K.R. Justin Thomas et al. / Dyes and Pigments 91 (2011) 33e43
35
35.0, 34.9, 30.8, 30.7. FAB MS: m/z 589.2 [Mþ]. HRMS: Calcd. for
reaction was quenched by cooling to room temperature and
subsequently 20 ml methanol added to induce precipitation of the
product. The yellow solid thus obtained was dissolved in
dichloromethane and adsorbed with silica gel. It was purified by
column chromatography using hexane/dichloromethane mixture
(3:2) as eluant. Dark yellow solid. Yield: 1.04 g (74%). 1H NMR
C42H39NS 589.2803. Found: 589.2791 [Mþ].
2.4. 5-(2,6-Di-tert-butyl-10-(naphthalen-1-yl(phenyl)amino)
anthracen-9-yl)thiophene-2-carbaldehyde (4)
Compound 3 (1.18 g, 2 mmol) was dissolved in dry tetrahydro-
furan (50 ml) and cooled to ꢂ70 ꢁC. To this mixture n-butyl lithium
(1.4 ml (1.6 M solution in n-hexane) 2.2 mmol) was added drop by
drop for 30 min with vigorous stirring. The reaction mixture was
stirred for another 90 min at this temperature and 2 ml dry dime-
thylformamide added at once. It was allowed to attain room
temperature overnight. The resulting yellow solution was poured
into ice-water and treated with saturated ammonium chloride
solution briefly. It was extracted with diethyl ether (3 ꢀ 25 ml) and
the combined organic extracts dried over anhydrous MgSO4.
Evaporation of the diethyl ether solution produced the crude
aldehyde which was further purified by column chromatography
on silica gel using 1:1 mixture of hexane and dichloromethane.
Dark yellow solid. Yield: 0.67 g (54%). 1H NMR (CDCl3, 500 MHz,
(CDCl3, 500 MHz, ppm): d 1.10 (s, 9 H), 1.31 (s, 9 H), 6.70e6.74 (m,
2 H), 6.84 (t, J ¼ 8.2 Hz, 1 H), 7.05e7.14 (m, 3 H), 7.18e7.27 (m, 2 H),
7.35 (d, J ¼ 4.0 Hz, 1 H), 7.40e7.56 (m, 4 H), 7.60e7.64 (m, 2 H), 7.71
(d, J ¼ 4.0 Hz, 1 H), 7.88e7.98 (m, 3 H), 8.21e8.26 (m, 2 H0, 8.32
(d, J ¼ 8.2 Hz, 1 H), 9.92 (s, 1 H). 13C NMR (CDCl3, 125 MHz, ppm):
