by reduction of the available 2-trifluoro-
acetyl-5-arylpyrroles. The synthesized dyes fluoresce in a
longer wavelength region (626–698 nm) with high quantum
yield (0.84–0.99).
16
41
11
achieved by introducing a strong electron acceptor such as
Introduction
[15,16]
pentafluorobenzene[14] or CF3
at the meso-position of
BODIPY dyes (4,4-difluoro-4-bora-3a,4a-diaza-s-indac-
ene) possess many distinctive and desirable properties such
as high molar absorption coefficient, fluorescence quantum
yields and long wavelength emission.[1] They have found nu-
merous applications as optical chemosensors,[2] fluorescent
biolabels,[3] light-harvesting molecules,[4] emitters in organic
light-emitting diodes,[5] and light absorbers for solar cells.[6]
Biochemical applications of BODIPYs include conjuga-
tion with a variety of biomolecules such as lipids,[7] pro-
teins,[8] DNA,[9] carbohydrates[10] and cholesterol.[11]
BODIPYs that absorb and emit in the near-infrared
(NIR) region are efficiently used to visualize and investigate
in vivo molecular targets.[12] Therefore, it is of applied inter-
est to shift the absorption or fluorescence maximum of
BODIPYs into the red or NIR region as far as possible and
increasing simultaneously the quantum yield.
An efficient way to red-shift the absorption and emission
maxima is to extend the conjugated π-system of the
BODIPY molecule by introducing aromatic substituents in
the 5- and/or 3-positions at the indacene core.[13] This ap-
proach allows both absorption and emission to be shifted
by 100–200 nm towards red. Very important shifts towards
the NIR end of the visible spectra have been recently
the BODIPY core, though the asymmetrical representatives
with a meso-CF3 moiety can only be synthesized by using
a specific methodology.[16]
21
26
31
36
We have concisely reported that the presence of a CF3
group in the meso-position of the BODIPY core does cause
a deep bathochromic shift relative to congeners with other
substituents in this position.[16] Despite this progress, syn-
thesis of new meso-CF3-BODIPY derivatives with aryl
groups remains challenging because the fluorescence max-
ima of BODIPY strongly depend on the nature of the aryl
substituent.[17]
46
51
Results and Discussion
The key step in the meso-CF3-BODIPYs synthesis has
been briefly outlined.[16] The step represents the P2O5-pro-
moted condensation of available 2,2,2-trifluoro-1-(pyrrol-2-
yl)-1-ethanols with pyrroles. It should be noted that this
methodology makes it possible to synthesize both symmet-
rical and asymmetrical BODIPYs as opposed to other
methods[14,15] affording exclusively symmetrical BODIPYs.
Inspired by this success, we have undertaken the synthe-
56
61
66
71
[a] A. E. Favorsky Irkutsk Institute of Chemistry Siberian Branch, sis of BODIPY derivatives combining aryl groups and a
Russian Academy of Science,
meso-CF3 substituent.
1 Favorsky Str., 664033 Irkutsk, Russian Federation
We disclose herein the further development of the above-
mentioned synthesis and describe the preparation of a vari-
ety of new meso-trifluoromethylated BODIPY dyes with
aryl and heteroaryl substituents at the C-3 and C-5 posi-
tions. The synthesis starts from easily available 2-phenylpyr-
roles 1a–1g, which have different substituents at the p-posi-
tion of the benzene ring.
Fax: +7-3952-419346
E-mail: boris_trofimov@irioch.irk.ru
Homepage: http://www.irkinstchem.ru
[b] Laboratoire de Photophysique et Photochimie
Supramoleculaires et Macromoleculaires (CNRS UMR 8531),
Ecole Normale Superieure de Cachan,
61 Avenue du President Wilson, 94235 Cachan cedex, France
Supporting information for this article is available on the
WWW under http://dx.doi.org/10.1002/ejoc.201300212.
2
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Difluorobora-s-diazaindacene Dyes
Pyrroles 1a–1e are readily obtained from alkylarylketox- one-pot procedure to furnish target BODIPY dyes 3 in 36–
imes and acetylene through the Trofimov reaction[18] in a 90% yields (Scheme 3, Table 1).
one-pot procedure (Scheme 1).
This general strategy allows, depending on the structure
of pyrroles 1a–1g and ethanols 5c–5g, both symmetric and
asymmetric BODIPY dyes 3 to be easily assembled.
Thus, the synthesis of asymmetric BODIPY dyes, which
was a long-standing challenge, has been incidentally an ele-
gantly overcome.
96
In some cases the synthesis of asymmetric dipyrrometh- 101
anes is accompanied by the formation of insignificant quan-
tities (2–3%) of two symmetric ones. For instance, dipyrro-
methanes 6bb and 6ff have been identified (19F NMR spec-
troscopy) in the synthesis of the asymmetric dipyrrometh-
Scheme 1. Synthesis of pyrroles 1a–1e.
Previously unknown 2-[(1,1-biphenyl)-4-yl]pyrrole (1f)
and 2-[(1,1-biphenyl)-4-yl]-3-phenylpyrrole (1g) have been
synthesized by devinylation[19] of the corresponding N-vinyl
derivatives 2f and 2g, which are the major products of the
Trofimov reaction owing to rapid vinylation of the interme-
diate NH-pyrroles (Scheme 2).
ane 6bf (Scheme 4).
106
76
Scheme 4. The formation of dipyrromethanes 6bf, 6bb and 6ff.
Scheme 2. Synthesis of pyrroles 1f and 1g.
The formation of symmetric dipyrromethanes as minor
81
86
91
Scheme 3 shows the synthetic route to BODIPY dyes 3 products may be rationalized as follows: under the acidic
from pyrroles 1a–1g. The reaction sequence includes tri- conditions of the synthesis, the asymmetric dipyrrometh-
fluoroacetylation of pyrroles 1c–1g to afford 2-trifluoro- anes (for instance 6bf) disproportionate partially into pyr-
acetylpyrroles 4c–4g. The reduction products of pyrroles role carbocations (7b and 7f) and pyrroles (1b and 1f; 111
4c–4g with NaBH4, 2,2,2-trifluoro-1-(pyrrol-2-yl)-1-ethan- Scheme 5). Cation 7b may attack pyrrole 1b to afford sym-
ols 5c–5g, reacted with pyrroles 1a–1g in the presence of metric dipyrromethane 6bb. Analogously, attack of pyrrole
P2O5 (equimolar ratio) to give dipyrromethanes 6. The lat- 1f at cation 7f gives dipyrromethane 6ff.
ter are easily isolated and can be used as intermediates in
Another plausible pathway to symmetric dipyrrometh-
syntheses of other compounds, in particular, porphyrins.[20] anes, and hence to symmetric BODIPYs, may be the disso- 116
Oxidation of dipyrromethanes 6 with 2,3-dichloro-5,6-di- ciation of starting pyrrolylethanols 5c–5g to the free pyrrole
cyanobenzoquinone (DDQ) and subsequent complexation and trifluoroacetaldehyde, the latter able to react with the
of the resulting dipyrromethenes with BF3 is realized as a two same pyrrole molecules (Scheme 6).
Scheme 3. Synthesis of BODIPY dyes 3.
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Table 1. Preparation of BODIPY dyes 3 from ethanols 5c–5g and
pyrroles 1a–1g through Scheme 3.
Table 1. (Continued).
Scheme 5. Proposed symmetrisation of dipyrromethanes 6bb and
6ff.
4
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Difluorobora-s-diazaindacene Dyes
towards the red region according to the electron-donating
ability of the substituents (Cl Ͻ CH3 Ͻ OCH3) and their 136
number (Table 2). Relative to known meso-4Ј-iodophenyl-
BODIPYs[13a] bearing the same substituents in the C-3 and
C-5 positions, dyes 3 absorb and emit in longer-wave re-
gions and have much higher Φf values. For example, 4,4-
difluoro-8-(4Ј-iodophenyl)-3,5-diphenyl-4-bora-3a,4a-di- 141
aza-s-indacene has λmax,abs = 558 nm, λmax,fl = 592 nm and
Φf = 0.15,[13a] whereas BODIPY dye 3aa has λmax,abs
=
586 nm, λmax,fl = 626 nm and Φf = 0.74 and 4,4-difluoro-8-
(4Ј-iodophenyl)-3,5-bis(4-methoxyphenyl)-4-bora-3a,4a-di-
aza-s-indacene has λmax,abs = 585 nm, λmax,fl = 629 nm, Φf 146
Scheme 6. Alternative pathway to symmetric dipyrromethane 6bb
(dipyrromethane 6ff is formed analogously).
= 0.33,[13a] and 3dd has λmax,abs = 616 nm, λmax,fl
=
665.5 nm, Φf = 0.98. On average, replacing a 4Ј-iodophenyl
substituent by a CF3 group in the meso-position leads to a
shift in the most long-wave absorption band and fluores-
cence band by ca. 900 cm–1. Replacement of the meso-aryl 151
with a trifluoromethyl moiety reduces the non-radiative de-
cay through rotation, and leads to fluorophores with higher
quantum yields.[15b]
The extension of the π-system owing to the increase in
number of phenyl substituents in the BODIPY molecules 156
also favors the red shift of the absorption and fluorescence
bands (BODIPY 3ff, 3ag, 3bg, 3gg; Table 2). At the same
time, asymmetric BODIPYs have decreased red-shift values.
Relative to BODIPY 3af and 3ag, their thienyl analogs
Figure 1 depicts the absorption and fluorescence spectra
121 of synthesized dyes 3cc, 3ff and 3bf. The spectra show in-
tense long-wave absorption bands and almost symmetrical
corresponding fluorescence bands. Detailed spectroscopic
and photophysical characteristics of BODIPY dyes 3 in-
cluding lifetime (τf), fluorescence rate constant (kf, kf = -
126 1/τf) as well as rate constants of radiative (kr) and non-radi-
ative (knr) deactivation are given in Table 2. The same data
for
4,4-difluoro-3,5-diphenyl-8-trifluoromethyl-4-bora-
3a,4a-diaza-s-indacene (3aa) synthesized earlier[16] are also
given in Table 2 and Figure 1.
131
Simple, “transparent”, substituents (-Cl, -CH3, -OCH3)
in the p-position of the benzene ring do not change the 3bf and 3bg absorb and fluoresce at longer wave lengths, 161
general character of absorption and fluorescence spectra. their absorption and fluorescent bands are narrower and
Nevertheless, the bands maxima are progressively shifted they have lower ΔνSt values. The aforementioned changes in
Figure 1. Normalized absorption (1–4) and fluorescence spectra (5–8) of BODIPYs 3aa (1, 5), 3cc (2, 6), 3ff (3,7) and 3bf (4, 8) in MeCN.
Table 2. Spectroscopic and photophysical data of BODIPYs 3 recorded in MeCN at 22 °C.
BODIPY
λmax,abs
Absorption coeffi-
cient
(ε [m–1 cm–1])
λmax,fl λmax,ex
Stokes shift
τf
Fluorescence quantum
kfϫ109 krϫ109
k
nr ϫ109
yield (Φf)[a]
[nm]
[nm]
[nm]
(ΔνSt [cm–1])
[ns]
[s–1 [s–1 [b]
]
]
[s–1 [c]
]
3aa[16]
3ac
3cc
3ad
3dd
3ae
3ee
3af
3bf
3ff
3ag
3bg
3gg
586
593
599
606
616
589
592
599
636
612
613
644
637
46000
57800
56400
55700
57200
55700
56800
54500
57600
55800
53000
52300
52000
626.0
632.5
640.5
650.5
665.5
629.0
634.0
646.5
674.0
667.0
673.0
688.5
698.0
586
592
598
606
617
588
592
598
635
611
614
643
638
1090
1050
1080
1130
1180
1080
1120
1200
890
1350
1450
1000
1370
6.4
6.2
6.2
5.7
5.7
6.3
6.3
5.9
5.6
5.7
0.6
1.2
1.0
0.74
0.92
0.88
0.89
0.98
0.89
0.89
0.88
0.84
0.91
0.05
0.13
0.07
0.16
0.16
0.16
0.18
0.18
0.16
0.16
0.17
0.18
0.18
1.67
0.83
1.00
0.12
0.15
0.14
0.16
0.17
0.14
0.14
0.15
0.15
0.16
0.08
0.11
0.07
0.04
0.01
0.02
0.02
0.01
0.02
0.02
0.02
0.03
0.02
1.59
0.72
0.93
[a] Nile blue as standard [Φf = 0.27, 0.5% (v/v) 0.1 m HCl in ethanol]. [b] kr = Φf/τf. [c] knr = τf–1 – kr.
