Isoindole-BODIPY dyes as red to near-infrared fluorophores

Article abstract of DOI:10.1002/chem.201200398

Three-in-one go: One-pot synthesis of isoindole-BODIPY dyes was developed based on nucleophilic substitution (S_NAr) reactions of in situ formed chlorinated dipyrromethene by pyrrole. These dyes have long wavelengths, sharp absorption and fluorescence, high fluorescence quantum yields, and high photostability. The wavelength is finely tunable over a wide range (590-714 nm) by variation of substituent groups and functionalization (see scheme). Copyright

Full text of DOI:10.1002/chem.201200398

Supporting Information
ꢀ
Copyright Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, 2012
Isoindole-BODIPY Dyes as Red to Near-Infrared Fluorophores
Changjiang Yu, Yajun Xu, Lijuan Jiao,* Jinyuan Zhou, Zhaoyun Wang, and
[
a]
Erhong Hao*
chem_201200398_sm_miscellaneous_information.pdf

Contents:
General Methods…………………………………………………………...........2
. Crystal Data of Compounds ……………………………………………….........2
Syntheses and Characterizations of Compounds…………………………...........7
1
.
2
3
.
1
13
4
. Copies of H NMR, C NMR for All New Compounds …………………….......12
5
. HRMS for All New Compounds………………………………………………...62
1
.
General Methods
Reagents were purchased as reagentꢀgrade and used without further purification unless otherwise stated.
Solvents were used as received from commercial suppliers unless noted otherwise. Toluene was distilled from
CaH . All reactions were performed in ovenꢀdried or flameꢀdried glassware unless otherwise stated, and were
2
1
13
monitored by TLC using 0.25 mm silica gel plates with UV indicator (60Fꢀ254). Hꢀ and CꢀNMR were
1
obtained on a 300 spectrometer at 298 K. Chemical shifts (δ) are given in ppm relative to CDCl 7.26 ( H) and
3
13
7
7.16 ppm ( C). Coupling constants J are given in [Hz] and the multiplicities are expressed as follows: s =
singlet, d = doublet, t = triplet, m = multiplet. Highꢀresolution mass spectras were obtained by using ESIꢀTOF
with positive mode. The isotope peaks were matched with the calculated pattens; only the most abundant peaks
for all the compounds are listed.
UVꢀvisible absorption spectra were recorded on a Hitachi Uꢀ3010 Spectrophotometer (190ꢀ1100 nm scan
range). Fluorescence emission spectra were recorded on a Hitachi Fꢀ4600 FL Spectrophotometer. Relative
quantum efficiencies of fluorescence of BODIPY derivatives were obtained by comparing the areas under the
1
a
corrected emission spectrum of the test sample in various solvent with that of methylene blue or Rhodamin B
1
b
(
0.49 in EtOH) . Nonꢀdegassed, spectroscopic grade solvents and a 10 mm quartz cuvette were used. Dilute
solutions (0.01<A<0.05) were used to minimize the reabsorption effects. Quantum yields were determined using
2
the following equation :
2
Φ = Φ (I /I ) (A /A ) (η /η )
X
S
X
S
S
X
X
S
Where Φ stands for the reported quantum yield of the standard, I stands for the integrated emission spectra, A
S
stands for the absorbance at the excitation wavelength and η stands for the refractive index of the solvent being
1

