added DMF (20 mL). The reaction mixture was stirred at 90 ꢁC
for 12 h. After cooling, the reaction was quenched by adding
methanol and KF(aq) (saturated 15 mL). The mixture was
extracted with dichloromethane and the organic layer dried over
anhydrous MgSO4. Evaporation of the solvent gave the crude,
which was purified by silica gel with dichloromethane/hexane (1/
5) as eluent. Yellow solid of 3-C1 was obtained in 64% yield (1.64
g, 3.08 mmol). dH (400 MHz, CDCl3) 9.79 (s, 1H), 7.96 (d, 1H,
J ¼ 8.4 Hz), 7.90 (d, 1H, J ¼ 8.4 Hz), 7.79 (d, 1H, J ¼ 8.0 Hz),
7.65 (dd, 1H, J ¼ 1.6, 8.4 Hz), 7.63 (d, 1H, J ¼ 1.6 Hz), 7.45–7.51
(m, 2H), 7.20–7.37 (m, 8H), 7.03–7.10 (m, 4H), 6.97 (t, 1H, J ¼
7.2 Hz), 6.84 (d, 2H, J ¼ 8.4 Hz), 3.41 (s, 3H); dC (100 MHz,
CDCl3) 189.9, 150.7, 148.0, 147.7, 143.1, 142.4, 136.2, 135.2,
132.2, 131.1, 130.9, 130.4, 129.1, 128.3, 127.8, 127.2, 126.9, 126.5,
126.4, 126.3, 126.1, 125.5, 124.9, 124.1, 123.5, 122.7, 122.1, 121.9,
121.5, 114.8, 113.5, 35.7; m/z (FAB) 535.1844 ((M + H)+,
C36H27ON2S requires 535.1844).
6.74 (d, 1H, J ¼ 8.4 Hz), 3.77 (t, 2H, J ¼ 7.1 Hz), 1.71–1.78
(m, 2H), 1.39–1.42 (m, 2H), 1.25–1.29 (m, 4H), 0.85 (t, 3H, J ¼
6.4 Hz); dC (100 MHz, CDCl3) 189.7, 150.0, 147.8, 143.2, 143.0,
142.1, 140.7, 135.2, 131.1, 130.9, 130.1, 130.0, 129.1, 128.4, 128.2,
127.2, 126.6, 126.4, 126.3, 126.2, 126.1, 124.5, 124.1, 124.0, 124.0,
123.4, 122.8, 122.3, 122.2, 121.2, 115.9, 114.5, 47.9, 31.3, 26.5,
26.4, 22.5, 13.9; m/z (FAB) 686.2424 (M+, C45H38ON2S2 requires
686.2426).
7-(5-(p-(Naphthylphenylamino)phenyl)thiophen-2-yl)-N-(p-
ditolylaminophenyl)phenothiazine-3-carbaldehyde (4-T)
Compound 4-T was synthesized according to the same procedure
as that of 4-C6, as yellow solid in 56% yield. dH (500 MHz,
CDCl3) 9.70 (s, 1H), 7.92 (d, 1H, J ¼ 8.5 Hz), 7.89 (d, 1H, J ¼ 8.5
Hz), 7.79 (d, 1H, J ¼ 8.0 Hz), 7.45–7.50 (m, 3H), 7.32–7.41 (m,
5H), 7.08–7.23 (m, 20H), 6.96–6.99 (m, 3H), 6.31 (d, 1H, J ¼
8.5 Hz), 6.24 (d, 1H, J ¼ 9.0 Hz), 2.35 (s, 6H); dC (125 MHz,
CDCl3) 189.6, 149.0, 148.7, 148.0, 144.5, 143.3, 143.1, 141.8,
140.8, 135.3, 133.8, 131.5, 131.1, 130.9, 130.8, 130.2, 130.1, 129.9,
128.4, 127.4, 127.3, 127.2, 126.6, 126.4, 126.3, 126.1, 125.5, 124.2,
124.1, 123.3, 123.2, 122.8, 122.4, 122.3, 122.2, 121.3, 119.6, 119.5,
116.7, 115.1, 20.9; m/z (FAB) 874.2926 ((M + H)+, C59H44ON3S2
requires 874.2926).