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B. A. Trofimov et al.
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spectroscopic characteristics indicate a more planar struc- cantly twisted from the molecule plane relative to com-
ture for the thienyl-containing BODIPY, likely owing to pound 3af. The phenyl substituent itself in the 2 position
166 lower steric hindrance from the five-membered thienyl deviates from the BODIPY core by ca. 40°.
ring.[16,21]
Of special interest is the dependence of value rate con-
stants kr and knr on the presence or absence of the phenyl
substituents conjugated with the BODIPY core in the 2
171 and/or 6 positions. The BODIPYs containing no such sub-
stituents have kr ϾϾ knr, and their Φf = (kr/kr + knr) values
are close to 1. However compounds 3ag, 3bg and 3gg bear-
ing substituents possess approximately two-times lower kr
values and 40-times higher knr constants. For these BODI-
176 PYs, radiative transitions are much less probable than non-
radiative deactivation and they have low Φf values (Table 2).
Apparently, the main cause for the drop of kr value and
increase of knr value is the decrease of 3ag, 3bg and 3gg
planarity in the S0 and S1 states from steric strain between
181 bulky phenyl substituents. This is supported by high ΔνSt
and half-width absorption band values as well as by quan-
tum-chemical calculations of similar systems.[16] The drop
of kr values with the decrease of planarity is a natural con-
sequence of weakening of the π-orbitals interaction, and
186 growth of knr values results from non-radiative losses owing
to significant changes of torsion angles in the S1 state.
These inferences are in accordance with quantum-chemi-
cal calculations of BODIPY 3af and 3ag, which have been
selected as molecules containing or not containing phenyl
191 substituents at the 2 position. Geometries for the molecules
in the S0 state were optimized by using the RI-DFT/BP86/
def2-TZVP method. Energies of S0 ǞSi (i = 1–3) transitions
Figure 2. Optimized structures of BODIPY 3af and 3ag in state S0
were determined by using a time-dependent DFT (TDDFT)
method RI-TD-BP86/def2-TZVP based on the optimized
196 geometries of the S0 state. To decrease the calculation time
the resolution identity (RI) was applied.
according to RI-BP86/def2-TZVP.
The increase in torsion angle between the BODIPY core
and biphenyl moiety should lead to a hypsochromic shift of 216
Optimized structures 3af and 3ag and calculated values the absorption band of compound 3ag relative to 3af owing
of excitation energy are given in Figure 2 and Table 3, to the partial loss of conjugation. However, experimentally
respectively. Both molecules have an almost planar struc- (Table 2) a bathochromic shift is observed. Probably, any
201 ture for the BODIPY core with a tetragonal boron atom, hypsochromic shift is compensated for by the bathochromic
two fluorine atoms perpendicular to the BODIPY plane shift exerted by the phenyl substituent in the 2 position.
221
and phenyl substituents deviated from the BODIPY skel-
The calculated (on the basis of optimized geometries) en-
eton. In compound 3af, the torsion angle between the ergy values of vertical S0 ǞS1 transitions for compounds
BODIPY plane and biphenyl fragment is ca. 30°. The intro- 3af and 3ag are 614.1 and 642.6 nm, respectively (Table 3)
206 duction of another phenyl substituent in the 2 position and are in good agreement with experimental data: 599
(compound 3ag) increases this angle up to ca. 50°, whereas (3af) and 614 nm (3ag) (Table 2). Theoretical values of exci- 226
the torsion angle between the phenyl moieties in the bi- tation energies and oscillator strength allow one to evaluate
phenyl fragments remains the same (ca. 36°; Figure 2). the radiation rate constants for emission of 3af and 3ag by
Thus, based on the phenyl substituent size it can be con- using the Einstein transition probabilities[22] (au): kr = 2E2
211 cluded the biphenyl fragment of BODIPY 3ag is signifi- f/c3, in which c is the velocity of light, E is the transition
Table 3. Excitation energies and oscillator strength of BODIPY 3af and 3ag in the gas phase (RI-TD-BP86/def2-TZVP).
BODIPY
Transition
Energy [eV]
λ [nm]
f
Main configuration
Coefficient [%]
3af
S0 ǞS1
S0 ǞS2
S0 ǞS3
S0 ǞS1
S0 ǞS2
S0 ǞS3
2.02
2.48
2.59
1.93
2.16
2.49
614.1
500.6
479.0
642.6
573.7
498.7
0.48
0.23
0.0001
0.35
0.09
0.12
HOMO–LUMO
HOMO–1–LUMO
HOMO–2–LOMO
HOMO–LUMO
HOMO–1–LUMO
HOMO–3–LUMO
75.8
72.8
96.6
68.2
64.6
53.6
3ag
6
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Difluorobora-s-diazaindacene Dyes
reference system used is Nile blue [Φf = 0.27, 0.5% (v/v) 0.1 m HCl
in ethanol].
231 energy, and f is the oscillator strength. The theoretical value
of kr (3af)/kr (3ag), is 1.5, which correlates well with the
experimental value (1.9).
Quantum-chemical calculations were performed by using Turbom-
ole v.6.1 software.[23]
286
291
It should be noted that attempts to evaluate the exci-
tation-induced changes in geometries of BODIPY 3af and
General Procedure for the Preparation of 2-(1,1-biphenyl-4-yl)pyr-
236 3ag have not met with success at this stage. Geometry opti- roles 1f and 1g: 1,1-Biphenyl-4-yl-methylketoxime or 1,1-biphenyl-
4-yl-benzylketoxime (25 mmol), KOH·0.5H2O (1.63 g, 25 mmol)
and dimethyl sulfoxide (DMSO; 120 mL) were placed into a 0.25 L
steel rotating autoclave and acetylene was fed from a cylinder at
room temperature (initial pressure 14 atm). The autoclave was
heated (100 °C) for 3 h. The reaction mixture, after cooling to room
temperature, was diluted with a threefold volume excess of water
and extracted with diethyl ether (5ϫ30 mL). Ether extracts were
mization (TDDFT) of both molecules in the excited S1 state
give a structure with an orthogonal location for the bi-
phenyl fragment and an almost forbidden S1 ǞS0 transition
(f ≈ 0.001) and unreal low fluorescence energy values (ca.
241 1000 nm) that contradict the experimental data.
washed with water (5ϫ30 mL) to remove DMSO and dried with 296
Na2SO4. The residue after removing diethyl ether was fractionated
by column chromatography (Al2O3, n-hexane) to afford 1-vinyl-2-
(1,1-biphenyl-4-yl)pyrrole (2f) or 1-vinyl-2-(1,1-biphenyl-4-yl)-3-
phenylpyrrole (2g).
Conclusions
In conclusion, an expedient strategy for the synthesis of
highly efficient BODIPY fluorophores that combine tri-
fluoromethyl and 3,5-aryl or heteroaryl substituents
246 fluorescing in the 626–698 nm region with quantum yields
close to unity has been developed. The key step of the strat-
egy is the P2O5-promoted condensation of readily accessible
2,2,2-trifluoro-1-(5-arylpyrrol-2-yl)-1-ethanols with diverse
2-arylpyrroles. Additionally, the strategy proved to be an
251 easy and general route to previously inaccessible asymmet-
ric BODIPY fluorophores.
A suspension of pyrrole 2f or 2g (5 mmol) and mercury acetate
(1.59 g, 5 mmol) in aqueous acetonitrile (200 mL, 1:2) was stirred
for 2 h at room temperature and then heated at 55–60 °C for
15 min. The reaction mixture was diluted with water (100 mL) and
the solid formed was filtered off and dried. The solid was purified
by flash-chromatography (Al2O3, hexane/diethyl ether, 1:1) to af-
ford pyrrole 1f or 1g.
301
306
2-(1,1-Biphenyl-4-yl)pyrrole (1f): Yield 0.48 g (44%) as grayish crys-
tals, m.p. 213-215 °C. IR (KBr): ν
= 3433, 3395, 1488, 1426,
˜
max
836, 800, 763, 719, 691 cm–1. 1H NMR ([D6]DMSO): δ = 11.40 (br.
s, 1 H, NH), 7.72 (m, 2 H, Ph-2a,6a), 7.68 (m, 2 H, Ph-2b,6b), 7.65
(m, 2 H, Ph-3a,5a), 7.45 (m, 2 H, Ph-3b,5b), 7.33 (m, 1 H, Ph-4b),
6.86 (m, 1 H, 2-H), 6.56 (m, 1 H, 4-H), 6.13 (m, 1 H, 3-H) ppm.
13C NMR ([D6]DMSO): δ = 139.9 (C-1b), 136.9 (C-4a), 132.2 (C-
1a), 130.8 (C-5), 129.0 (C-3b,5b), 127.3 (C-4b), 127.0 (C-3a,5a),
126.3 (C-2b,6b), 123.9 (C-2a,6a), 119.7 (C-2), 109.3 (C-3), 106.0 316
(C-4) ppm. 15N NMR ([D6]DMSO): δ = –228.4 ppm. C16H13N
(219.29): calcd. C 87.64, H 5.98, N 6.39; found C 87.38, H 5.85, N
6.23.
311
Experimental Section
General: IR spectra were obtained with a Bruker IFS-25 spectro-
meter (400–4000 cm–1, KBr pellets). 1H (400.1 MHz), 13C
256 (100.6 MHz), 19F (376.5 MHz) and 15N (40.5 MHz) NMR spectra
were recorded with a Bruker Avance 400 instrument in CDCl3 and
[D6]DMSO. The assignment of signals in the 1H NMR spectra was
made by using COSY and NOESY experiments. Resonance signals
of carbon atoms were assigned based on H–13C HSQC and H–
13C HMBC experiments. Chemical shifts for 15N NMR spectra
were measured through 2D 1H–15N HMBC experiments. The 1H
and 13C chemical shifts were referenced to hexamethyldisilazane,
19F to CFCl3, and 15N to CH3NO2. UV/Vis absorption spectra
were measured with a Lambda-35 (Perkin–Elmer) spectrophotome-
ter. The absorption coefficients have been determined with an accu-
racy of Ϯ500 m–1 cm–1. Excitation and emission spectra were mea-
sured with a FLSP-920 combined steady-state and time-resolved
fluorescence spectrometers (Edinburgh Instrument). All fluores-
cence and excitation spectra were corrected. Fluorescence decay
curves were obtained with a time-correlated single-photon-count-
ing method. The experimental errors in the determination of τf
values were estimated to be 1%. For samples, a right-angle configu-
ration was used and to avoid re-absorption, the maximum ab-
sorbance was kept below 0.1. The solvent used was CH3CN (spec-
troscopic grade) from Sigma–Aldrich. The fluorescence quantum
yields (Φf) of the BODIPY systems were calculated by using the
following relationship [Equation (1)].
1
1
2-(1,1-Biphenyl-4-yl)-1-vinylpyrrole (2f): Yield 3.25 g (53%) as white
261
266
271
276
crystals, m.p. 126–127 °C. IR (KBr): νmax = 3145, 1640, 1465, 1316,
321
˜
1
1290, 971, 960, 875, 841, 766, 713, 700 cm–1. H NMR (CDCl3): δ
= 7.73 (m, 4 H, Ph-2a,6a,2b,6b), 7.55 (m, 4 H, Ph-3a,5a,3b,5b),
7.45 (m, 1 H, Ph-4b), 7.24 (m, 1 H, 5-H), 7.07 (dd, J = 15.6, 8.8 Hz,
1 H, HX), 6.42 (m, 2 H, 3-H,4), 5.30 (d, J = 15.6 Hz, 1 H, HB),
4.82 (d, J = 8.8 Hz, 1 H, HA) ppm. 13C NMR (CDCl3): δ = 140.7 326
(C-1b), 140.0 (C-4a), 134.0 (C-1a), 132.1 (Cα), 131.5 (C-2), 129.6
(C-3b,5b), 128.9 (C-2a,6a), 127.5 (C-4b), 127.2 (C-3a,5a), 127.1 (C-
2b,6b), 118.6 (C-5), 110.2 (C-3,4), 99.0 (Cβ) ppm. C18H15N
(245.32): calcd. C 88.13, H 6.16, N 5.71; found C 88.12, H 6.38, N
5.54.