used (η = 1 when the same solvent was used for both the test sample and the standard). X subscript stands for the
test sample, and S subscript stands for the standard.
2
. Crystal Data of Compounds
.1 Methods and crystal data
2
Crystals of BODIPYs 3ac, 3ba, 5 and 6c suitable for Xꢀray analysis were obtained by slow evaporation
of their dichloromethane solutions. The vial containing this solution was placed, loosely capped, to
promote the crystallization.
Crystal data for BODIPYs 3ac, 3ba, 5 and 6c were collected using a Bruker SMART
APEXⅡdiffractometer with CCD area detector and multiꢀlayer mirror monochromated MoꢀKα radiation
(λ = 0.71073 Å) at 293 K.
The structures were solved by the direct method using the SHELXSꢀ974 program and refined by the leastꢀ
2
3
4
squares method on F , SHELXLꢀ97, incorporated in SHELXTL V5.10. All nonꢀhydrogen atoms were refined
anisotropically. Hydrogen atoms were assigned to idealized positions and were included in structure factors
calculations.
CCDCꢀ859405 (3ac), 859406 (3ba), 859407 (5), and 859408 (6c) contain the supplementary crystallographic
data for this paper. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre
via www.ccdc.cam.ac.uk/data_request/cif.
Crystal data for 3ac: C H BF N , M = 363.21, purple, monoclinic, space group P2(1)/n, a = 11.177(1), b =
2
1
20
2
3
w
3
ꢀ3
7
.630(1), c = 21.521(4) Å, α = 90, β = 97.98 (0), γ = 90°, V = 1817.6(5) Å , Z = 4, D
= 1.327 gcm , T =
calcd
–1
2
2
2
93(2) K, ꢁ = 0.093 mm , F(000) = 760, GooF(F ) = 1.007, R = 0.0408, wR = 0.0940 for I>2σ(I), R = 0.0653,
1
1
2
wR = 0.1074 for all data, 12536 independent reflections [2θ ≤ 50.0°].
Crystal data for 3ba: C H BF N , M = 321.13, purple, monoclinic, space group C2/c, a = 27.768(2), b =
18
14
2
3
w
3
ꢀ3
7
.7158(6), c = 16.7367(1) Å, α = 90, β = 119.6960 (1), γ = 90°, V = 2993.8(4) Å , Z = 8, Dcalcd = 1.425 gcm , T
–
1
2
2
=
293(2) K, ꢁ = 0.103 mm , F(000) = 1328, GooF(F ) = 1.054, R = 0.0411, wR = 0.0985 for I>2σ(I), R =
1 1
2
0
.0647, wR = 0.1107 for all data, 12512 independent reflections [2θ ≤ 55.18°].
Crystal data for 5: C H BF N , M = 335.16, purple, monoclinic, space group P2(1)/n, a = 10.1992(1), b =
1
9
16
2
3
w
3
ꢀ3
7
2
.0097(8), c = 22.155(3) Å, α = 90, β = 94.6710 (1), γ = 90°, V = 1578.7(3) Å , Z = 4, Dcalcd = 1.410 gcm , T =
–1
2
2
93(2) K, ꢁ = 0.101 mm , F(000) = 696, GooF(F ) = 1.069, R = 0.0704, wR = 0.1998 for I>2σ(I), R = 0.0937,
1
1
2
wR = 0.2194 for all data, 12128 independent reflections [2θ ≤ 55.12°].
Crystal data for 6c: C H BF N O , M = 567.43, purple, triclinic, space group P1, a = 10.248(6), b = 11.011(7),
3
3
32
2
3
3
w
3
ꢀ3
c = 13.670(9) Å, α = 73.817(8), β = 79.085 (9), γ = 86.538(9)°, V = 1454.5(1) Å , Z = 2, D
= 1.296 gcm , T
calcd
–
1
2
2
=
293(2) K, ꢁ = 0.091 mm , F(000) = 596, GooF(F ) = 1.090, R = 0.0867, wR = 0.2169 for I>2σ(I), R =
1 1
2
0
.1820, wR = 0.2633 for all data, 12222 independent reflections [2θ ≤ 55.3°].
.2 The packing of BODIPYs 3ac, 3ba, 5 and 6c
2
2

Figure S1. Crystal structure of the dimer of BODIPY 3ac through intermolecular Hꢀbonding. Dashed
line was used to show Hꢀbonding.
3

Figure S2. Intermolecular Hꢀbonding of Crystal structure of 3ba (top) and its crystal packing structure
bottom). Dashed line was used to show intermolecular Hꢀbonding.
(
4

Figure S3. Intermolecular Hꢀbonding of Crystal structure of 5 (top) and its crystal packing structure
bottom). Dashed line was used to show intermolecular Hꢀbonding.
(
5