N-Hexyl-7-(p-(naphthylphenylamino)phenyl)phenothiazine-3-
carbaldehyde (3-C6)
Compound 3-C6 was synthesized according to the same proce-
dure as that of 3-C1, as yellow liquid in 62% yield. dH (400 MHz,
CDCl3) 9.77 (s, 1H), 7.94 (d, 1H, J ¼ 8.4 Hz), 7.89 (d, 1H, J ¼ 8.2
Hz), 7.78 (d, 1H, J ¼ 8.2 Hz), 7.62 (dd, 1H, J ¼ 1.6, 8.4 Hz), 7.57
(d, 1H, J ¼ 1.6 Hz), 7.44–7.50 (m, 2H), 7.19–7.38 (m, 8H), 7.02–
7.09 (m, 4H), 6.96 (t, 1H, J ¼ 7.2 Hz), 6.88 (d, 2H, J ¼ 8.4 Hz),
3.88 (t, 2H, J ¼ 7.2 Hz), 1.78–1.86 (m, 2H), 1.41–1.46 (m, 2H),
1.30–1.33 (m, 4H), 0.88 (t, 3H, J ¼ 6.8 Hz); dC (100 MHz, CDCl3)
189.9, 150.4, 148.0, 147.7, 143.2, 141.8, 136.2, 135.2, 132.3, 131.2,
130.9, 130.0, 129.1, 128.4, 127.2, 127.0, 126.6, 126.4, 126.3, 126.1,
125.4, 125.2, 124.4, 124.1, 123.9, 122.1, 122.0, 121.5, 116.0, 114.5,
48.0, 31.3, 26.6, 26.4, 22.5, 13.9; m/z (FAB) 605.2627 ((M + H)+,
C41H37ON2S requires 605.2626).
N-Hexyl-5-(3-(p-(naphthylphenylamino)phenyl)phenothiazin-7-yl)
thiophene-2-carbaldehyde (5-C6)
Compound 5-C6 was synthesized from 1-C6 and p-(tributyl-
stannyl)phenylnaphthylphenylamine according to the same
procedure as that of 3-C1, as yellow liquid in 38% yield of 2 steps.
dH (400 MHz, CDCl3) 9.83 (s, 1H), 7.96 (d, 1H, J ¼ 8.4 Hz), 7.87
(d, 1H, J ¼ 8.4 Hz), 7.77 (d, 1H, J ¼ 8.4 Hz), 7.66 (d, 1H, J ¼
3.9 Hz), 7.18–7.49 (m, 13H), 7.02–7.08 (m, 4H), 6.95 (t, 1H, J ¼
7.3 Hz), 6.81–6.87 (m, 2H), 3.84 (t, 2H, J ¼ 7.2 Hz), 1.79–1.82
(m, 2H), 1.42–1.46 (m, 2H), 1.30–1.32 (m, 4H), 0.87 (t, 3H, J ¼
4.5 Hz); dC (100 MHz, CDCl3) 182.5, 153.6, 148.1, 147.6, 146.1,
143.3, 142.8, 141.5, 137.6, 135.6, 135.3, 132.6, 131.2, 129.1, 128.4,
127.3, 127.2, 127.0, 126.6, 126.4, 126.3, 126.2, 125.6, 125.5, 125.2,
125.1, 124.9, 124.2, 123.9, 123.0, 122.1, 121.9, 121.7, 115.6, 115.3,
47.7, 31.4, 26.7, 26.6, 22.6, 14.0; m/z (FAB) 686.2426
(M+, C45H38ON2S2 requires 686.2426).
