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extracted three times using chloroform and water. The or-
ganic layer was separated and dried with anhydrous magne-
sium sulfate, and then the solvent was removed using a ro-
tary evaporator. The crude product was purified by column
chromatography using chloroform as the eluent. The product
yield was 20.4 g (88.5%). 1H NMR (300 MHz, CDCl3, d)
7.31–7.28 (d, 2H), 7.11–7.08 (d, 2H), 6.99–6.96 (m, 2H),
6.85–6.74 (m, 4H), 6.19–6.16 (m, 2H), 3.88 (s, 3H). 13C NMR
(CDCl3, 80 MHz, d) 159.46, 144.98, 133.58, 132.49, 127.03,
126.83, 122.46, 119.86, 116.10, 115.85, 55.75. Anal. Calcd.
for C19H15NOS: C, 74.77; H, 4.91; N, 4.57; O, 5.24; S, 10.50.
Found: C, 74.72; H, 4.95; N, 4.59; O, 5.24; S, 10.50.
under N2 conditions. A solution of TiCl4 (1.16 mL, 5.3 mmol)
was added carefully to the suspension with stirring at ꢁ40
ꢂC for 30 min, and then the suspension was heated to reflux
at 80 ꢂC for 12 h. After cooling to room temperature, satu-
rated aqueous NaHCO3 (200 mL) was added, and the reac-
tion mixture was stirred for a further 1 h. The reaction mix-
ture was extracted with chloroform, and the combined
organic layer was dried over anhydrous magnesium sulfate,
filtered, and concentrated under reduced pressure. The resi-
due was purified using flash chromatography on silica gel
(chloroform:n-hexane (1:2 [v/v]) to afford the crude product.
The crude product was precipitated in methanol with a yield
of 64% (1.8 g). 1H NMR (300 MHz, CDCl3, d): 7.26–7.24 (d,
4H), 7.11–7.06 (m, 8H), 6.89–6.84 (m, 4H), 6.67 (s, 2H),
6.10–6.07 (d, 2H), 6.00–5.97 (d, 2H), 3.89 (s, 3H). 13C NMR
(80 MHz, CDCl3, d): 159.49, 143.44, 143.24, 132.79, 132.12,
131.94, 129.43, 128.65, 125.49, 123.88, 121.46, 119.08,
116.81, 116.13, 115.76, 114.24, 55.58. Anal. Calcd. for
10-(4-Methoxyphenyl)-10H-phenothiazine-3-carbaldehyde
(2a)
Into a solution of compound 1a (15.0 g, 49.1 mmol) and an-
hydrous DMF (40.0 mL) in 250 mL of 1,1,2-trichloroethane
at 0 ꢂC was added, by syringe, 18.3 mL (196.4 mmꢂol) of
phosphorus oxychloride. The mixture was stirred at 0 C for
30 min, and then heated to 95 ꢂC and stirred for a further
3 h. The reaction mixture was extracted three times using
chloroform and brine. The organic layer was separated and
dried with anhydrous magnesium sulfate, and then the sol-
vent was removed using a rotary evaporator. The product
was precipitated in methanol. The product yield was 13.9 g
(85%). 1H NMR (300 MHz, CDCl3, d) 9.67 (s, 1H) 7.44 (s,
1H), 7.29–7.26 (d, 3H), 7.14–7.11 (d, 2H), 6.97–6.94 (m, 1H),
6.84–6.81 (m, 2H), 6.20–6.13 (m, 2H), 3.90 (s, 3H). 13C NMR
(CDCl3, 80 MHz, d) 189.72, 159.67, 149.56, 142.88, 132.34,
131.72, 130.93, 129.90, 127.45, 127.11, 126.64, 123.56,
120.05, 118.99, 116.41, 116.25, 114.99, 55.59. Anal. Calcd.
for C20H15NO2S : C, 72.05; H, 4.55; N, 4.25; O, 9.67; S, 9.69.
Found: C, 72.05; H, 4.53; N, 4.20; O, 9.60; S, 9.62.