Figure S4. Intermolecular Hꢀbonding of Crystal structure of 6c (top) and its crystal packing structure
bottom). Dashed line was used to show intermolecular Hꢀbonding.
(
3
. Syntheses and Characterizations of Compounds
5
Compounds 1 and 2 were synthesized from literature or purchased from commercial sources.
General procedure for the preparation of BODIPYs 3: To the mixture of compound 1 (0.5 mmol) and pyrrole
(
5 mmol) were added 20 ml CH Cl and POCl (470  l, 5 mmol) in 1 ml CH Cl almost at the same time and
2 2 3 2 2
quickly at iceꢀcold condition under argon. The reaction mixture was stirred at room temperature and was
monitored by TLC. When compound 1 had been consumed, to the reaction mixture was added Et N (1 ml) under
3
iceꢀcold condition, and the mixture was stirred for 10 min before addition of BF ꢂOEt (1.2 ml) under iceꢀcold
3
2
condition through syringe. The reaction mixture was left stirring for overnight, poured into water and extracted
with CH Cl . Organic layers were combined, and solvent was removed under vacuum. The crude product was
2
2
purified from chromatograph (silica gel, petroleum/CH Cl = 2/1, v/v), affording the desired compound as
2
2
greenish (or bluish, or reddish) powder.
BODIPY 3aa: To compound 1a (90 mg, 0.5 mmol) in pyrrole (0.69 ml, 10 mmol) were added 20 ml CH Cl and
2
2
POCl (470 ꢀl, 5 mmol) in 1 ml CH Cl almost at the same time and quickly at iceꢀcold condition under argon.
3
2
2
The reaction mixture was stirred at room temperature (35 ℃) for 16 h. Reaction was monitored by TLC. When
compound 1 had been consumed, to the reaction mixture was added Et N (1 ml) under iceꢀcold condition, and
3
6

the mixture was stirred for 10 min before addition of BF ꢂOEt (1.2 ml) under iceꢀcold condition through syringe.
3
2
The reaction mixture was left stirring for overnight, poured into water and extracted with CH Cl . Organic layers
2
2
were combined, and solvent was removed under vacuum. The crude product was purified from chromatograph
(
silica gel, petroleum/CH Cl = 2/1, v/v), affording the desired compound 3aa as reddish powder in 35% yield
2 2
1
(
54 mg). H NMR (300 MHz, CDCl ): δ 10.10(s, 1H), 7.95(d, J = 7.2 Hz, 1H), 7.75(d, J = 7.2 Hz, 1H), 7.41ꢀ
3
13
7
.31(m, 2H), 7.14(s, 1H), 7.02(s, 1H), 6.90(s, 1H), 6.80(s, 1H), 6.50(s, 1H), 6.32(s, 1H), 6.14(s, 1H). C NMR
(
75 MHz, CDCl ): δ 150.2, 136.9, 133.4, 132.7, 131.6, 131.4, 131.3, 127.7, 127.5, 125.1, 122.2, 120.6, 120.0,
3
+
1
19.7, 115.8, 114.5, 112.5. HRMS (EI) Calcd. for C H N BF [M] : 307.1092, found 307.1087.
1
7
12
3
2
BODIPY 3ab: To compound 1a (90 mg, 0.5 mmol) in 2ꢀmethylpyrrole ( 0.42 ml, 5 mmol) were added 20 ml