7-(p-(Naphthylphenylamino)phenyl)-N-(p-ditolylaminophenyl)
phenothiazine-3-carbaldehyde (3-T)
Compound 3-T was synthesized according to the same procedure
as that of 3-C1, as yellow solids in 60% yield. dH (400 MHz,
CDCl3) 9.69 (s, 1H), 7.93 (d, 1H, J ¼ 8.4 Hz), 7.88 (d, 1H, J ¼ 8.2
Hz), 7.78 (d, 1H, J ¼ 8.2 Hz), 7.44–7.50 (m, 3H), 7.28–7.38 (m,
5H), 7.00–7.23 (m, 20H), 6.95 (t, 1H, J ¼ 7.3 Hz), 6.29 (t, 2H, J ¼
8.7 Hz), 2.34 (s, 6H); dC (100 MHz, CDCl3) 189.6, 149.3, 148.6,
148.0, 147.7, 144.5, 143.2, 141.4, 136.1, 135.2, 133.7, 132.2, 131.6,
131.2, 130.9, 130.8, 130.2, 129.9, 129.1, 128.4, 127.4, 127.2,
126.89, 126.6, 126.4, 126.3, 126.1, 125.5, 124.9, 124.4, 124.1,
122.2, 122.1, 122.0, 121.5, 119.7, 119.3, 116.7, 115.0, 20.8; m/z
(FAB) 792.3049 ((M + H)+, C55H42ON3S requires 792.3048).
5-(3-(p-(Naphthylphenylamino)phenyl)-N-(p-ditolylaminophenyl)
phenothiazin-7-yl)thiophene-2-carbaldehyde (5-T)
Compound 5-T was synthesized from 1-T according to the same
procedure as that of 5-C6, as yellow liquid in 58% yield. dH (400
MHz, CDCl3) 9.82 (s, 1H), 7.94 (d, 1H, J ¼ 8.5 Hz), 7.88 (d, 1H,
J ¼ 8.2 Hz), 7.77 (d, 1H, J ¼ 8.2 Hz), 7.66 (d, 1H, J ¼ 3.9 Hz),
7.44–7.49 (m, 2H), 7.33 (t, 2H, J ¼ 7.2 Hz), 7.29 (d, 2H, J ¼
8.6 Hz), 7.32–7.41 (m, 5H), 7.01–7.26 (m, 18H), 6.95 (t, 1H, J ¼
7.4 Hz), 6.29 (t, 2H, J ¼ 9.1 Hz), 2.34 (s, 6H); dC (100 MHz,
CDCl3) 182.5, 153.6, 148.5, 148.1, 147.6, 145.4, 144.7, 143.3,
142.3, 141.3, 137.6, 135.5, 135.3, 133.6, 132.5, 132.1, 131.2, 131.1,
130.2, 129.1, 128.4, 127.3, 127.0, 126.8, 126.6, 126.5, 126.4, 126.2,
125.5, 125.2, 125.0, 124.4, 124.2, 124.1, 122.8, 122.5, 122.1, 121.9,
120.2, 119.1, 116.2, 115.8, 20.9; m/z (FAB) 874.2926 ((M + H)+,
C59H44ON3S2 requires 874.2926).
N-Hexyl-7-(5-(p-(naphthylphenylamino)phenyl)thiophen-2-yl)
phenothiazine-3-carbaldehyde (4-C6)
Compound 4-C6 was synthesized from 1-C6 and p-(5-(tributyl-
stannyl)thiophen-2-yl)phenylnaphthylphenylamine according to
the same procedure as that of 3-C1, as yellow liquid in 89% yield.
dH (400 MHz, CDCl3) 9.72 (s, 1H), 7.92 (d, 1H, J ¼ 8.4 Hz), 7.85
(d, 1H, J ¼ 8.4 Hz), 7.74 (d, 1H, J ¼ 8.2 Hz), 7.55 (d, 1H, J ¼ 8.5
Hz), 7.52 (s, 1H), 7.20–7.45 (m, 8H), 7.18 (t, 2H, J ¼ 7.9 Hz),
7.06–7.07 (m, 4H), 6.92–6.97 (m, 3H), 6.79 (d, 1H, J ¼ 8.4 Hz),
4042 | J. Mater. Chem., 2012, 22, 4040–4049
This journal is ª The Royal Society of Chemistry 2012