331
2-(1,1-Biphenyl-4-yl)-3-phenylpyrrole (1g): Yield 0.92 g (62%) as
beige crystals, m.p. 184–185 °C. IR (KBr): νmax = 3409, 1604, 1501,
˜
1
1488, 1095, 895, 838, 764, 722, 699, 689 cm–1. H NMR (CDCl3):
δ = 8.27 (br. s, 1 H, NH), 7.59 (m, 2 H, Ph-2b,6b), 7.53 (m, 2 H,
Ph-3a,5a), 7.41 (m, 6 H, Ph-2a,6a,3b,5b,2c,6c), 7.33 (m, 1 H, Ph- 336
4b), 7.27 (m, 2 H, Ph-3c,5c), 7.20 (m, 1 H, Ph-4c), 6.89 (dd, J =
2.5, 2.8 Hz, 1 H, 2-H), 6.43 (dd, J = 2.5, 2.8 Hz, 1 H, 3-H) ppm.
13C NMR (CDCl3): δ = 140.6 (C-1b), 139.4 (C-4a), 136.7 (C-1c),
132.4 (C-1a), 128.9 (C-2a,6a), 128.6 (C-2c,6c), 128.4 (C-3c,5c),
Φf = Φref Fsampl Aref n2sampl/Fref Asampl n2
(1)
ref
F denotes the integral of the corrected fluorescence spectrum, A is
the absorbance at the excitation wavelength, and n is the refractive
index of the medium, and ref and sampl denote parameters from
the reference and unknown experimental samples, respectively. The
128.0 (C-5), 127.8 (C-3b,5b), 127.4 (C-4b), 127.3 (C-3a,5a), 126.9
(C-2b,6b), 125.8 (C-4c), 122.4 (C-4), 118.3 (C-2), 111.3 (C-3) ppm.
C22H17N (295.38): calcd. C 89.46, H 5.80, N 4.74; found C 89.12,
H 5.39, N 4.51.
341
281
Eur. J. Org. Chem. 0000, 0–0
© 0000 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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7

Job/Unit: O30212
/KAP1
Date: 08-05-13 18:37:42
Pages: 13
B. A. Trofimov et al.
FULL PAPER
2-(1,1-Biphenyl-4-yl)-3-phenyl-1-vinylpyrrole (2g): Yield 3.21 g
(40%) as white crystals, m.p. 113–114 °C. IR (KBr): ν = 3449,
1636, 1599, 1494, 1472, 1446, 1423, 1382, 1316, 1297, 1281, 1253,
1075, 958, 929, 910, 855, 841, 768, 736, 723, 693 cm–1. 1H NMR
(CDCl3): δ = 7.61 (m, 2 H, Ph-2b,6b), 7.58 (m, 2 H, Ph-3a,5a),
7.42 (m, 2 H, Ph-3b,5b), 7.32 (m, 3 H, Ph-2a,6a,4b), 7.20 (m, 2 H, chromatography (Al2O3, diethyl ether) to give products 5c–g.
Ph-2c,6c), 7.17 (d, J = 3.2 Hz, 1 H, 2-H), 7.16 (m, 2 H, Ph-3c,5c),
7.08 (m, 1 H, Ph-4c), 6.76 (dd, J = 15.9, 9.1 Hz, 1 H, HX), 6.51 (d,
J = 3.2 Hz, 1 H, 3-H), 5.15 (d, J = 15.9 Hz, 1 H, HB), 4.63 (d, J =
NaBH4 (2 equiv., 0.378 g, 10 mmol) was added in portions over
10 min and the reaction mixture was stirred for 30 min. The residue
after removal of MeOH was diluted with water (30 mL), extracted
with diethyl ether (4ϫ10 mL) and dried with Na2SO4. The diethyl
ether was removed and the resulting residue was purified by flash
346
351
356
˜
max
411
416
1-[5-(4-Methylphenyl)-1H-pyrrol-2-yl]-2,2,2-trifluoro-1-ethanol (5c):
Yield 1.23 g (96%) as beige crystals, m.p. 156–157 °C. IR (KBr):
ν
max = 3487, 3404, 3308, 1525, 1381, 1269, 1254, 1171, 1124, 1075,
˜
9.1 Hz, 1 H, HA) ppm. 13C NMR (CDCl3): δ = 140.5 (C-1b), 140.4
(C-4a), 136.0 (C-1c), 131.9 (C-2a,6a), 131.7 (Cα), 130.8 (C-1a),
129.6 (C-5), 128.9 (C-3b,5b), 128.3 (C-3c,5c), 128.0 (C-2c,6c), 127.6
(C-4b), 127.2 (C-3a,5a), 127.1 (C-2b,6b), 125.6 (C-4c), 124.2 (C-4),
117.3 (C-2), 110.8 (C-3), 98.4 (Cβ) ppm. 15N NMR (CDCl3): δ =
–207.6 ppm. C24H19N (321.42): calcd. C 89.68, H 5.96, N 4.36;
found C 89.41, H 5.78, N 4.38.
1049, 995, 853, 824, 792, 700 cm–1. 1H NMR (CDCl3): δ = 8.60
(br. s, 1 H, NH), 7.36 (m, 2 H, Ph-2,6), 7.17 (m, 2 H, Ph-3,5), 6.40
(m, 1 H, 4-H), 6.32 (m, 1 H, 3-H), 5.10 (q, J = 6.6 Hz, 1 H,
CHCF3), 2.34 (s, 3 H, Me), 2.61 (br. s, 1 H, OH) ppm. 13C NMR
(CDCl3): δ = 136.8 (C-4, Ph), 134.1 (C-5), 129.7 (C-3,5, Ph), 129.4
(C-1, Ph), 124.2 (C-2,6, Ph), 124.0 (C-2), 124.0 (q, JCF = 280.9 Hz, 421
CF3), 110.9 (C-3), 105.8 (C-4), 67.7 (q, JCF = 33.6 Hz, C-OH),
21.2 (Me) ppm. 19F NMR (CDCl3): δ = –78.2 (d, J = 6.6 Hz) ppm.
C13H12F3NO (255.24): calcd. C 61.17, H 4.74, F 22.33, N 5.49;
found C 61.01, H 4.92, F 22.67, N 5.36.
361
366
371
Preparation of 2,2,2-trifluoro-1-(5-aryl-1H-pyrrol-2-yl)-1-ethanones
4f and 4g: A solution of trifluoroacetic anhydride (6.30 g, 30 mmol)
in dry diethyl ether (10 mL) was added dropwise to a mixture of 2-
(1,1-biphenyl)-4-ylpyrroles 1f or 1g (20 mmol) and pyridine (2.37 g,
30 mmol) in dry diethyl ether (50 mL) and stirred for 30 min. Then
the reaction mixture was stirred for 2 h and diluted with a saturated
solution of Na2CO3. The organic layer was separated and the aque-
ous layer was extracted with diethyl ether (3ϫ10 mL). The com-
bined extracts were washed with water (3ϫ10 mL) and dried with
MgSO4. After removing the solvent the residue was washed with
cold ethanol to give compound 4f and 4g.
1-[5-(4-Methoxyphenyl)-1H-pyrrol-2-yl]-2,2,2-trifluoro-1-ethanol
426
431
436
(5d): Yield 1.06 g (78%) as beige crystals, m.p. 120–121 °C. IR
1
(KBr): ν
= 3355, 3322 (NH, OH) cm–1. H NMR (CDCl3): δ =
˜
max
8.60 (br. s, 1 H, NH), 7.42 (m, 2 H, Ph-2,6), 6.93 (m, 2 H, Ph-3,5),
6.37 (m, 1 H, 4-H), 6.35 (m, 1 H, 3-H), 5.12 (q, J = 6.7 Hz, 1 H,
CHCF3), 3.84 (s, 3 H, MeO), 2.81 (br. s, 1 H, OH) ppm. 13C NMR
(CDCl3): δ = 158.8 (C-4, Ph), 134.0 (C-5), 125.6 (C-2,6, Ph), 125.2
(C-1, Ph), 124.0 (q, JCF = 281.8 Hz, CF3), 123.8 (C-2), 114.5 (C-
3,5, Ph), 110.9 (C-3), 105.3 (C-4), 67.7 (q, JCF = 33.6 Hz, C-OH),
The 2,2,2-trifluoro-1-(5-aryl-1H-pyrrol-2-yl)-1-ethanones 4c–4e
were obtained analogously. Their spectroscopic data are described
in ref.[24]
55.4 (MeO) ppm. 19F NMR (CDCl3):
δ = –78.2 (d, J =
6.7 Hz) ppm. 15N NMR (CDCl3): δ = –240.7 ppm. C13H12F3NO2
(271.24): calcd. C 57.57, H 4.46, F 21.01, N 5.16; found C 57.23,
H 4.23, F 20.87, N 5.16.
1-[5-(1,1-Biphenyl)-4-yl]-1H-pyrrol-2-yl-2,2,2-trifluoro-1-ethanone
(4f): Yield 5.61 g (89%) as light-violet crystals, m.p. 238–239 °C.
376
381
386
IR (KBr): ν
= 3308, 1644, 1479, 1266, 1201, 1138, 1076, 882,
1-[5-(4-Chlorophenyl)-1H-pyrrol-2-yl]-2,2,2-trifluoro-1-ethanol (5e):
˜
max
840, 796, 764, 756 cm–1. 1H NMR ([D6]DMSO): δ = 12.92 (br. s, 1
H, NH), 8.06 (m, 2 H, Ph-2a,6a), 7.74 (m, 4 H, Ph-3a,5a,2b,6b),
7.47 (m, 2 H, Ph-3b,5b), 7.39 (m, 1 H, Ph-4b), 7.29 (dd, J = 4.0,
2.0 Hz, 1 H, 3-H), 6.96 (dd, J = 4.2, 2.2 Hz, 1 H, 4-H) ppm. 13C
NMR ([D6]DMSO): δ = 167.6 (q, J = 34.7 Hz, CO), 143.4 (C-5),
140.6 (C-1b), 139.2 (C-4a), 129.1 (C-3b,5b), 128.9 (C-1a), 128.0 (C-
3), 127.2 (C-3a,5a), 127.0 (C-2b,6b), 126.7 (C-2a,6a), 126.1 (C-4b),
123.6 (C-2), 117.3 (q, J = 290.3 Hz, CF3), 111.1 (C-4) ppm. 19F
NMR ([D6]DMSO): δ = –70.9 ppm. C18H12F3NO (315.29): calcd.
C 68.57, H 3.84, F 18.08, N 4.44; found C 68.12, H 3.69, F 17.82,
N 4.54.
Yield 1.32 g (96%) as beige crystals, m.p. 112–113 °C. IR (KBr):
1
ν
= 3504, 3413, 3297 (NH, OH) cm–1. H NMR (CDCl3): δ = 441
˜
max
8.61 (br. s, 1 H, NH), 7.38 (m, 2 H, Ph-2,6), 7.32 (m, 2 H, Ph-3,5),
6.44 (m, 1 H, 4-H), 6.33 (m, 1 H, 3-H), 5.12 (q, J = 6.5 Hz, 1 H,
CHCF3), 2.61 (br. s, 1 H, OH) ppm. 13C NMR (CDCl3): δ = 132.6
(C-4, Ph), 132.5 (C-5), 130.5 (C-1, Ph), 129.1 (C-3,5, Ph), 125.3 (C-
2,6, Ph), 124.7 (C-2), 123.8 (q, JCF = 281.8 Hz, CF3), 111.0 (C-3),
107.0 (C-4), 67.6 (q, JCF = 33.6 Hz, C-OH) ppm. 19F NMR
(CDCl3): δ = –78.4 (d, J = 6.7 Hz) ppm. C12H9ClF3NO (275.66):
calcd. C 52.29, H 3.29, Cl 12.86, F 20.68, N 5.08; found C 52.29,
H 2.94, Cl 12.73, F 20.28, N 4.77.