CH Cl and POCl (470 ꢀl, 5 mmol) in 1 ml CH Cl almost at the same time and quickly at iceꢀcold condition
2
2
3
2
2
under argon. The reaction mixture was stirred at room temperature (35 ℃) for 2 h. Reaction was monitored by
TLC. When compound 1 had been consumed, to the reaction mixture was added Et N (1 ml) under iceꢀcold
3
condition, and the mixture was stirred for 10 min before addition of BF ꢂOEt (1.2 ml) under iceꢀcold condition
3
2
through syringe. The reaction mixture was left stirring for overnight, poured into water and extracted with
CH Cl . Organic layers were combined, and solvent was removed under vacuum. The crude product was purified
2
2
from chromatograph (silica gel, petroleum/CH Cl = 2/1, v/v), affording the desired compound 3ab as bluish
2
2
1
powder in 41% yield (69 mg). H NMR (300 MHz, CDCl ): δ 10.59(s, 1H), 8.12(d, J = 7.8 Hz, 1H), 7.78(d, J =
3
7
.5 Hz, 1H), 7.54(t, J = 7.5 Hz, 1H), 7.40(t, J = 7.8, 1H), 7.19(s, 1H), 6.64 (s, 1H), 6.24(s, 1H), 6.13(s, 1H), 2.59
1
3
(
s, 3H), 2.50(s, 3H). C NMR (75 MHz, CDCl ): δ 146.8, 138.5, 136.6, 132.1, 131.7, 131.4, 130.6, 127.0, 125.0,
3
+
1
21.5, 121.2, 120.6, 119.5, 114.8, 114.4, 111.6, 14.5, 14.0. HRMS(EI) calcd. for C H N BF [M+H] :
19
17
3
2
336.1478, found 336.1473.
3
BODIPY 3ac: Prepared using the procedure above by reacting compound 1a (90 mg, 0.5 mmol) with 2, 4ꢀ
dimethylpyrrole (0.5 ml, 5 mmol) under POCl (470 ꢀl, 5 mmol) using the same procedure described above
3
(
35 ℃) for 2 h, and purified from chromatograph (silica gel, petroleum/CH Cl = 2/1, v/v), the desired
2 2
1
compound 3ac was obtained as bluish powder in 43% yield (78 mg). H NMR (300 MHz, CDCl ): δ 9.70(s, 1H),
3
7
.82ꢀ7.77(m, 2H), 7.49(d, J = 7.2 Hz, 1H), 7.34ꢀ7.26(m, 2H), 6.03ꢀ5.98 (m, 2H), 2.50 (s, 3H), 2.40(s, 3H), 2.30(s,
13
6
H). C NMR (75 MHz, CDCl ): δ 149.4, 147.8, 136.2, 134.7, 134.6, 131.2, 131.0, 130.5, 130.1, 127.2, 125.8,
3
+
1
25.7, 119.1, 118.5, 116.7, 113.6, 112.3, 14.5, 13.7, 11.4. HRMS (EI) Calcd. for C H N BF [M] : 363.1718,
2
1
20
3
2
found 363.1714.
3
BODIPY 3ad: Prepared using the procedure above by reacting compound 1a (90 mg, 0.5 mmol) with 2, 4ꢀ
dimethylꢀ3ꢀethylpyrrole (0.65 ml, 5 mmol) under POCl (470 ꢀl, 5 mmol) using the same procedure described
3
above (35 ℃) for 2 h, and purified from chromatograph (silica gel, petroleum/CH Cl = 4/1, v/v), the desired
2
2
1
compound 3ad was obtained as greenish powder in 38% yield (79 mg). H NMR (300 MHz, CDCl ): δ 9.64(s,
3
1
H), 7.81ꢀ7.74(m, 2H), 7.46(d, J = 7.2 Hz, 1H), 7.31ꢀ7.22(m, 2H), 2.52ꢀ2.35(m, 10H), 2.45ꢀ2.22(m, 6H), 1.16(d,
13
J = 7.5 Hz, 3H), 1.09(d, J= 7.5 Hz, 3H). C NMR (75 MHz, CDCl ): δ 147.5, 146.9, 136.0, 132.0, 131.0, 130.3,
3
7