d
182.5, 150.7, 148.4, 148.0, 147.7, 147.2, 142.8, 141.8, 141.6, 140.8,
137.4, 137.2, 135.2, 132.4, 131.5, 130.8, 130.3, 129.7, 129.0, 129.0,
128.3, 126.4, 126.3, 126.28, 126.1, 125.9, 125.8, 125.7, 125.6, 125.3,
125.1, 124.4, 124.2, 123.7, 123.2, 123.0, 121.0, 119.8, 119.4, 118.6, 35.0,
30.7. FAB MS: m/z 699.2 [Mþ]. HRMS: Calcd. for C47H41ONS2:
699.2630. Found: 699.2629 [Mþ].
2.7. (E)-2-Cyano-3-(50-(2,6-di-tert-butyl-10-(naphthalen-1-yl
(phenyl)amino)anthracen-9-yl)-2,20-bithiophen-5-yl)acrylic
acid (7)
ppm):
d 1.12 (s, 9 H), 1.31 (s, 9 H), 6.72e6.77 (m, 2 H), 6.84 (t,
J ¼ 7.4 Hz, 1 H), 7.11e7.27 (m, 5H), 7.37 (d, J ¼ 4.0 Hz, 1 H), 7.43e7.54
(m, 4 H), 7.62 (d, J ¼ 8.2 Hz,1 H), 7.75e7.85 (m, 2 H), 7.94 (dd, J ¼ 1.8,
9.2 Hz, 1H), 8.01 (d, J ¼ 4.0 Hz, 1 H), 8.25e8.32 (m, 2 H), 8.35
(d, J ¼ 8.2 Hz, 1 H), 10.08 (s, 1 H). 13C NMR (CDCl3, 125 MHz, ppm):
The title dye was prepared from the aldehyde 6 by following the
procedure described above for 5. Red solid. Yield: 77%. 1H NMR
(DMSO-d6, 500 MHz, ppm):
d 0.95 (s, 9 H), 1.17 (s, 9 H), 6.49
d
182.9, 150.7, 148.5, 148.3, 144.8, 136.5, 131.1, 131.0, 129.1, 129.0,
(d, J ¼ 7.4 Hz, 1 H), 6.56 (d, J ¼ 7.4 Hz, 1 H), 6.75e6.79 (m, 1 H), 6.96
(d, J ¼ 7.4 Hz,1 H), 7.03e7.07 (m, 2 H), 7.21 (t, J ¼ 7.4 Hz,1 H), 7.35 (d,
J ¼ 1.8 Hz, 1 H), 7.45e7.67 (m, 6 H), 7.79e7.82 (m, 3 H), 7.96e7.98
(m, 2 H), 8.07e8.14 (m, 3 H), 8.51 (s, 1 H). 13C NMR (DMSO-d6,
128.9, 126.1, 126.0, 125.9, 125.8, 125.7, 125.6, 125.1, 124.5, 123.0,
120.6, 119.9, 119.5, 118.6, 115.3, 35.0, 30.7.
2.5. (E)-2-Cyano-3-(5-(2,6-di-tert-butyl-10-(naphthalen-1-yl
125 MHz, ppm): d 164.0, 150.7, 148.9, 148.4, 146.6, 145.5, 142.6,
(phenyl)amino)anthracen-9-yl)thiophen-2-yl)acrylic acid (5)
141.5, 140.8, 140.7, 137.0, 135.3, 134.7, 132.2, 132.17, 131.3, 129.8,
129.6, 129.5, 128.7, 127.9, 127.7, 126.8, 126.4, 126.3, 125.73, 125.66,
125.2, 124.4, 122.9, 120.9, 120.5, 119.0, 118.5, 117.0, 99.2, 35.1, 30.8,
30.7. FAB MS: m/z 766.3 [Mþ]. HRMS: Calcd. for C50H42O2N2S2:
766.2688. Found: 766.2693 [Mþ].
A mixture of the aldehyde 4 (0.618 g, 1 mmol), 2-cyanoacetic
acid (0.102 g, 1.2 mmol), ammonium acetate (0.039 g, 0.5 mmol)
and acetic acid (5 ml) was refluxed for 8 h. The resulting dark red
solution was poured into water. The solid was filtered and thor-
oughly washed with water and hexane/diethyl ether mixture. It
was recrystallized from dichloromethane/hexane mixture. Red
powder. Yield: 0.47 g (69%). 1H NMR (DMSO-d6, 500 MHz, ppm):
2.8. 5-(7-(5-(2,6-Di-tert-butyl-10-(naphthalen-1-yl(phenyl)amino)
anthracen-9-yl)thiophen-2-yl)benzo[c][1,2,5]thiadiazol-4-yl)
thiophene-2-carbaldehyde (8)
d
0.99 (s, 9 H), 1.21 (s, 9 H), 6.51 (d, J ¼ 7.6 Hz,1 H), 6.58 (d, J ¼ 7.6 Hz,
1 H), 6.82 (t, 7.4 Hz, 1 H), 6.96 (d, J ¼ 7.4 Hz, 1 H), 7.09e7.14 (m, 2 H),
7.29 (t, 7.4 Hz, 1 H), 7.52-7.73 (m, 8 H), 8.02 (d, J ¼ 8.2 Hz, 1 H),
8.08e8.18 (m, 3 H), 8.38 (d, J ¼ 4.0 Hz, 1 H), 8.69 (s, 1 H). 13C NMR
It was obtained in 72% yield as described above for the aldehyde
6, but 5-(7-bromobenzo[c][1,2,5]thiadiazol-4-yl)thiophene-2-car-
baldehyde was used instead of 5-bromothiophene-2-carbaldehyde.