446
1-{5-[(1,1-Biphenyl)-4-yl]-4-phenyl-1H-pyrrol-2-yl}-2,2,2-trifluoro-1-
ethanone (4g): Yield 5.64 g (72%) as light yellow crystals, m.p. 202–
1-(5-[1,1-Biphenyl]-4-yl-1H-pyrrol-2-yl)-2,2,2-trifluoro-1-ethanol
(5f): Yield 1.43 g (90 %) as beige crystals, m.p. 171–172 °C. IR
451
456
461
391
396
401
203 °C. IR (KBr): νmax = 3300, 1660, 1642, 1478, 1453, 1263, 1220,
(KBr): νmax = 3430, 1608, 1596, 1272, 1215, 1174, 1123, 1046, 837,
˜
˜
1194, 1177, 1141, 896, 846, 765, 758, 735, 701 cm–1. 1H NMR ([D6]-
787, 764, 702, 695 cm–1. 1H NMR ([D6]DMSO): δ = 11.55 (br. s, 1
DMSO): δ = 13.03 (br. s, 1 H, NH), 7.69 (m, 4 H, Ph-2a,6a,2b,6b),
7.53 (m, 2 H, Ph-3a,5a), 7.51 (m, 2 H, Ph-3b,5b), 7.46 (m, 7 H, 3- 2 H, Ph-3a,5a), 7.45 (m, 2 H, Ph-3b,5b), 7.33 (m, 1 H, Ph-4b), 6.77
H, NH), 7.76 (m, 2 H, Ph-2a,6a), 7.68 (m, 2 H, Ph-2b,6b), 7.66 (m,
H, Ph-4b,2c-6c) ppm. 13C NMR ([D6]DMSO): δ = 168.1 (q, J =
34.8 Hz, CO), 141.0 (C-1b), 140.7 (C-4a), 139.6 (C-1c), 134.7 (C-
1a), 130.0 (C-3b,5b), 129.6 (C-5), 129.5 (C-3c,5c), 129.1 (C-2c,6c),
129.0 (C-2a,6a), 128.4 (C-4b), 127.5 (C-2), 127.2 (C-2b,6b), 127.1
(C-3a,5a), 126.5 (C-4), 125.4 (C-4c), 122.8 (C-3), 117.6 (q, J =
290.2 Hz, CF3) ppm. 19F NMR ([D6]DMSO): δ = –70.8 ppm.
C24H16F3NO (391.39): calcd. C 73.65, H 4.12, F 14.56, N 3.58;
found C 73.46, H 4.08, F 14.71, N 3.52.
(d, J = 6.1 Hz, 1 H, OH), 6.56 (m, 1 H, 4-H), 6.24 (m, 1 H, 3-H),
5.14 (q, J = 6.5 Hz, 1 H, CHCF3) ppm. 13C NMR ([D6]DMSO): δ
= 139.8 (C-1b), 137.4 (C-4a), 131.7 (C-1a), 131.4 (C-5), 129.0 (C-
3b,5b), 127.8 (C-2), 127.3 (C-4b), 127.0 (C-3a,5a), 126.4 (C-2b,6b),
124.9 (q, JCF = 281.1 Hz, CF3), 124.2 (C-2a,6a), 109.0 (C-3), 106.4
(C-4), 65.9 (q, JCF = 31.7 Hz, C-OH) ppm. 19F NMR ([D6]-
DMSO): δ = –76.6 (d, J = 7.2 Hz) ppm. C18H14F3NO (317.31):
calcd. C 68.13, H 4.45, F 17.96, N 4.41; found C 68.29, H 4.24, F
18.28, N 4.65.
General Procedure for the Preparation of 2,2,2-Trifluoro-1-(5-aryl-
pyrrol-2-yl)-1-ethanols 5c–5g: To an rigorously stirred mixture of
1-(5-[1,1-Biphenyl]-4-yl-4-phenyl-1H-pyrrol-2-yl)-2,2,2-trifluoro-1- 466
2,2,2-trifluoro-1-(5-arylpyrrol-2-yl)-1-ethanones 4c–4g (5 mmol) ethanol (5g): Yield 1.79 g (91%) as white crystals, m.p. 129 °C. IR
and NaHCO3 (2.1 equiv., 0.882 g, 10.5 mmol) in MeOH (15 mL), (KBr): νmax = 3449, 3330, 3290, 1265, 1207, 1183, 1165, 1130, 1045,
406
˜
8
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Job/Unit: O30212
/KAP1
Date: 08-05-13 18:37:42
Pages: 13
Difluorobora-s-diazaindacene Dyes
1001, 845, 805, 766, 699 cm–1. 1H NMR ([D6]DMSO): δ = 11.46
2 H, Ph-2a,6a), 7.19 (m, 1 H, Ph-4b), 6.47 (m, 1 H, 4Ј-H), 6.44 (m, 531
(br. s, 1 H, NH), 7.66 (m, 2 H, Ph-2b,6b), 7.60 (m, 2 H, Ph-3a,5a), 1 H, 3-H), 6.31 (m, 2 H, 3Ј,4-H), 4.85 (q, JHF = 8.9 Hz, 1 H,
471
476
7.43 (m, 2 H, Ph-3b,5b), 7.42 (m, 2 H, Ph-2a,6a), 7.32 (m, 1 H,
Ph-4b), 7.27 (m, 2 H, Ph-2c,6c), 7.25 (m, 2 H, Ph-3c,5c), 7.18 (m,
1 H, Ph-4c), 6.83 (d, J = 6.1 Hz, 1 H, OH), 6.38 (d, J = 2.2 Hz, 1
H, 3-H), 5.16 (m, 1 H, CHCF3) ppm. 13C NMR ([D6]DMSO): δ =
139.6 (C-1b), 138.3 (C-4a), 136.8 (C-1c), 132.1 (C-1a), 129.1 (C-
CH) ppm. 13C NMR (CDCl3): δ = 133.4 (C-5Ј), 132.3 (C-4a), 132.2
(C-1b), 132.1 (C-2), 130.7 (C-1a), 129.2 (C-3a,5a), 129.0 (C-3b,5b),
126.8 (C-4b), 125.2 (C-2a,6a), 125.2 (q, JCF = 280.1 Hz, CF3),
124.2 (C-5), 124.0 (C-2b,6b), 123.6 (C-2Ј), 111.3 (C-4), 111.2 (C- 536
3Ј), 107.1 (C-3), 106.6 (C-4Ј), 43.7 (q, JCF = 30.2 Hz, CH) ppm.
3b,5b), 128.6 (C-3c,5c), 128.2 (C-2c,6c), 128.1 (C-2a,6a), 127.7 (C- 19F NMR (CDCl3): δ = –68.2 (d, J = 8.9 Hz) ppm. 15N NMR
4b), 127.6 (C-5), 127.1 (C-2), 126.7 (C-3a,5a), 126.5 (C-2b,6b), (CDCl3): δ = –236.9 (N,NЈ) ppm. C22H16ClF3N2 (400.83): calcd. C
126.0 (C-4c), 125.0 (q, JCF = 282.5 Hz, CF3), 122.0 (C-4), 109.9 (C- 65.92, H 4.02, Cl 8.85, F 14.22, N 6.99; found C 65.60, H 4.07, Cl
3), 66.0 (q, JCF = 32.3 Hz, C-OH) ppm. 19F NMR ([D6]DMSO): δ
8.47, F 14.38, N 6.71.
541
= –76.6 (d, J = 7.2 Hz) ppm. 15N NMR ([D6]DMSO): δ =
2-[1,1-Biphenyl]-4-yl-5-[2,2,2-trifluoro-1-(5-phenyl-1H-pyrrol-2-yl)-
ethyl]-1H-pyrrole (6af): Yield 0.201 g (96%) as light violet solid,
m.p. 108–110 °C. IR (KBr): ν
481 –222.3 ppm. C24H18F3NO (393.41): calcd. C 73.27, H 4.61, F
14.49, N 3.56; found C 73.00, H 4.38, F 14.28, N 3.69.
= 3457, 3422, 1607, 1495, 1473,
˜
max
Preparation of Dipyrromethanes 6: A mixture of 2,2,2-trifluoro-1-
(5-arylpyrrol-2-yl)-1-ethanol 5c–5g and pyrrole 1a–1g (molar ratio
1a–1g:5c–5g 1:1) in dry CH2Cl2 was added to P2O5 (1 equiv.) under
argon and stirred at room temperature for 16 h. Then NaHCO3
(1.5 equiv.) was added and the mixture was stirred at room tem-
perature for 1 h. The precipitate was filtered off and washed with
CH2Cl2 (5 times). Compounds 6 were isolated by column
chromatography (SiO2, n-hexane/CH2Cl2, 3:1 or 2:1).
1424, 1257, 1210, 1167, 1102, 1072, 1051, 836, 804, 781, 764, 754,
705, 692 cm–1. H NMR (CDCl3): δ = 8.35 (br. s, 1 H, NH), 8.33 546
(br. s, 1 H, NHЈ), 7.57 (m, 4 H, Ph-3a,5a,2b,6b), 7.47 (m, 2 H, Ph-
2a,6a), 7.42 (m, 4 H, Ph-3b,5b,2c,6c), 7.34 (m, 3 H, Ph-4b,3c,5c),
7.20 (m, 1 H, Ph-4c), 6.52 (m, 1 H, 4-H), 6.49 (m, 1 H, 3Ј-H), 6.34
(m, 2 H, 3,4Ј-H), 4.86 (q, JHF = 8.8 Hz, 1 H, CH) ppm. 13C NMR
(CDCl3): δ = 140.6 (C-1b), 139.4 (C-4a), 133.3 (C-5Ј), 132.9 (C-2), 551
132.2 (C-1c), 131.1 (C-1a), 129.0 (C-3b,5b), 128.9 (C-3c,5c), 127.6
(C-3a,5a), 127.4 (C-4b), 126.9 (C-2b,6b), 126.8 (C-4c), 125.3 (q,
JCF = 280.3 Hz, CF3), 124.3 (C-2a,6a), 124.0 (C-2c,6c), 123.9 (C-
5), 123.8 (C-2Ј), 111.2 (C-4), 111.1 (C-3Ј), 106.8 (C-3), 106.6 (C-
4Ј), 43.7 (q, JCF = 30.2 Hz, CH) ppm. 19F NMR (CDCl3): δ = –68.2 556
(d, J = 8.8 Hz) ppm. 15N NMR (CDCl3): δ = –236.9 (N,NЈ) ppm.
C28H21F3N2 (442.48): calcd. C 76.00, H 4.78, F 12.88, N 6.33;
found C 75.96, H 4.67, F 12.92, N 6.31.
1
486
491 2-(4-Methylphenyl)-5-[2,2,2-trifluoro-1-(5-phenyl-1H-pyrrol-2-yl)-
ethyl]-1H-pyrrole (6ac): Yield 0.314 g (55%) as dark cherry crystals,
m.p. 70–72 °C. IR (KBr): ν
= 3438, 3026, 2956, 2924, 1607,
˜
max
1523, 1512, 1474, 1454, 1256, 1210, 1190, 1162, 1109, 1072, 1046,
819, 777, 757, 710 cm–1. 1H NMR (CDCl3): δ = 8.29 (br. s, 1 H,
496 NHЈ), 8.25 (br. s, 1 H, NH), 7.40 (m, 2 H, Ph-2b,6b), 7.32 (m, 4
H, Ph-2a,6a,3b,5b), 7.19 (m, 1 H, Ph-4b), 7.14 (m, 2 H, Ph-3a,5a),
6.47 (m, 1 H, 4Ј-H), 6.43 (m, 1 H, 3-H), 6.30 (m, 2 H, 3Ј,4-H), 4.88
(q, JHF = 8.8 Hz, 1 H, CH), 2.32 (s, 3 H, Me) ppm. 13C NMR
(CDCl3): δ = 136.6 (C-4a), 133.5 (C-2), 133.3 (C-5Ј), 132.2 (C-1b),
2-[1,1-Biphenyl]-4-yl-3-phenyl-5-[2,2,2-trifluoro-1-(5-phenyl-1H-pyr-
rol-2-yl)ethyl]-1H-pyrrole (6ag): Yield 0.060 g (45%) as a violet so-
lid, m.p. 72–74 °C. IR (KBr): ν = 3429, 1604, 1511, 1492, 1472,
561
566
571
576
˜
max
501
129.7 (C-3a,5a), 129.5 (C-1a), 129.0 (C-3b,5b), 126.8 (C-4b), 125.2
(q, JCF = 280.1 Hz, CF3), 124.0 (C-2a,6a,2b,6b), 123.8 (C-2Ј), 123.3
(C-5), 111.1 (C-3Ј), 111.0 (C-4), 106.6 (C-4Ј), 106.0 (C-3), 43.7 (q,
JCF = 30.2 Hz, CH), 21.2 (Me) ppm. 19F NMR (CDCl3): δ = –68.3
(d, J = 8.8 Hz) ppm. 15N NMR (CDCl3): δ = –236.9 ppm.