1
30.1, 129.7, 129.6, 125.9, 125.2, 125.2, 124.9, 119.0, 117.8, 112.9, 17.9, 17.5, 15.3, 15.0, 13.0, 12.0, 9.6.
+
HRMS (EI) Calcd. for C H N BF [M] : 419.2344, found 419.2347.
25
28
3
2
3
BODIPY 3ae: Prepared using the procedure above by reacting compound 1a (165 mg, 0.92 mmol) with 3ꢀ
methylindole ( 1.2 g, 9.2 mmol) under POCl (0.86 ml, 9.2 mmol) using the same procedure described above
3
(
35 ℃) for 8.5 h, and purified from chromatograph (silica gel, petroleum/CH Cl = 2/1, v/v), the desired
2 2
1
compound 3ad was obtained as brown powder in 22% yield (95 mg). H NMR (300 MHz, CDCl ): δ 10.06(s,
3
1
H), 8.00(d, J = 4.2 Hz, 1H), 7.89(d, J = 7.2 Hz, 1H), 7.72ꢀ7.66(m, 4H), 7.54ꢀ7.53(m, 2H), 7.42ꢀ7.37(t, J = 6.6
1
3
Hz, 1H), 7.29ꢀ7.21(m, 3H), 7.06(s, 1H), 2.61ꢀ2.59(m, 6H). C NMR (75 MHz, CDCl ): δ 152.8, 132.0, 131.4,
3
1
1
4
31.4, 127.7, 127.5, 127.4, 127.2, 127.0, 126.7, 126.1, 125.6, 125.1, 122.9, 122.5, 120.7, 120.5, 120.1, 120.0,
+
19.5, 115.8, 114.1, 113.1, 111.9, 109.7, 12.0, 9.3. HRMS (EI) Calcd. for C H N BF [M] : 436.1791, found
27
21
3
2
36.1782.
BODIPY 3ba: Prepared using the procedure above by reacting compound 1b (97 mg, 0.5 mmol) with pyrrole
0.69 ml, 10 mmol) under POCl (470 ꢀl, 5 mmol) using the same procedure described above for 16h, the crude
(
3
product was purified from chromatograph (silica gel, petroleum/CH Cl = 2/1, v/v), affording the desired
2
2
1
compound 3ba as reddish powder in 42% yield (67 mg). H NMR (300 MHz, CDCl ): δ 10.79(s, 1H), 8.19(d, J =
3
7
2
1
3
.8 Hz, 1H), 8.00(d, J = 7.2, 1H), 7.59(t, J = 7.5 Hz, 1H), 7.48ꢀ1.30(m, 4H), 6.90(s, 1H), 6.51ꢀ6.43(m, 2H),
13
.76(s, 3H). C NMR (75 MHz, CDCl ): δ 149.1, 136.4, 133.6, 132.4, 132.4, 132.0, 131.3, 130.8, 126.7, 126.2,
3
+
25.7, 122.9, 121.6, 119.7, 118.3, 114.1, 111.9, 16.5. HRMS (EI) Calcd. for C H N BF [M] : 321.1249, found
1
8
14
3
2
21.1242.
BODIPY 3bc: Prepared using the procedure above by reacting compound 1b (97 mg, 0.5 mmol) with 2, 4ꢀ
dimethylpyrrole (0.5 ml, 5 mmol) under POCl (470 ꢀl, 5 mmol) using the same procedure described above
3
(
35 ℃) for 2 h, the crude product was purified from chromatograph (silica gel, petroleum/CH Cl = 2/1, v/v),
2 2
1
affording the desired compound 3bc as blue powder in 43% yield (81 mg). H NMR (300 MHz, CDCl ): δ 9.52(s,
3
1
5
1
1
H), 8.00(d, J = 8.1 Hz, 1H), 7.78(d, J = 8.1 Hz, 1H), 7.49(t, J = 7.5 Hz, 1H), 7.30(t, J = 7.5 Hz, 1H), 6.01ꢀ
1
3
.98(m, 2H), 2.85(s, 3H), 2.53(s, 3H), 2.48ꢀ2.38(m, 9H), 2.23(s, 3H). C NMR (75 MHz, CDCl ): δ 147.7,
3
35.5, 134.9, 133.3, 131.0, 130.1, 126.7, 126.2, 125.7, 124.8, 122.4, 119.4, 117.8, 112.6, 111.9, 16.9, 16.7, 14.3,
+
4.1, 13.6. HRMS (EI) Calcd. for C H N BF [M] : 377.1875, found 377.1882.
2
2
22
3
2
BODIPY 3bd: Prepared using the procedure above by reacting compound 1b (97 mg, 0.5 mmol) with 2, 4ꢀ
dimethyꢀ3ꢀethyllpyrrole (0.65 ml, 5 mmol) under POCl (470 ꢀl, 5 mmol) using the same procedure described
3
above (35 ℃) for 2 h, and purified from chromatograph (silica gel, petroleum/CH Cl = 2/1, v/v), the desired
2
2
1
compound 3bd was obtained as greenish powder in 40% yield (87 mg). H NMR (300 MHz, CDCl ): δ 9.46(s,
3
1
3
H), 8.00(d, J = 8.4 Hz, 1H), 7.76(d, J = 8.1 Hz, 1H), 7.46(t, J = 7.8 Hz, 1H), 7.29(d, J = 7.8 Hz, 1H), 2.88(s,
1
3
H), 2.50ꢀ2.34(m, 13H), 2.18(s, 3H), 1.16(t, J = 7.5 Hz, 3H), 1.06(t, J = 7.5 Hz, 3H). C NMR (75 MHz,
8