(DMSO-d6, 125 MHz, ppm):
d
162.5, 149.3, 147.6, 147.4, 147.2, 145.8,
Orange solid. 1H NMR (CDCl3, 500 MHz, ppm):
d 1.09 (s, 9 H), 1.29
141.3, 139.7, 139.3, 136.3, 134.0, 130.8, 130.5, 129.7, 128.5, 128.3,
128.1, 127.3, 126.6, 125.4, 125.1,124.6,124.4,123.9, 123.1, 121.6, 119.3,
117.7, 117.3, 115.6, 99.0, 33.8, 29.5, 29.4. FAB MS: m/z 684.2 [Mþ].
HRMS: Calcd for C46H40O2N2S: 684.2811. Found: 684.2811 [Mþ].
(s, 9 H), 6.70e6.74 (m, 2 H), 6.83 (t, J ¼ 7.4 Hz, 1 H), 7.09e7.27
(m, 4 H), 7.33e7.56 (m, 5 H), 7.63 (d, J ¼ 8.2 Hz, 1 H), 7.85
(d, J ¼ 4.0 Hz, 1 H), 7.92e8.06 (m, 5 H), 8.21e8.25 (m, 3 H), 8.33
(d, J ¼ 8.2 Hz, 1 H), 8.49 (d, J ¼ 4.0 Hz, 1 H), 10.0 (s, 1 H). 13C NMR
(CDCl3, 125 MHz, ppm):
d 183.0, 152.5, 152.45, 150.8, 148.7, 148.4,
2.6. 50-(2,6-Di-tert-butyl-10-(naphthalen-1-yl(phenyl)amino)
anthracen-9-yl)-2,20-bithiophene-5-carbaldehyde (6)
147.9, 143.4, 142.9, 142.3, 140.6, 140.1, 136.8, 135.2, 132.5, 131.6,
130.9, 129.7, 129.0, 128.98, 128.8, 128.3, 128.0, 127.9, 127.5, 127.1,
126.7, 126.2, 125.9, 125.8, 125.7, 125.2, 125.0, 124.9, 124.4, 124.3,
123.0, 121.3, 119.8, 119.4, 118.6, 35.0, 30.8. FAB MS: m/z 833.3 [Mþ].
HRMS: Calcd. for C53H43ON3S3: 833.2568. Found: 833.2575 [Mþ].
A tetrahydrofuran (50 ml) solution of compound 3 (1.17 g,
2.0 mmol) was cooled to ꢂ70 ꢁC and n-butyl lithium (1.4 ml (1.6 M
solution in n-hexane) 2.2 mmol) was added dropwise for 15 min
with vigorous stirring. The reaction mixture was stirred for another
60 min at this temperature and 0.72 g (2.2 mmol) of tributyl-
chlorostannane added at once. The resulting solution was allowed
to attain room temperature overnight. It was quenched by the
addition of ice-cold water and extracted with diethyl ether
(3 ꢀ 30 ml). The combined organic extracts was dried over anhy-
drous MgSO4 and evaporated to yield orange syrup.
2.9. (E)-2-Cyano-3-(5-(7-(5-(2,6-di-tert-butyl-10-(naphthalen-1-
yl(phenyl)amino)anthracen-9-yl)thiophen-2-yl)benzo[c][1,2,5]
thiadiazol-4-yl)thiophen-2-yl)acrylic acid (9)
It was prepared in 63% yield from the aldehyde 8 by following
a procedure similar to 5. Dark red solid. 1H NMR (DMSO-d6,
500 MHz, ppm):
d
0.98 (s, 9 H), 1.18 (s, 9 H), 6.52 (d, J ¼ 7.4 Hz,
The above syrup was mixed with 5-bromothiophene-2-carbal-
dehyde (0.38 g, 2.0 mmol), Pd(PPh3)2Cl2 (0.014 g, 0.02 mmol)
and dimethylformamide (10 ml) and heated at 70 ꢁC for 24 h. The
1 H), 6.59 (d, J ¼ 7.4 Hz, 1 H), 6.80 (t, J ¼ 7.4 Hz, 1 H), 6.98e7.12 (m,
3 H), 7.26e7.29 (m, 1 H), 7.47e7.57 (m, 5 H), 7.71 (d, J ¼ 4.0 Hz, 1 H),
7.85e7.89 (m, 2 H), 8.00e8.31 (m, 8 H), 8.45e8.53 (m, 2 H). 13C NMR