1
1446, 1254, 1199, 1160, 1108, 1073, 843, 760, 697 cm–1. H NMR
(CDCl3): δ = 8.38 (br. s, 1 H, NHЈ), 8.15 (br. s, 1 H, NH), 7.54 (m,
2 H, Ph-2b,6b), 7.48 (m, 2 H, Ph-3a,5a), 7.40 (m, 4 H, Ph-
3b,5b,2c,6c), 7.29–7.37 (m, 7 H, Ph-2a,6a,4b,2d,6d,3d,5d), 7.26 (m,
2 H, Ph-3c,5c), 7.18 (m, 2 H, Ph-4c,4d), 6.48 (m, 1 H, 3Ј-H), 6.44
(m, 1 H, 4-H), 6.35 (m, 1 H, 4Ј-H), 4.92 (q, JHF = 8.8 Hz, 1 H,
CH) ppm. 13C NMR (CDCl3): δ = 140.5 (C-1b), 139.9 (C-4a),
136.1 (C-1c), 133.5 (C-5Ј), 132.2 (C-1d), 131.7 (C-1a), 129.1 (C-
3d,5d), 128.9 (C-3b,5b, C-2), 128.5 (C-2c,6c), 128.4 (C-3c,5c), 127.9
(C-2a,6a), 127.5 (C-4b), 127.4 (C-3a,5a), 127.0 (C-2b,6b), 126.8 (C-
4d), 126.2 (C-4c), 125.2 (q, JCF = 280.1 Hz, CF3), 124.1 (C-2d,6d),
123.5 (C-2Ј), 123.4 (C-5), 122.8 (C-3), 111.9 (C-4), 111.3 (C-3Ј),
106.6 (C-4Ј), 43.7 (q, JCF = 30.2 Hz, CH) ppm. 19F NMR (CDCl3):
δ = –68.1 (d, J = 8.8 Hz) ppm. 15N NMR (CDCl3): δ = –237.6
(NЈ), –231.5 (N) ppm. C34H25F3N2 (518.58): calcd. C 78.75, H 4.86,
F 10.99, N 5.40; found C 78.55, H 4.90, F 11.09, N 5.36.
506 C23H19F3N2 (380.41): calcd. C 72.62, H 5.03, F 14.98, N 7.36;
found C 72.29, H 4.94, F 14.58, N 7.65.
2-(4-Methoxyphenyl)-5-[2,2,2-trifluoro-1-(5-phenyl-1H-pyrrol-2-yl)-
ethyl]-1H-pyrrole (6ad): Yield 0.285 g (72%) as red needles, m.p.
132–135 °C. IR (KBr): ν
= 3459, 3431 1522, 1263, 1251, 1245,
˜
max
511 1166, 1103, 1020, 780, 772, 760, 707, 691, 529 cm–1 1H NMR
.
(CDCl3): δ = 8.31 (br. s, 1 H, NHЈ), 8.20 (br. s, 1 H, NH), 7.40 (m,
2 H, Ph-2b,6b), 7.34 (m, 2 H, Ph-2a,6a), 7.33 (m, 2 H, Ph-3b,5b),
7.19 (m, 1 H, Ph-4b), 6.88 (m, 2 H, Ph-3a,5a), 6.48 (m, 1 H, 4Ј-H),
6.36 (m, 1 H, 3-H), 6.32 (m, 1 H, 3Ј-H), 6.29 (m, 1 H, 4-H), 4.88
516 (q, JHF = 8.8 Hz, 1 H, CH), 3.79 (s, 3 H, Me) ppm. 13C NMR
(CDCl3): δ = 158.7 (C-4a), 133.4 (C-2), 133.2 (C-5Ј), 132.2 (C-1b),
2-[1,1-Biphenyl]-4-yl-5-{2,2,2-trifluoro-1-[5-(2-thienyl)-1H-pyrrol-2-
yl]ethyl}-1H-pyrrole (6bf): Yield 0.168 g (79%) as a violet solid,
129.0 (C-3b,5b), 126.7 (C-4b), 125.5 (C-2a,6a), 125.3 (q, JCF
=
280.7 Hz, CF3), 125.3 (C-1a), 124.0 (C-2b,6b), 123.9 (C-2Ј), 123.0
(C-5), 114.5 (C-3a,5a), 111.0 (C-3Ј, C-4), 106.6 (C-4Ј), 105.5 (C-3),
55.4 (Me), 43.7 (q, JCF = 30.1 Hz, CH) ppm. 19F NMR (CDCl3):
δ = –68.3 (d, J = 8.8 Hz) ppm. 15N NMR (CDCl3): δ = –237.0
(N,NЈ) ppm. C23H19F3N2O (396.41): calcd. C 69.69, H 4.83, F
14.38, N 7.07; found C 69.90, H 4.97, F 14.20, N 7.00.
m.p. 138–140 °C. IR (KBr): ν
= 3451, 3422, 2919, 1607, 1596,
581
586
591
˜
max
1528, 1495, 1426, 1259, 1169, 1102, 1052, 1040, 836, 781, 764, 705,
691 cm–1. 1H NMR (CDCl3): δ = 8.32 (br. s, 1 H, NH), 8.18 (br. s,
1 H, NHЈ), 7.57 (m, 4 H, Ph-2b,6b,3a,5a), 7.47 (m, 2 H, Ph-2a,6a),
7.41 (m, 2 H, Ph-3b,5b), 7.31 (m, 1 H, Ph-4b), 7.12 (m, 1 H, 5-H
of thiophene), 7.00 (m, 1 H, 3-H of thiophene), 6.96 (m, 1 H, 4-H
521
526
2-(4-Chlorophenyl)-5-[2,2,2-trifluoro-1-(5-phenyl-1H-pyrrol-2-yl)- of thiophene), 6.51 (m, 1 H, 3-H), 6.37 (m, 1 H, 4Ј-H), 6.33 (m, 1
ethyl]-1H-pyrrole (6ae): Yield 0.263 g (66%) as violet solid, m.p.
118–120 °C. IR (KBr): ν = 3452 1507, 1260, 1212, 1182, 1162,
H, 4-H), 6.29 (m, 1 H, 3Ј-H), 4.88 (q, JHF = 8.8 Hz, 1 H, CH) ppm.
13C NMR (CDCl3): δ = 140.6 (C-1b), 139.5 (C-4a), 135.5 (C-2 of
˜
max
1101, 827, 781, 772, 758, 705, 690, 514 cm–1. H NMR (CDCl3): δ thiophene), 133.0 (C-2), 131.1 (C-1a), 128.9 (C-3b,5b), 127.8 (C-
1
= 8.27 (br. s, 1 H, NHЈ), 8.22 (br. s, 1 H, NH), 7.39 (m, 2 H, Ph- 3a,5a), 127.7 (C-4 of thiophene, C-5Ј), 127.4 (C-4b), 126.9 (C-
2b,6b), 7.32 (m, 2 H, Ph-3b,5b), 7.30 (m, 2 H, Ph-3a,5a), 7.27 (m,
2b,6b), 125.2 (q, JCF = 280.2 Hz, CF3), 124.4 (C-,a), 123.8 (C-5 of
Eur. J. Org. Chem. 0000, 0–0
© 0000 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
9

Job/Unit: O30212
/KAP1
Date: 08-05-13 18:37:42
Pages: 13
B. A. Trofimov et al.
FULL PAPER
thiophene, C-5), 123.7 (C-2Ј), 121.6 (C-3 of thiophene), 111.3 (C-
4), 111.0 (C-3Ј), 107.4 (C-4Ј), 106.8 (C-3), 43.7 (q, JCF = 30.2 Hz,
CH) ppm. 19F NMR (CDCl3): δ = –68.2 (d, J = 8.8 Hz) ppm. 15N
NMR (CDCl3): δ = 8.25 (br. s, 2 H, NH), 7.32 (m, 4 H, Ph-3a,5a),
7.29 (m, 4 H, Ph-2a,6a), 6.46 (m, 2 H, 3,4Ј-H), 6.32 (m, 2 H, 3Ј,4- 656
H), 4.88 (q, JHF = 8.8 Hz, 1 H, CH) ppm. 13C NMR (CDCl3): δ =
596
NMR (CDCl3): δ = –236.8 (N), –235.6 (NЈ) ppm. C26H19F3N2S 132.4 (C-2,5Ј), 132.3 (C-4a,4aЈ), 130.6 (C-1a,1aЈ), 129.2 (C-
(448.50): calcd. C 69.63, H 4.27, F 12.71, N 6.25, S 7.15; found C
69.57, H 4.52, F 12.49, N 6.07, S 7.27.
3a,5a,3aЈ,5aЈ), 125.2 (C-2a,6a,2aЈ,6aЈ), 125.1 (q, JCF = 280.1 Hz,
CF3), 124.0 (C-2Ј,5), 111.3 (C-4,3Ј), 107.1 (C-3,4Ј), 43.7 (q, JCF
=
29.8 Hz, CH) ppm. 19F NMR (CDCl3): δ = –68.2 (d, J =
8.8 Hz) ppm. 15N NMR (CDCl3): δ = –236.9 (N,NЈ) ppm.
C22H15Cl2F3N2 (435.27): calcd. C 60.71, H 3.47, Cl 16.29, F 13.09,
N 6.44; found C 60.61, H 3.38, Cl 16.19, F 13.18, N 6.30.
661
2-[1,1-Biphenyl]-4-yl-3-phenyl-5-{2,2,2-trifluoro-1-[5-(2-thienyl)-1H-
pyrrol-2-yl]ethyl}-1H-pyrrole (6bg): Yield 0.144 g (68%) as a dark
601
606
611
616
blue solid, m.p. 76–78 °C. IR (KBr): νmax = 3420, 1601, 1527, 1510,
˜
1
1492, 1473, 1253, 1184, 1160, 1107, 843, 764, 697 cm–1. H NMR
(CDCl3): δ = 8.25 (br. s, 1 H, NHЈ), 8.15 (br. s, 1 H, NH), 7.56 (m,
2 H, Ph-2b,6b), 7.50 (m, 2 H, Ph-3a,5a), 7.40 (m, 2 H, Ph-3b,5b), 2,2,2-trifluoroethyl}-1H-pyrrole (6ff): Yield 0.186 g (91%) as a light
7.36 (m, 4 H, Ph-2a,6a,2c,6c), 7.32 (m, 1 H, Ph-4b), 7.27 (m, 2 H, pink solid, m.p. 184–185 °C. IR (KBr): ν = 3472, 3454, 3412,
Ph-3c,5c), 7.19 (m, 1 H, Ph-4c), 7.14 (m, 1 H, 5-H of thiophene),
7.01 (m, 1 H, 3-H of thiophene), 6.98 (m, 1 H, 4-H of thiophene),
6.44 (m, 1 H, 4-H), 6.38 (m, 1 H, 4Ј-H), 6.23 (m, 1 H, 3Ј-H), 4.88 s, 2 H, NH), 7.58 (m, 8 H, Ph-3a,5a,2b,6b), 7.48 (m, 4 H, Ph-
(dd, JHF = 8.8 Hz, 1 H, CH) ppm. 13C NMR (CDCl3): δ = 140.5
2a,6a), 7.42 (m, 4 H, Ph-3b,5b), 7.32 (m, 2 H, Ph-4b), 6.54 (m, 2
(C-1b), 140.0 (C-4a), 136.0 (C-1c), 135.5 (C-2 of thiophene), 131.7 H, 3,4Ј-H), 6.36 (m, 2 H, 3Ј,4-H), 4.92 (q, JHF = 8.8 Hz, 1 H,
(C-1a), 129.0 (C-2), 128.9 (C-3b,5b), 128.5 (C-2c,6c), 128.4 (C-
CH) ppm. 13C NMR (CDCl3): δ = 140.6 (C-1b,1bЈ), 139.5 (C-
3c,5c), 127.8 (C-2a,6a), 127.7 (C-4 of thiophene, C-5Ј), 127.5 (C- 4a,4aЈ), 133.0 (C-2,5Ј), 131.2 (C-1a,1aЈ), 128.9 (C-3b,5b,3bЈ,5bЈ),
2-[1,1-Biphenyl]-4-yl-5-{1-[5-(1,1-biphenyl)-4-yl-1H-pyrrol-2-yl]-
666
671
676
681
˜
max
1610, 1598, 1528, 1494, 1253, 1241, 1210, 1169, 1150, 1105, 847,
1
837, 781, 765, 705, 694, 519 cm–1. H NMR (CDCl3): δ = 8.37 (br.