CDCl ): δ 146.0, 145.3, 135.3, 133.9, 132.3, 131.4, 129.7, 129.6, 128.7, 126.3, 124.3, 123.6, 122.3, 117.0, 17.9,
3
+
1
7.2, 16.9, 15.2, 13.9, 12.5, 12.1, 11.8. HRMS (EI) Calcd. for C H N BF [M] : 433.2501, found 433.2506.
2
6
30
3
2
Dipyrromethene 4: To compound 1a (179 mg, 1 mmol) in 20 ml CH Cl were added 2,4ꢀdimethylpyrrole (103
2
2
ꢀ
l, 1 mmol) in 1 ml CH Cl , and POCl (94 ꢀl, 1 mmol) in 1 ml CH Cl at iceꢀcold condition under argon. The
2
2
3
2
2
reaction mixture was stirred in iceꢀcold condition for 30 min. The starting material disappeared according to
TLC. After that, the mixture was quenched by Et N (1.2 ml), poured into water and extracted with CH Cl .
3
2
2
Organic layers were combined, dried and was removed under vacuum. The crude product was purified from
chromatograph (silica gel, petroleum/CH Cl = 2/1, v/v), affording the desired compound 4 as reddish powder in
2
2
1
9
0% yield (230 mg). H NMR (300 MHz, CDCl ): δ 10.81(s, 1H), 7.76(d, J = 7.5 Hz, 1H), 7.62(d, J = 7.5 Hz,
3
13
1
H), 7.44(t, J = 7.2 Hz, 1H), 7.34(t, J = 7.2 Hz, 1H), 7.10(s, 1H), 5.88(s, 1H), 2.38(s, 3H), 2.28(s, 3H). C NMR
(
75 MHz, CDCl ): δ 152.8, 140.3, 138.4, 137.6, 133.0, 130.8, 128.4, 127.1, 125.8, 120.5, 118.7, 114.8, 111.6,
3
+
1
3.8, 11.4. HRMS (EI) calcd for C H N Cl [M] : 256.0767, found 256.0774.
1
5
13
2
BODIPY 5: To compound 4 (128 mg, 0.5 mmol) in 20 ml CH Cl were added pyrrole (0.69 ml, 10mmol), and
2
2
POCl (470 ꢀl, 5 mmol) in 1 ml CH Cl at iceꢀcold condition under argon. The reaction mixture was stirred at
3
2
2
room temperature for 12 h. To the reaction mixture was added Et N (1 ml), and the mixture was stirred for 10
3
min before addition of BF ꢂOEt (1.2 ml) through syringe. The reaction mixture was left stirring for overnight,
3
2
poured into water and extracted with CH Cl . Organic layers were combined, and solvent was removed under
2
2
vacuum. The crude product was purified from chromatograph (silica gel, petroleum/CH Cl = 2/1, v/v), affording
2
2
1
the desired compound 5 as greenish powder in 48% yield (80 mg). H NMR (300 MHz, CDCl ): δ 10.73(s, 1H),
3
8
2
1
.12(d, J = 8.1 Hz, 1H), 7.81(d, J = 7.8 Hz, 1H), 7.51(t, 7.5 Hz, 1H), 7.40ꢀ7.33(m, 2H), 6.49(s, 1H), 5.99(s, 1H),
1
3
.54(s, 3H), 2.27(s, 3H). C NMR (75 MHz, CDCl ): δ 149.1, 146.4, 136.2, 134.6, 131.0, 130.8, 130.4, 130.2,
3
26.6, 125.5, 124.8, 122.7, 119.3, 118.3, 116.8, 113.6, 111.7, 14.5, 11.3. HRMS (EI) Calcd. for C H N BF
2
1
9
16
3
+
[
M] : 335.1405, found 335.1408.
Monostyryl-BODIPY 6a: To compound 3ac (40 mg, 0.11 mmol) and ethylꢀ2ꢀ(4ꢀformyphenoxy)acetate (46mg,
.22 mmol) in 20 ml toluene were added piperidine (1 ml) through syringe, and a crystal of pꢀTsOH. The
0
solution was refluxed over its boiling point up to 140 for 14 h in a roundꢀbottomed flask and any water formed
during the reaction was removed by using a Soxhlet extractor containing anhydrous CaCl . Reaction was
2
monitored by TLC. When 3ac had been consumed, the resulting mixture was cooled to room temperature,
poured into water and extracted with CH Cl . Organic layers were combined, and solvent was removed under
2
2
vacuum. The crude product was purified from chromatograph (silica gel, petroleum/CH Cl = 2/1, v/v) and then
2
2
1
recrystallized from CH OH, affording the desired compound 6a (52 mg) in 87% yield. H NMR (300 MHz,
3
CDCl ): δ 9.71(s, 1H), 7.85ꢀ7.77(m, 2H), 7.50ꢀ7.47(m, 3H), 7.41(s, 1H), 7.33(t, J = 7.5 Hz, 1H), 7.11(d, J = 12.9
3
Hz, 1H), 6.91ꢀ6.89(m, 2H), 6.62(s, 1H), 6.07(s, 1H), 4.65(s, 2H), 4.29(q, J = 6.9 Hz, 2H), 2.45(s, 3H), 2.32(s,
1
3
6
1
1
H), 1.31(t, J = 6.9 Hz, 3H). C NMR (75 MHz, CDCl ): δ 168.9, 158.1, 148.6, 147.5, 135.8, 134.9, 134.8,
3
32.9, 132.0, 131.1, 130.0, 128.5, 127.3, 125.8, 119.3, 118.7, 118.3, 115.1, 113.9, 112.9, 112.2, 65.7, 61.6, 14.5,
+
4.3, 13.8, 11.4. UPLC MS (EI) Calcd. for C H N O BF [M + H] : 554.2421, found 554.2419.
3
2
31
3
3
2
9

