184
H. Dinçalp et al. / Dyes and Pigments 91 (2011) 182e191
1,7-Dibromo-perylene-3,4,9,10-tetracarboxylic dianhydride (I)
2.2.4. Synthesis of 3-(4-bromo-5-methyl-thien-2-yl)-2-
cyanoacrylic acid (T2)
Following the published procedure [30],
compound T1 (0.1 g, 0.49 mmol), cyanoacetic acid (54 mg,
0.63 mmol), piperidine (10 L, 0.1 mmol), and MeeCN (10 mL)
and N,N0-bis(2,6-diisopropylphenyl)-1,7-dibromoperylene-3,4,9,10-
tetracarboxylic diimide (II) were synthesized according to literature
[26]. N-bromosuccinimide (NBS), benzoyl peroxide, piperidine, NaBH4,
triethylamine, propionic acid, DMF, t-BuOH, I2 and NH4Br were
obtained from Merck Company. Bis(pinacolato)diboron, P(t-Bu)3,
tris(dibenzylideneacetone)dipalladium(0) [Pd2(dba)3], K2CO3, 5-
methyl-2-thiophenecarboxaldehyde, 6-undecanone and 2,6-diiso-
propyl aniline were purchased from Aldrich. 4-iodoaniline, imidazole,
perylene-3,4,9,10-tetracarboxylic acid dianhydride were purchased
from Acros Organics. Cyanoacetic acid (from Alfa Aesar), bromine
(Carlo Erba) and 2-aminonicotinic acid (from ABCR GmbH) were used
as received. Other chemical reagents and organic solvents were
analytical grade and used without further purification.
a
mixture of
m
was refluxed for 10 h. The crude product was crystallized from
the solvent. The product was obtained as yellowish crystals.
C9H6BrNO2S, Yield: 90%, FT-IR (NaCl disc, cmꢁ1): 3431 (carbox-
ylic acid OeH stretching), 2949 (aliphatic nCeH), 2841 (aliphatic
nCeH), 2808 (aliphatic nCeH), 2215 (nC]N), 1742 (nC]O), 1599 (nC]
C), 1514 (aromatic nC]C), 1458, 1342, 1240 (nCeO), 1150, 999, 830,
775 cmꢁ1
s), 8.05 (1H, s), 7.34 (1H, s), 2.44 (3H, s) ppm. 13C NMR [100 MHz,
CDCl3, 77.0 ppm (3 peaks)]: 173.1 (C]O), 140.4, 130.0, 108.7,
.
1H NMR (400 MHz, CDCl3,
d
7.26 ppm):
d
¼ 8.74 (1H,
d
Solvent dependent kinetics and photophysical properties of dyes
IIIeVII were investigated in four different solvents of increasing
101.8, 88.7, 87.5, 84.5, 15.8 ppm.
polarities including toluene (
3
¼ 2.4), chloroform (
3
¼ 4.8), ethanol
2.2.5. Synthesis of 3-[4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-
yl)-5-methyl-thien-2-yl]-2-cyanoacrylic acid (T3)
(3
¼ 24.6) and benzonitrile ( ¼ 26.0) [27].
3
Following the published procedure [31], compound T2
2.2. Synthesis
(50 mg, 0.18 mmol), triethylamine (25
colato)diboron (53 mg, 0.21 mmol), tris(dibenzylideneacetone)
dipalladium(0) [Pd2(dba)3] [(21.8 mM in toluene), 211 L,
4.6 mol], P(t-Bu)3 [(0.4 M in toluene), 11.5 L, 4.6 mol], and
mL, 0.18 mmol), Bis(pina-
2.2.1. Preparation of [(t-Bu)3PH]BF4
Title compound was prepared according to a literature proce-
dure [28]. HBF4 [(48% aqueous solution), 185 L, 1.40 mmol] was
m
m
m
m
m
2 mL of anhydrous THF were placed in a Schlenk tube. The
solution was stirred at 40 ꢀC under argon atmosphere for 6 h.
The reaction progress was controlled by TLC. The reaction
mixture was then cooled to room temperature and diluted with
methylene chloride. Black particles were removed by filtration.
The organic solvent was removed at reduced pressure. Pure
sample was obtained by column chromatography on silica gel
using chloroform:methanol (35:15) as eluent. C15H18BNO4S,
Yield: 75%, FT-IR (NaCl disc, cmꢁ1): 3444 (carboxylic acid OeH
stretching), 2923 (aliphatic nCeH), 2852 (aliphatic nCeH), 2252
poured into a solution of P(t-Bu)3 [(0.4 M in toluene), 0.5 mL,
0.20 mmol] in 5 mL of methylene chloride at room temperature.
The resulting mixture was stirred vigorously for 5 min. Then,
organic layer was dried over magnesium sulfate, and concentrated
under vacuum. The white product was obtained. C12H28BF4P, Yield:
95%, FT-IR (KBr pellet, cmꢁ1): 2957 (aliphatic nCeH), 2873 (aliphatic
nCeH), 2300 (nPeH), 1476, 1395, 1370, 1247, 1104 (nBeF), 1020 (nBeF),
942, 811, 674, 640 cmꢁ1
.