4b), 127.4 (C-3a,5a), 126.9 (C-2b,6b), 126.2 (C-4c), 125.2 (q, JCF
=
127.7 (C-3a,5a,3aЈ,5aЈ), 127.4 (C-4b,4bЈ), 126.9 (C-2b,6b,2bЈ,6bЈ),
125.3 (q, JCF = 280.0 Hz, CF3), 124.4 (C-2a,6a,2aЈ,6aЈ), 123.9 (C-
2Ј,5), 111.3 (C-3Ј,4), 106.8 (C-3,4Ј), 43.8 (q, JCF = 30.1 Hz,
CH) ppm. 19F NMR (CDCl3): δ = –68.2 (d, J = 8.8 Hz) ppm. 15N
NMR (CDCl3): δ = –237.4 (N,NЈ) ppm. C34H25F3N2 (518.58):
calcd. C 78.75, H 4.86, F 10.99, N 5.40; found C 78.96, H 4.67, F
11.12, N 5.25.
278.6 Hz, CF3), 123.4 (C-2Ј), 123.3 (C-5), 123.2 (C-5 of thiophene),
122.9 (C-3), 121.6 (C-3 of thiophene), 112.0 (C-4), 111.2 (C-3Ј),
107.4 (C-4Ј), 43.6 (q, JCF = 30.5 Hz, CH) ppm. 19F NMR (CDCl3):
δ = –68.1 (d, J = 8.8 Hz) ppm. 15N NMR (CDCl3): δ = –236.8
(NЈ), –231.9 (N) ppm. C32H23F3N2S (524.60): calcd. C 73.26, H
4.42, F 10.86, N 5.34, S 6.11; found C 72.98, H 4.35, F 10.90, N
5.45, S 6.21.
2-[1,1-Biphenyl]-4-yl-5-{1-[5-(1,1-biphenyl)-4-yl-4-phenyl-1H-pyrrol-
2-yl]-2,2,2-trifluoroethyl}-3-phenyl-1H-pyrrole (6gg): Yield 0.120 g
621
626
2-(4-Methylphenyl)-5-{2,2,2-trifluoro-1-[5-(4-methylphenyl)-1H-pyr-
rol-2-yl]ethyl}-1H-pyrrole (6cc): Yield 0.167 g (28%) as a dark vi-
(70%) as a dark blue solid, m.p. 112–114 °C. IR (KBr): ν
=
˜
max
olet solid, m.p. 85–86 °C. IR (KBr): νmax = 3437, 3023, 2989, 2953,
3427, 3056, 3027, 1602, 1510, 1492, 1443, 1253, 1160, 1108, 909,
˜
2921, 2864, 1637, 1616, 1523, 1480, 1451, 1433, 1384, 1336, 1299,
843, 764, 731, 697 cm–1. 1H NMR (CDCl3): δ = 8.25 (br. s, 2 H,
686
1256, 1190, 1161, 1109, 1069, 1044, 865, 818, 802, 774, 709, NH), 7.57 (m, 4 H, Ph-2b,6b), 7.53 (m, 4 H, Ph-3a,5a), 7.41 (m, 4
1
518 cm–1. H NMR (CDCl3): δ = 8.25 (br. s, 2 H, NH), 7.30 (m, 4
H, Ph-2a,6a), 7.14 (m, 4 H, Ph -3a,5a), 6.43 (m, 2 H, 3,4Ј-H), 6.30 7.28 (m, 4 H, Ph-3c,5c), 7.20 (m, 2 H, Ph-4c), 6.50 (d, J = 2.7 Hz,
(m, 2 H, 3Ј,4-H), 4.88 (q, JHF = 8.8 Hz, 1 H, CH), 2.32 (s, 6 H,
2 H, 4,3Ј-H), 4.94 (q, JHF = 8.8 Hz, 1 H, CH) ppm. 13C NMR
Me) ppm. 13C NMR (CDCl3): δ = 136.5 (C-4a,4aЈ), 133.4 (C-2,5Ј), (CDCl3): δ = 140.5 (C-1b,1bЈ), 140.0 (C-4a,4aЈ), 136.0 (C-1c,1cЈ), 691
H, Ph-3b,5b), 7.38 (m, 8 H, Ph-2a,6a,2c,6c), 7.32 (m, 2 H, Ph-4b),
129.7 (C-3a,5a, 3aЈ,5aЈ), 129.5 (C-1a,1aЈ), 125.3 (q, JCF = 280.4 Hz,
131.7 (C-1a,1aЈ), 129.1 (C-2,5Ј), 128.9 (C-3b,5b,3bЈ,5bЈ), 128.6 (C-
2c,6c,2cЈ,6cЈ), 128.5 (C-3c,5c,3cЈ,5cЈ), 127.9 (C-2a,6a,2aЈ,6aЈ),
127.5 (C-4b,4bЈ), 127.4 (C-3a,5a,3aЈ,5aЈ), 127.0 (C-2b,6b,2bЈ,6bЈ),
631 CF3), 123.4 (C-2Ј,5), 124.0 (C-2a,6a,2aЈ,6aЈ), 111.0 (C-3Ј,4), 106.0
(C-3,4Ј), 43.7 (q, JCF = 30.2 Hz, CH), 21.2 (Me, MeЈ) ppm. 19F
NMR (CDCl3): δ = –68.3 (d, J = 8.8 Hz) ppm. 15N NMR (CDCl3): 126.2 (C-4c,4cЈ), 125.2 (q, JCF = 280.1 Hz, CF3), 123.2 (C-2Ј,5),
δ = –236.8 (N,NЈ) ppm. C24H21F3N2 (394.44): calcd. C 73.08, H
5.37, F 14.45, N 7.10; found C 72.89, H 5.44, F 14.28, N 7.29.
122.8 (C-3,4Ј), 112.1 (C-3Ј,4), 43.6 (q, JCF = 29.7 Hz, CH) ppm.
19F NMR (CDCl3): δ = –67.9 (d, J = 8.8 Hz) ppm. 15N NMR
(CDCl3): δ = –231.9 (N,NЈ) ppm. C46H33F3N2 (670.77): calcd. C
82.37, H 4.96, F 8.50, N 4.18; found C 82.55, H 4.86, F 8.39, N
4.16.
696
636
641
646
2-(4-Methoxyphenyl)-5-{2,2,2-trifluoro-1-[5-(4-methoxyphenyl)-1H-
pyrrol-2-yl]ethyl}-1H-pyrrole (6dd): Yield 0.095 g (64%) as a violet
solid, m.p. 156–157 °C. IR (KBr): ν
= 3465, 3399, 1613, 1589,
˜
max
1522, 1480, 1469, 1439, 1255, 1244, 1180, 1159, 1101, 1028, 1019,
General Procedure for the Synthesis of BODIPY 3: A mixture of 701
dipyrromethanes 6 and DDQ (molar ratio 1:1) in dry CH2Cl2 was
1
828, 772, 706, 611, 537 cm–1. H NMR (CDCl3): δ = 8.23 (br. s, 2
H, NH), 7.31 (m, 4 H, Ph-2a,6a), 6.85 (m, 4 H, Ph-3a,5a), 6.34 (m, stirred at room temperature for 1 h. Then iPr2NEt (10 equiv.) was
2 H, 3,4Ј-H), 6.28 (m, 2 H, 3Ј,4-H), 4.82 (q, JHF = 8.8 Hz, 1 H, added and the solution was stirred for 10 min, before BF3·OEt2
CH), 3.76 (s, 6 H, OMe) ppm. 13C NMR (CDCl3): δ = 158.6 (C- (15 equiv.) was added dropwise. The reaction mixture was stirred
4a,4aЈ), 133.2 (C-2,5Ј), 125.3 (q, JCF = 280.3 Hz, CF3), 125.3 (C-
1a,1aЈ), 125.4 (C-2a,6a,2aЈ,6aЈ), 123.2 (C-2Ј,5), 114.5 (C-
3a,5a,3aЈ,5aЈ), 110.8 (C-3Ј,4), 105.5 (C-3,4Ј), 55.4 (OMe, OMeЈ),
43.6 (q, JCF = 30.2 Hz, CH) ppm. 19F NMR (CDCl3): δ = –68.3
(d, J = 8.8 Hz) ppm. 15N NMR (CDCl3): δ = –236.8 (N,NЈ) ppm.
C24H21F3N2O2 (426.44): calcd. C 67.60, H 4.96, F 13.37, N 6.57;
found C 67.79, H 4.98, F 13.42, N 6.37.
at room temperature for 1 h, then approximately two thirds of the
solvent was removed under reduced pressure and residue obtained
was purified by column chromatography (SiO2, n-hexane/CH2Cl2,
2:1or 3:1) to yield BODIPY 3.
706
711
4,4-Difluoro-3-(4-methylphenyl)-5-phenyl-8-trifluoromethyl-4-bora-
3a,4a-diaza-s-indacene (3ac): Yield 0.129 g (55%) as a dark blue
solid with metallic luster, m.p. 90–92 °C. IR (KBr): ν
= 2924,
˜
max
651
2-(4-Chlorophenyl)-5-{2,2,2-trifluoro-1-[5-(4-chlorophenyl)-1H-pyr-
rol-2-yl]ethyl}-1H-pyrrole (6ee): Yield 0.292 g (67%) as a violet so-
2853, 1739, 1708, 1566, 1477, 1454, 1300, 1277, 1228, 1178, 1142,
1
1087, 1054, 970, 949, 750 cm–1. H NMR (CDCl3): δ = 7.88 (m, 2
lid, m.p. 110–111 °C. IR (KBr): ν
= 3462, 3433, 1631, 1507,
H, Ph-2b,6b), 7.82 (m, 2 H, Ph-2a,6a), 7.45 (m, 1 H, 1-H), 7.44 (m,
3 H, Ph-3b,4b,5b), 7.43 (m, 1 H, 7-H), 7.25 (m, 2 H, Ph-3a,5a), 716
˜
max
1268, 1259, 1212, 1192, 1159, 1104, 826, 772, 705, 516 cm–1. 1H
10
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© 0000 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Org. Chem. 0000, 0–0

Job/Unit: O30212
/KAP1
Date: 08-05-13 18:37:42
Pages: 13
Difluorobora-s-diazaindacene Dyes
6.70 (d, J = 4.5 Hz, 1 H, 6-H), 6.74 (d, J = 4.5 Hz, 1 H, 2-H), 2.40
= –192.8 ppm. C28H18BF5N2 (488.26): calcd. C 68.88, H 3.72, B
(s, 3 H, Me) ppm. 13C NMR (CDCl3): δ = 162.4 (C-3), 161.1 (C- 2.21, F 19.46, N 5.74; found C 69.25, H 3.42, F 19.41, N 5.40.
5), 141.2 (C-4a), 133.8 (C-8a), 133.1 (C-7a), 132.0 (C-1b), 130.5 (C-
1), 130.2 (C-4b), 129.8 (C-7), 129.7 (t, J = 4.2 Hz, C-2a,6a), 129.6
(t, J = 3.8 Hz, C-2b,6b), 129.3 (C-3a,5a), 129.1 (C-1a), 128.3 (C-
3b,5b), 126.2 (q, J = 33.6 Hz, C-8), 123.1 (C-2), 122.7 (q, J =
275.9 Hz, CF3), 122.6 (C-6), 21.6 (Me) ppm. 19F NMR (CDCl3): δ
= –132.4 (m, JBF = 31.1 Hz, BF2), –54.5 (t, JHF = 2.3 Hz,
CF3) ppm. 15N NMR (CDCl3): δ = –193.4 ppm. C23H16BF5N2
(426.19): calcd. C 64.82, H 3.78, B 2.54, F 22.29, N 6.57; found C
65.10, H 3.68, F 22.16, N 6.36.