Monostyryl-BODIPY 6b : Prepared using the procedure above from compound 3ad (40 mg, 92 ꢁmol), ethylꢀ2ꢀ
4ꢀformyphenoxy)acetate (38 mg, 184 ꢁmol), piperidine (1 ml), and a crystal of pꢀTsOH in toluene (20 ml), and
purified from chromatograph (silica gel, petroleum/CH Cl = 2/1, v/v), the desired compound 6b was
(
2
2
1
recrystallized from CH OH and obtained as greenish power(17 mg) in 30% yield. H NMR (300 MHz, CDCl ):
3
3
δ 9.56(s, 1H), 8.03(d, J = 8.4, 1H), 7.79 (d, J = 8.1Hz, 1H), 7.55ꢀ7.47(m, 4H), 7.32(t, J = 7.5 Hz, 1H), 7.03ꢀ
6
2
1
6
.89(m, 2H), 4.65(s, 2H), 4.29(q, J = 7.2 Hz, 2H), 2.91(s, 3H), 2.70(q, J = 7.5 Hz, 2H), 2.50(q, J = 7.5 Hz, 2H),
1
3
.43(s, 3H), 2.35(s, 3H), 2.20(s, 3H), 1.33ꢀ1.15(m, 9H). C NMR (75 MHz, CDCl ): δ 169.0, 157.8, 143.5,
3
35.5, 132.2, 132.0, 131.7, 131.6, 130.7, 130.3, 130.1, 128.3, 126.7, 124.9, 124.5, 122.8, 119.1, 117.2, 115.0,
5.7, 61.6, 18.5, 18.1, 17.3, 15.4, 14.9, 14.3, 13.7, 12.8, 12.1. UPLC MS (EI) Calcd. for C H N O BF [M +
3
7
41
3
3
2
+
H] : 624.3204, found 624.3200.
Monostyryl-BODIPY 6c: Prepared using the procedure above from compound 3ac (40 mg, 106 ꢁmol), ethylꢀ2ꢀ
4ꢀformyphenoxy)acetate (44 mg, 212ꢁmol), piperidine (1 ml), and a crystal of pꢀTsOH in toluene (20 ml), and
purified from chromatograph (silica gel, petroleum/CH Cl = 2/1, v/v), the desired compound 6c was
(
2
2
1
recrystallized from CH OH and obtained as reddish power (20 mg) in 33% yield. H NMR (300 MHz, CDCl ): δ
3
3
9
2
2
1
6
5
.60(s, 1H), 7.96(d, J = 8.1 Hz, 1H), 7.76(d, J = 7.8 Hz, 1H), 7.55ꢀ7.52(m, 2H), 7.35ꢀ7.18(m, 4H), 7.01ꢀ6.98(m,
H), 6.88(d, J = 16.5 Hz, 1H), 6.03ꢀ5.98(m, 2H), 4.69(s, 2H), 4.31(q, J = 7.2 Hz, 2H), 2.50(s, 3H), 2.40(s, 3H),
13
.28ꢀ2.26(m, 6H), 1.33(t, J = 7.2 Hz, 3H). C NMR (75 MHz, CDCl ): δ 168.9, 158.6, 148.2, 147.1, 137.6,
3
35.8, 134.3, 133.8, 131.8, 129.9, 129.4, 128.4, 126.3, 125.9, 125.1, 122.8, 120.7, 118.9, 118.2, 115.4, 112.2,
+
5.5, 61.7, 16.6, 14.4, 14.3, 13.7. UPLC MS (EI) Calcd. for C H N O BF [M + H] : 568.2578, found
3
3
33
3
3
2
68.2573.
Distyryl-BODIPY 6d: Prepared using the procedure above from compound 3bc (40 mg, 106 ꢁmol), ethylꢀ2ꢀ(4ꢀ
formyphenoxy)acetate (88 mg, 424 ꢁmol), piperidine (1 ml), and a crystal of pꢀTsOH in toluene (20 ml), and
purified from chromatograph (silica gel, petroleum/CH Cl = 1/1, v/v), the desired compound 6d was