2.2.2. Preparation of 6-undecanol
(
nC]N), 1714 (nC]O), 1609 (nC]C), 1565 (aromatic nC]C), 1418,
1384 (nBeO), 1151 (nCeO), 1093, 888, 704 cmꢁ1. 1H NMR (400 MHz,
CDCl3, 7.25 ppm):
¼ 8.19 (1H, s), 7.65 (1H, s), 2.52 (3H, s), 1.25
(12H, s) ppm. 13C NMR [100 MHz, CDCl3,
77.0 ppm (3 peaks)]:
50 mL of 1.2 N NaBH4 (60 mmol) solution in ethanol was slowly
added to a solution containing 6-undecanone (2.4 mL, 11.7 mmol)
in 100 mL of ethanol at room temperature. The solution was stirred
for 1 h. Then, the 50 mL of saturated NH4Br solution was poured
into the reaction mixture. The resulting solution was stirred for 1 h,
and then extracted with ethyl acetate. White powder was obtained
after concentration of the solution under vacuum. C11H24O, Yield:
90%, FT-IR (KBr pellet, cmꢁ1): 3334 (OeH stretching), 2957
(aliphatic nCeH), 2930 (aliphatic nCeH), 2859 (aliphatic nCeH), 1468,
d
d
d
173.2 (C]O), 147.3, 137.4, 125.7, 111.5, 110.0, 107.6, 106.3, 75.3,
29.2, 25.0 ppm.
2.2.6. Synthesis of 3-[4-(4-aminophenyl)-5-methyl-thien-2-yl]-2-
cyanoacrylic acid (T4)
Following the published procedure [32], a Schlenk tube was
charged, in no specific order, with compound T3 (41 mg,
0.13 mmol), sodium fluoride (16 mg, 0.38 mmol), 4-iodoaniline
(28 mg, 0.13 mmol), potassium carbonate (106 mg, 0.77 mmol),
1423, 1395, 1329 (OeH bending), 1134 (nCeO), 1075, 909 cmꢁ1 1H
.
NMR (400 MHz, CDCl3,
d
7.25 ppm):
d
¼ 4.08 (1H, s), 3.59 (1H, s),
1.29 (16H, m), 0.87 (6H, t, J ¼ 7.0 Hz) ppm. 13C NMR [100 MHz,
CDCl3,
d
77.0 ppm (3 peaks)]: 72.1, 37.6, 32.1, 25.5, 22.8, 14.2 ppm.
Pd2(dba)3 [(21.8 mM in toluene), 89
mL, 1.9 mmol], [(t-Bu)3PH]BF4
[(23.4 mM in toluene), 186 L, 4.4 mol], and 1 mL of anhydrous
m
m
2.2.3. Synthesis of 4-bromo-5-methyl-2-thiophenecarboxaldehyde
(T1)
Following the published procedure [29], N-bromosuccinimide
(1.19 g, 6.69 mmol) and benzoyl peroxide (16.2 mg, 66.9 mmol) were
dissolved in 5 mL of acetic acid, and 5-methyl-2-thiophenecarbox-
aldehyde (0.7 mL, 6.5 mmol) was added slowly. The solution
was stirred at 70 ꢀC for 7 h and extracted with dichloromethane.
The combined organic layers were extracted with 1 M NaOH solu-
tion, washed with brine, dried over magnesium sulfate, and
concentrated under vacuum. The reaction mixture was purified by
column chromatography by using n-hexane:ethyl acetate (40:10).
C6H5BrOS, Yield: 70%, FT-IR (KBr pellet, cmꢁ1): 2920, 2855, 1673
THF. The mixture was stirred at room temperature under argon
atmosphere for 3 h. The reaction progress was controlled by TLC.
The reaction mixture was diluted with diethyl ether. Black
particles were removed by filtration. The organic layer was
evaporated to afford the crude product. The crude product was
purified by column chromatography on silica gel using n-hex-
ane:ethyl acetate (40:10) as eluent. C15H12N2O2S, Yield: 50%, FT-IR
(NaCl disc, cmꢁ1): 3420 (carboxylic acid OeH stretching), 3215
(NeH stretching), 2924 (aliphatic nCeH), 2857 (aliphatic nCeH),
2218 (nC]N), 1734 (nC]O), 1653 (NeH bending), 1619 (nC]C), 1496
(aromatic nC]C), 1448, 1367, 1339, 1183
(
nCeO), 1096, 979,
¼ 7.76 (1H, s),
875 cmꢁ1. 1H NMR (400 MHz, CDCl3,
d
7.25 ppm):
d
(
nC]O), 1520 (aromatic nC]C), 1450, 1384, 1307, 1223, 1133, 838, 798,
684, 485 cmꢁ1. 1H NMR (400 MHz, CDCl3,
7.26 ppm):
¼ 9.77 (1H,
s), 7.58 (1H, s), 2.49 (3H, s) ppm. 13C NMR [100 MHz, CDCl3,
77.0 ppm (3 peaks)]: 181.7 (C]O), 145.9, 140.3, 138.8, 111.4,
16.0 ppm.
7.72 (1H, s), 7.62 (2H, d, J ¼ 7.4 Hz, benzene H), 7.52 (2H, s), 7.40
d
d
(2H, d, J ¼ 7.4 Hz, benzene H), 7.10 (1H, s), 3.00 (3H, s) ppm. 13C
NMR [100 MHz, CDCl3,
d 77.0 ppm (3 peaks)]: 175.2 (C]O), 147.6,
d
141.9, 139.4, 138.0, 137.9, 132.8, 129.1, 126.3, 123.6, 114.5, 109.9,
12.0 ppm.