4,4-Difluoro-3-[(1,1-biphenyl)-4-yl]-2,5-diphenyl-8-trifluoromethyl-4-
bora-3a,4a-diaza-s-indacene (3ag): Yield 0.047 g (73%) as a dark
781
786
791
796
721
726
blue solid with metallic luster, m.p. 212–214 °C. IR (KBr): ν
=
˜
max
1602, 1562, 1520, 1479, 1471, 1451, 1410, 1398, 1251, 1224, 1208,
1138, 1126, 1087, 1073, 1064, 1006, 998, 881, 844, 772, 753, 744,
738, 699, 687 cm–1. 1H NMR (CDCl3): δ = 7.83 (m, 2 H, Ph-2d,6d),
7.60 (m, 2 H, Ph-2b,6b), 7.56 (m, 4 H, Ph-2a,6a,3a,5a), 7.53 (m, 1
H, 1-H), 7.47 (m, 1 H, 7-H), 7.40 (m, 5 H, Ph-3d,5d,4d,3b,5b), 7.33
(m, 1 H, Ph-4b), 7.22 (m, 3 H, Ph-3c,4c,5c), 7.09 (m, 2 H, Ph-
4,4-Difluoro-3-(4-methoxyphenyl)-5-phenyl-8-trifluoromethyl-4- 2c,6c), 6.73 (d, J = 4.5 Hz, 1 H, 6-H) ppm. 13C NMR (CDCl3): δ
bora-3a,4a-diaza-s-indacene (3ad): Yield 0.110 g (75%) as dark blue
needles with metallic luster, m.p. 136–138 °C. IR (KBr): ν
= 162.3 (C-5), 159.4 (C-3), 142.3 (C-4a), 140.3 (C-1b), 136.8 (C-
1c), 133.9 (C-7a), 133.2 (C-2), 131.9 (C-8a), 131.8 (C-1d), 130.9 (C-
2a,6a), 130.6 (C-4d), 130.5 (C-7), 130.1 (C-1a), 129.7 (t, J = 4.2 Hz,
C-2d,6d), 128.9 (C-3b,5b), 128.6 (C-2c,6c), 128.5 (C-3c,5c,3d,5d),
127.9 (C-4b), 127.8 (C-1), 127.7 (C-4c), 127.2 (C-2b,6b), 126.6 (C-
3a,5a), 126.4 (q, J = 33.3 Hz, C-8), 123.1 (C-6), 122.7 (q, J =
=
˜
max
731
736
741
1604, 1562, 1474, 1452, 1434, 1398, 1299, 1272, 1222, 1188, 1171,
1134, 1086, 1070, 1052, 838, 795, 750, 735, 730 cm–1. 1H NMR
(CDCl3): δ = 7.89 (m, 2 H, Ph-2a,6a), 7.83 (m, 2 H, Ph-2b,6b),
7.43 (m, 1 H, 7-H), 7.42 (m, 3 H, Ph-3b,4b,5b), 7.37 (m, 1 H, 1-
H), 6.94 (m, 2 H, Ph-3a,5a), 6.75 (d, J = 4.5 Hz, 1 H, 6-H), 6.67 (d,
276.2 Hz, CF3) ppm. 19F NMR (CDCl3): δ = –132.3 (m, JBF
=
J = 4.4 Hz, 1 H, 2-H), 3.83 (s, 3 H, Me) ppm. 13C NMR (CDCl3): δ 30.5 Hz, BF2), –54.6 (CF3) ppm. C34H22BF5N2 (564.36): calcd. C
= 162.5 (C-5), 161.9 (C-4a), 160.2 (C-3), 134.1 (C-7a), 132.8 (C-
8a), 132.3 (C-1b), 131.8 (t, J = 4.0 Hz, C-2a,6a), 130.7 (C-1), 130.5
(C-4b), 129.6 (t, J = 4.2 Hz, C-2b,6b), 129.2 (C-7), 128.4 (C-3b,5b),
126.0 (q, J = 32.8 Hz, C-8), 124.1 (C-1a), 123.3 (C-6), 122.8 (q, J
72.36, H 3.93, B 1.92, F 16.83, N 4.96; found C 72.18, H 3.59, F
17.20, N 4.69.
4,4-Difluoro-3-[(1,1-biphenyl)-4-yl]-5-(2-thienyl)-8-trifluoromethyl-
4-bora-3a,4a-diaza-s-indacene (3bf): Yield 0.133 g (79%) as dark
801
806
= 276.7 Hz, CF3), 122.2 (C-2), 114.2 (C-3a,5a), 55.4 (Me) ppm. 19
F
green needles with metallic luster, m.p. 214–216 °C. IR (KBr): ν
˜
max
NMR (CDCl3): δ = –132.8 (m, JBF = 30.1 Hz, BF2), –54.5
(CF3) ppm. C23H16F5N2O (431.38): calcd. C 62.47, H 3.65, B 2.44,
F 21.48, N 6.34; found C 62.67, H 3.30, F 21.73, N 6.17.
= 1566, 1527, 1473, 1296, 1275, 1138, 1119, 1102, 1088, 1045, 1036,
1
852, 841, 790, 755 cm–1. H NMR (CDCl3): δ = 8.24 (dd, J = 3.9,
1.0 Hz, 1 H, 3-H of thiophene), 8.07 (m, 2 H, Ph-2a,6a), 7.74 (m,
2 H, Ph-3a,5a), 7.70 (m, 2 H, Ph-2b,6b), 7.60 (dd, J = 4.9, 1.0 Hz,
1 H, 5-H of thiophene), 7.50 (m, 2 H, Ph-3b,5b), 7.43 (m, 1 H, 7-
H), 7.42 (m, 1 H, 1-H), 7.40 (m, 1 H, Ph-4b), 7.20 (dd, J = 3.9,
4.9 Hz, 1 H, 4-H of thiophene), 6.96 (d, J = 4.5 Hz, 1 H, 6-H),
4,4-Difluoro-3-(4-chlorophenyl)-5-phenyl-8-trifluoromethyl-4-bora-
3a,4a-diaza-s-indacene (3ae): Yield 0.155 g (83%) as a dark blue
746
751
solid with metallic luster, m.p. 136–137 °C. IR (KBr): νmax = 1595,
˜
1562, 1509, 1478, 1452, 1432, 1299, 1275, 1224, 1173, 1139, 1086,
1
1070, 1053, 970, 947, 763, 748, 731, 698 cm–1. H NMR (CDCl3): 6.82 (d, J = 4.6 Hz, 1 H, 2-H) ppm. 13C NMR (CDCl3): δ = 159.9 811
δ = 7.84 (m, 2 H, Ph-2b,6b), 7.77 (m, 2 H, Ph-2a,6a), 7.46 (m, 1 (C-3), 153.6 (C-5), 153.6 (C-2 of thiophene), 142.9 (C-4a), 140.3
H, 7-H), 7.45 (m, 1 H, Ph-4b), 7.44 (m, 2 H, Ph-3b,5b), 7.42 (m, 1
(C-1b), 134.3 (C-7a), 133.9 (C-2 of thiophene), 133.8 (C-3 of thio-
phene), 133.6 (C-8a), 131.8 (C-5 of thiophene), 131.0 (C-1a), 130.2
H, 1-H), 7.38 (m, 2 H, Ph-3a,5a), 6.73 (d, J = 4.5 Hz, 1 H, 6-H),
6.67 (d, J = 4.4 Hz, 1 H, 2-H) ppm. 13C NMR (CDCl3): δ = 162.7 (C-2a,6a), 130.1 (C-7), 129.7 (C-4 of thiophene), 129.2 (C-1), 128.9
(C-5), 159.9 (C-3), 136.7 (C-4a), 133.8 (C-7a), 133.4 (C-8a), 131.5
(C-3b,5b), 127.9 (C-4b), 127.3 (C-2b,6b), 127.2 (C-3a,5a), 124.5 (q, 816
(C-1b), 131.0 (C-2a,6a), 130.9 (C-4b), 130.8 (C-7), 130.4 (C-1a), J = 33.2 Hz, C-8), 123.2 (C-6), 122.6 (C-2), 122.8 (q, J = 275.8 Hz,
756 130.2 (C-1), 129.7 (t, J = 4.2 Hz, C-2b,6b), 128.8 (C-3a,5a), 128.6
(C-3b,5b), 126.7 (q, J = 33.5 Hz, C-8), 122.5 (q, J = 276.0 Hz, CF3),
123.3 (C-6), 122.4 (C-2) ppm. 19F NMR (CDCl3): δ = –132.4 (m,
JBF = 30.5 Hz, BF2), –54.6 (CF3) ppm. C22H13BClF5N2 (446.61):
calcd. C 59.16, H 2.93, B 2.42, Cl 7.94, F 21.27, N 6.27; found C
CF3) ppm. 19F NMR (CDCl3): δ = –135.9 (m, JBF = 32.0 Hz, BF2),
–54.5 (CF3) ppm. C26H16BF5N2S (494.29): calcd. C 63.18, H 3.26,
B 2.19, F 19.22, N 5.67, S 6.49; found C 63.38, H 3.22, F 19.09, N
5.70, S 6.31.
821
4,4-Difluoro-3-[(1,1-biphenyl)-4-yl]-2-phenyl-5-(2-thienyl)-8-trifluoro-
methyl-4-bora-3a,4a-diaza-s-indacene (3bg): Yield 0.066 g (87%) as
a dark green solid with metallic luster, m.p. 214–215 °C. IR (KBr):
761
59.42, H 2.80, Cl 7.89, F 21.12, N 6.04.
4,4-Difluoro-3-[(1,1-biphenyl)-4-yl]-5-phenyl-8-trifluoromethyl-4-
bora-3a,4a-diaza-s-indacene (3af): Yield 0.084 g (75%) as a dark
νmax = 1563, 1526, 1482, 1470, 1451, 1426, 1415, 1283, 1252, 1236,
˜
blue solid with metallic luster, m.p. 204–206 °C. IR (KBr): ν
=
1167, 1142, 1117, 1052, 1029, 915, 850, 755, 719, 696, 687 cm–1. 1H
NMR (CDCl3): δ = 8.14 (dd, J = 3.9, 1.0 Hz, 1 H, 3-H of thio-
phene), 7.65 (m, 2 H, Ph-2b,6b), 7.62 (m, 2 H, Ph-2a,6a), 7.59 (m,
826
831
836
˜
max
1603, 1570, 1522, 1471, 1448, 1410, 1372, 1329, 1292, 1272, 1236,
1205, 1154, 1122, 1082, 1043, 970, 907, 839, 819, 796, 763, 724,
766
683 cm–1. 1H NMR (CDCl3): δ = 7.95 (m, 2 H, Ph-2a,6a), 7.85 (m, 2 H, Ph-3a,5a), 7.54 (dd, J = 4.9, 1.0 Hz, 1 H, 5-H of thiophene),
2 H, Ph-2c,6c), 7.64 (m, 2 H, Ph-3a,5a), 7.60 (m, 2 H, Ph-2b,6b),
7.45 (m, 1 H, 1-H), 7.43 (m, 2 H, Ph-3b,5b), 7.41 (m, 2 H, Ph- Ph-4b), 7.22 (m, 3 H, Ph-3c,4c,5c), 7.20 (dd, J = 3.9, 4.9 Hz, 1 H,
3c,5c), 7.40 (m, 2 H, 7-H, Ph-4c), 7.35 (m, 1 H, Ph-4b), 6.78 (d, J 4-H of thiophene), 7.12 (m, 2 H, Ph-2c,6c), 6.94 (d, J = 4.5 Hz, 1
771 = 4.6 Hz, 1 H, 2-H), 6.70 (d, J = 4.5 Hz, 1 H, 6-H) ppm. 13C NMR H, 6-H) ppm. 13C NMR (CDCl3): δ = 157.5 (C-3), 154.2 (C-5),
(CDCl3): δ = 161.7 (C-5), 161.5 (C-3), 143.3 (C-4a), 140.3 (C-1b), 142.1 (C-4a), 140.4 (C-1b), 136.2 (C-1c), 136.1 (C-7a), 134.7 (C-
139.8 (C-8a), 133.5 (C-7a), 132.0 (C-1c), 130.7 (C-7), 130.4 (C- 8a), 133.9 (C-3 of thiophene), 133.8 (C-2 of thiophene), 133.4 (C-
1,4c), 130.2 (C-1a,2a,6a), 129.6 (t, J = 4.2 Hz, C-2c,6c), 128.4 (C-
3c,5c), 128.9 (C-3b,5b), 128.0 (C-4b), 127.3 (C-2b,6b), 127.2 (C-
776 3a,5a), 126.5 (q, J = 33.3 Hz, C-8), 123.1 (C-6), 122.8 (q, J =
275.7 Hz, CF3), 122.9 (C-2) ppm. 19F NMR (CDCl3): δ = –132.4
(m, JBF = 31.3 Hz, BF2), –54.5 (CF3) ppm. 15N NMR (CDCl3): δ
7.53 (m, 1 H, 1-H), 7.43 (m, 3 H, Ph-3b,5b, 7-H), 7.35 (m, 1 H,
2), 132.0 (C-5 of thiophene), 131.2 (C-2a,6a), 130.5 (C-7), 129.9
(C-1a), 129.7 (C-4 of thiophene), 128.9 (C-3b,5b), 128.6 (C-2c,6c),
128.5 (C-3c,5c), 127.8 (C-4b), 127.5 (C-4c), 127.2 (C-2b,6b), 126.7
(C-1), 126.5 (C-3a,5a), 125.9 (q, J = 33.2 Hz, C-8), 123.3 (C-6),
122.9 (q, J = 275.3 Hz, CF3) ppm. 19F NMR (CDCl3): δ = –136.4
Eur. J. Org. Chem. 0000, 0–0
© 0000 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
11

Job/Unit: O30212
/KAP1
Date: 08-05-13 18:37:42
Pages: 13
B. A. Trofimov et al.
(m, JBF = 31.3 Hz, BF2), –54.5 (CF3) ppm. C32H20BF5N2S –192.8 ppm. C34H22BF5N2 (564.36): calcd. C 72.36, H 3.93, B 1.92,
FULL PAPER
841
(570.38): calcd. C 67.38, H 3.53, B 1.90, F 16.65, N 4.91, S 5.62;
found C 67.77, H 3.25, F 16.93, N 4.71, S 5.49.