2
2
1
recrystallized from CH OH and obtained as greenish (33 mg) in 41% yield. H NMR (300 MHz, CDCl ): δ
3
3
9
3
3
1
1
.60(s, 1H), 7.98(d, J = 7.8 Hz, 1H), 7.76(d, J = 7.5 Hz, 1H), 7.55ꢀ7.47(m, 5H), 7.35ꢀ7.19(m, 4H), 7.12ꢀ6.98(m,
H), 6.91ꢀ6.86(m, 2H), 6.61(s, 1H), 6.07(s, 1H), 4.69(s, 2H), 4.64(s, 2H), 4.35ꢀ4.25(m, 4H), 2.45(s, 3H), 2.32(s,
1
3
H), 2.27(s, 3H), 1.36ꢀ1.26(m, 6H). C NMR (75 MHz, CDCl ): δ 168.9, 168.8, 158.7, 158.0, 147.5, 146.7,
3
37.7, 136.1, 135.9, 134.0, 133.0, 131.9, 131.8, 131.4, 131.2, 130.1, 129.9, 128.7, 128.5, 128.4, 126.3, 125.9,
25.2, 123.0, 120.7, 118.3, 116.0, 115.4, 115.0, 112.4, 110.1, 65.7, 65.5, 61.7, 61.6, 16.9, 14.3, 14.2, 13.8. UPLC
+
MS (EI) Calcd. for C H N O BF [M + H] : 758.3208, found 758.3212.
4
4
43
3
6
2
Monostyryl-BODIPY 6e: Prepared using the procedure above from compound 3ba (40 mg, 0.12 mmol), ethylꢀ
ꢀ(4ꢀformyphenoxy)acetate (50 mg, 0.24 mmol), piperidine (1 ml), and a crystal of pꢀTsOH in toluene (20 ml),
and purified from chromatograph (silica gel, petroleum/CH Cl = 2/1, v/v), the desired compound 6e was
2
2
2
1
recrystallized from CH OH and obtained as reddish power (46 mg) in 75% yield. H NMR (300 MHz, CDCl ): δ
3
3
1
6
0.85(s, 1H), 8.20(d, J = 7.8 Hz, 1H), 7.95(d, J = 7.8 Hz, 1H), 7.60ꢀ7.22(m, 9H), 7.02ꢀ6.99(m, 2H), 6.89(s, 1H),
1
3
.53(s, 1H), 6.43(s, 1H), 4.70(s, 2H), 4.31(q, J = 6.9 Hz, 2H), 1.34(d, J = 6.9 Hz, 3H). C NMR (75 MHz,
CDCl ): δ 158.9, 138.8, 136.4, 132.8, 132.7, 132.1, 130.1, 128.8, 127.2, 127.0, 126.5, 125.7, 123.5, 122.1, 120.4,
3
1
0

+
1
5
20.1, 119.8, 115.4, 114.2, 112.1, 65.5, 61.7, 14.3. UPLC MS (EI) Calcd. for C H N O BF [M + H] :
29 25 3 3 2
12.1952, found 512.1954.
1
1

1
13
3
. Copies of H NMR and C NMR spectra for all new compounds
1
H NMR compound 4 in CDCl3
1
2

1
3
C NMR of compound 4 in CDCl3
1
3

1
H NMR compound 3aa in CDCl3
1
4

1
3
C NMR of compound 3aa in CDCl3
1
5

1
6

1
H NMR compound 3ab in CDCl3
1
7

1
3
C NMR of compound 3ab in CDCl3
1
8

1
H NMR compound 3ac in CDCl3
1
9

1
3
C NMR of compound 3ac in CDCl3
2
0

2
1

1
H NMR compound 3ad in CDCl3
2
2

1
3
C NMR of compound 3ad in CDCl3
2
3

2
4

1
H NMR compound 3ae in CDCl3
2
5

1
3
C NMR of compound 3ae in CDCl3
2
6

2
7

1
H NMR compound 3ba in CDCl3
2
8

1
3
C NMR of compound 3ba in CDCl3
2
9