F 16.83, N 4.96; found C 71.98, H 3.90, F 17.18, N 4.65.
4,4-Difluoro-3,5-bis[(1,1-biphenyl)-4-yl]-2,6-diphenyl-8-trifluoro-
methyl-4-bora-3a,4a-diaza-s-indacene (3gg): Yield 0.071 g (90%) as
dark green needles with metallic luster, m.p. 296–298 °C. IR (KBr):
906
4,4-Difluoro-3,5-bis(4-methylphenyl)-8-trifluoromethyl-4-bora-
3a,4a-diaza-s-indacene (3cc): Yield 0.114 g (89%) as a dark blue
ν = 1570, 1406, 1275, 1245, 1226, 1141, 1082, 1002, 966, 919,
˜
max
846
851
856
solid with metallic luster, m.p. 118–120 °C. IR (KBr): νmax = 1565,
˜
842, 748, 629 cm–1. 1H NMR (CDCl3): δ = 7.57 (m, 4 H, Ph-2b,6b),
1474, 1426, 1392, 1301, 1275, 1226, 1170, 1139, 1085, 1052, 968,
1
946, 888, 822, 788, 750, 729 cm–1. H NMR (CDCl3): δ = 7.81 (m,
7.53 (m, 8 H, Ph-3a,5a,2a,6a), 7.52 (m, 2 H, 1,7-H), 7.39 (m, 4 H,
Ph-3b,5b), 7.31 (m, 2 H, Ph-4b), 7.22 (m, 6 H, Ph-3c,5c,4c), 7.10 911
(m, 4 H, Ph-2c,6c) ppm. 13C NMR (CDCl3): δ = 159.7 (C-3,5),
142.4 (C-4a,4aЈ), 140.3 (C-1b,1bЈ), 136.9 (C-1c,1cЈ), 133.2 (C-2,6),
132.1 (C-8a,7a), 131.0 (C-2a,6a,2aЈ,6aЈ), 130.0 (C-1a,1aЈ), 128.9 (C-
3b,5b,3bЈ,5bЈ), 128.7 (C-2c,6c,2cЈ,6cЈ), 128.5 (C-3c,5c,3cЈ,5cЈ),
127.8 (C-4b,4bЈ), 127.9 (C-1,7), 127.8 (C-4c,4cЈ), 127.2 (C- 916
2b,6b,2bЈ,6bЈ), 126.6 (C-3a,5a,3aЈ,5aЈ), 126.3 (q, J = 33.4 Hz, C-8),
125.5 (q, J = 276.4 Hz, CF3) ppm. 19F NMR (CDCl3): δ = –131.7
(m, JBF = 29.8 Hz, BF2), –54.6 (t, JHF = 2.0 Hz, CF3) ppm.
C46H30BF5N2 (716.56): calcd. C 77.10, H 4.22, B 1.51, F 13.26, N
4 H, Ph-2a,6a), 7.44 (m, 2 H, 1,7-H), 7.26 (m, 4 H, Ph-3a,5a), 6.72
(d, J = 4.6 Hz, 2 H, 2,6-H), 2.40 (s, 6 H, Me) ppm. 13C NMR
(CDCl3): δ = 161.7 (C-3,5), 140.9 (C-4a,4aЈ), 133.4 (C-8a,7a), 130.0
(C-1,7), 129.6 (t, J = 4.0 Hz, C-2a,6a,2aЈ,6aЈ), 129.2 (C-
3a,5a,3aЈ,5aЈ), 129.1 (C-1a,1aЈ), 125.8 (q, J = 33.2 Hz, C-8), 122.8
(q, J = 276.1 Hz, CF3) 122.7 (C-2,6), 21.6 (Me,MeЈ) ppm. 19F
NMR (CDCl3): δ = –132.5 (m, JBF = 31.1 Hz, BF2), –54.5 (t, JHF
= 2.3 Hz, CF3) ppm. 15N NMR (CDCl3): δ = –193.5 ppm.
C24H18BF5N2 (440.22): calcd. C 65.48, H 4.12, B 2.46, F 21.58, N
6.36; found C 65.21, H 4.02, F 21.92, N 6.12.
3.91; found C 77.02, H 3.98, F 13.62, N 3.52.
921
4,4-Difluoro-3,5-bis(4-methoxyphenyl)-8-trifluoro-methyl-4-bora-
3a,4a-diaza-s-indacene (3dd): Yield 0.113 g (57%) as a dark blue
Supporting Information (see footnote on the first page of this arti-
cle): Analytical data for compounds 6 and analytical data and ab-
sorption and fluorescence spectra of compounds 3 are reported.
861
866
871
solid with metallic luster, m.p. 180–182 °C. IR (KBr): νmax = 1604,
˜
1564, 1474, 1429, 1395, 1297, 1265, 1221, 1179, 1137, 1083, 1045,
1
833, 791, 742, 620 cm–1. H NMR (CDCl3): δ = 7.87 (m, 4 H, Ph-
2a,6a), 7.38 (m, 2 H, 1,7-H), 6.94 (m, 4 H, Ph-3a,5a), 6.70 (d, J =
4.6 Hz, 2 H, 2,6-H), 3.84 (s, 6 H, OMe) ppm. 13C NMR (CDCl3):
δ = 161.7 (C-4a,4a), 160.9 (C-3,5), 133.4 (C-8a,7a), 131.5 (t, J =
4.0 Hz, C-2a,6a,2aЈ,6aЈ), 129.2 (C-1,7), 126.3 (q, J = 33.2 Hz, C-
8), 124.3 (C-1a,1aЈ), 122.6 (q, J = 276.0 Hz, CF3), 122.5 (C-2,6),
114.1 (C-3a,5a,3aЈ,5aЈ), 55.4 (OMe,OMeЈ) ppm. 19F NMR
Acknowledgments
The authors thank Presidium of RAS (project numbers 8.2 and
5.9.1) for the support of this research.
926
931
[1] a) R. Ziessel, G. Ulrich, A. Harriman, New J. Chem. 2007, 31,
496–501; b) A. Loudet, K. Burgess, Chem. Rev. 2007, 107,
4891–4932; c) G. Ulrich, R. Ziessel, A. Harriman, Angew.
Chem. 2008, 120, 1202–1219; Angew. Chem. Int. Ed. 2008, 47,
1184–1201; d) A. C. Benniston, G. Copley, Phys. Chem. Chem.
Phys. 2009, 11, 4124–4131; N. Boens, V. Leen, W. Dehaen,
Chem. Soc. Rev. 2012, 41, 1130–1172.
(CDCl3): δ = –132.9 (m, JBF = 31.2 Hz, BF2), –54.5 (t, JHF
=
2.3 Hz, CF3) ppm. C24H18BF5N2O2 (472.22): calcd. C 61.04, H
3.84, B 2.29, F 20.12, N 5.93; found C 60.73, H 3.59, F 20.47, N
5.58.
4,4-Difluoro-3,5-bis(4-chlorophenyl)-8-trifluoromethyl-4-bora-3a,4a-
diaza-s-indacene (3ee): Yield 0.088 g (88%) as a lustrous bronze
[2] a) G. Meng, S. Velayudham, A. Smith, R. Luck, H. Liu, Mac-
876
881
886
solid, m.p. 176–178 °C. IR (KBr): ν
= 1593, 1569, 1559, 1471,
˜
max
romolecules 2009, 42, 1995–2001; b) Y. Shiraishi, H. Maehara, 936
T. Sugii, D. Wang, T. Hirai, Tetrahedron Lett. 2009, 50, 4293–
4296; c) S. Atilgan, I. Kutuk, T. Ozdemir, Tetrahedron Lett.
2010, 51, 892–894; d) M. Kamiya, K. Johnsson, Anal. Chem.
2010, 82, 6472–6479.
1429, 1313, 1299, 1277, 1224, 1145, 1112, 1081, 1053, 1012, 969,
888, 838, 791, 751, 728 cm–1. 1H NMR (CDCl3): δ = 7.77 (m, 4 H,
Ph-2a,6a), 7.44 (m, 2 H, 1,7-H), 7.39 (m, 4 H, Ph-3a,5a), 6.69 (d,
J = 4.6 Hz, 2 H, 2,6-H) ppm. 13C NMR (CDCl3): δ = 160.7 (C-
3,5), 137.0 (C-4a,4aЈ), 133.7 (C-8a,7a), 130.9 (t, J = 4.2 Hz, C-
2a,6a,2aЈ,6aЈ), 130.7 (C-1,7), 130.1 (C-1a,1aЈ), 128.9 (C-
3a,5a,3aЈ,5aЈ), 127.0 (q, J = 33.4 Hz, C-8), 122.9 (C-2,6), 122.6 (q,
[3] a) M. C. Yee, S. C. Fas, M. M. Stohlmeyer, T. J. Wandless,
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941
946
951
J = 276.2 Hz, CF3) ppm. 19F NMR (CDCl3): δ = –132.3 (m, JBF
=
31.3 Hz, BF2), –54.6 (t, JHF = 2.1 Hz, CF3) ppm. C22H12BCl2F5N2
(481.06): calcd. C 54.93, H 2.51, B 2.25, Cl 14.74, F 19.75, N 5.82;
found C 54.55, H 2.48, Cl 14.49, F 20.10, N 5.71.
4,4-Difluoro-3,5-bis[(1,1-biphenyl)-4-yl]-8-trifluoromethyl-4-bora-
3a,4a-diaza-s-indacene (3ff): Yield 0.102 g (36%) as dark blue need-
les with metallic luster, m.p. 234–236 °C. IR (KBr): ν
= 1604,
˜
max
891
896
901
1573, 1544, 1525, 1487, 1470, 1411, 1384, 1374, 1330, 1292, 1275,
1245, 1205, 1156, 1122, 1082, 1046, 972, 908, 837, 819, 800, 764,
733, 725, 694 cm–1. 1H NMR (CDCl3): δ = 7.98 (m, 4 H, Ph-2a,6a),
7.66 (m, 4 H, Ph-3a,5a), 7.61 (m, 4 H, Ph-2b,6b), 7.46 (m, 2 H,
1,7-H), 7.45 (m, 4 H, Ph-3b,5b), 7.35 (m, 2 H, Ph-4b), 6.80 (d, J =
4.6 Hz, 2 H, 2,6-H) ppm. 13C NMR (CDCl3): δ = 161.1 (C-3,5),
143.1 (C-4a,4aЈ), 140.1 (C-1b,1bЈ), 133.8 (C-8a,7a), 130.0 (C-1,7),
129.9 (C-2a,6a,2aЈ,6aЈ), 130.5 (C-1a,1aЈ), 127.1 (C-2b,6b,2bЈ,6bЈ),
128.6 (C-3b,5b,3bЈ,5bЈ), 127.8 (C-4b,4bЈ), 126.9 (C-3a,5a,3aЈ,5aЈ),
126.1 (q, J = 33.4 Hz, C-8), 122.9 (C-2,6), 122.7 (q, J = 276.2 Hz,
CF3) ppm. 19F NMR (CDCl3): δ = –132.4 (m, JBF = 31.3 Hz, BF2),
–54.5 (t, JHF = 2.1 Hz, CF3) ppm. 15N NMR (CDCl3): δ =
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Job/Unit: O30212
/KAP1
Date: 08-05-13 18:37:42
Pages: 13
Difluorobora-s-diazaindacene Dyes
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Received: February 8, 2013
Eur. J. Org. Chem. 0000, 0–0
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