C40H28Br2N2O2S2: C, 60.64; H, 3.54; N, 3.51; O, 4.13; S, 8.06.
Found: C, 60.61; H, 3.56; N, 3.53; O, 4.04; S, 8.09.
10-(4-Methoxyphenyl)-3-((E)-2-(10-(4-methoxyphenyl)-
3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-10H-
phenothiazin-7-yl)vinyl)-7-(4,4,5,5-tetramethyl-
1,3,2-dioxaborolan-2-yl)-10H-phenothiazine (5a)
To a solution of compound 4a (0.5 g, 0.63 mmol) in anhy-
drous THF (50 mL) at ꢁ78 ꢂC, 0.66 mL (1.51 mmol) of n-
butyllithium (2.3 M in hexane) was added by syringe. The
ꢂ
mixture was stirred at ꢁ78 C for 2 h. 2-Isopropoxy-4,4,5,5,-
tetramethyl-1,3,2-dioxaborolane (3.34 mL, 1.64 mmol) was
added to the solution, and the resulting mixture was stirred
ꢂ
at ꢁ78 C for 1 h, warmed to room temperature, and stirred
for a further 12 h. The mixture was poured into water,
extracted with chloroform, and dried over anhydrous magne-
sium sulfate. The solvent was removed via rotary evapora-
tion, and the residue was purified by recrystallization with
acetone. The product was obtained as a yellow solid to give
0.33 g (58%). 1H NMR (CDCl3, 300 MHz, d): 7.38 (s, 2H),
7.27–7.24 (t, 5H), 7.21 (s, 1H), 7.12–7.09(d, 4H), 7.06 (s,
2H), 6.84–6.81 (d, 2H), 6.66 (s, 2H), 6.09–6.03 (m, 4H), 3.90
(s, 6H), 1.33–1.26 (s, 24H). 13C NMR (CDCl3, 80 MHz, d):
159.56, 146.64, 143.24, 133.96, 133.21, 132.32, 132.20,
125.67, 125.34, 123.97, 120.30, 118.51, 116.22, 115.97,
115.83, 115.00, 83.84, 55.75, 25.01. Anal. Calcd. for
7-Bromo-10-(4-methoxyphenyl)-10H-phenothiazine-3-
carbaldehyde (3a)
Compound 2a (6.9 g, 20.7 mmol) was dissolved in chloroform
(50 mL) and acetic acid (50 mL) cosolvent, and then N-bro-
mosuccinimide (3.75 g, 21.1 mmol) was added, and the solu-
tion was stirred for 1 h at 65 ꢂC. After the reaction was fin-
ished, the reaction mixture was extracted three times using
chloroform and brine. Organic layer was separated and dried
with anhydrous magnesium sulfate, and then the solvent was
removed using a rotary evaporator. The crude product was
precipitated in methanol. The product yield was 7.0 g (82%).
1H NMR (300 MHz, CDCl3, d): 9.67 (s, 1H), 7.40 (s, 1H), 7.29–
7.26 (m, 3H), 7.14–7.11 (d, 2H), 7.04 (s, 1H), 6.90–6.86 (m,
1H), 6.19–6.16 (d, 1H), 6.00–5.97 (d, 1H), 3.90 (s,3H). 13C
NMR (CDCl3, 80 MHz, d): 189.63, 159.82, 149.07, 142.15,
131.94, 131.51, 131.13, 130.09, 129.75, 128.74, 127.46,
121.21, 119.32, 117.58, 116.41, 115.73, 115.17, 55.61. Anal.
Calcd. for C20H14BrNO2S: C, 58.24; H, 3.43; N, 3.40; O, 7.87; S,
7.78. Found: C, 58.26; H, 3.42; N, 3.40; O, 7.76; S, 7.78.
C52H52B2N2O6S2: C, 70.23; H, 5.91; N, 3.16; S, 7.10. Found: C,
70.43; H, 5.91; N, 3.16; S, 7.23.
10-(4-(Dodecyloxy)phenyl)-3-((E)-2-(10-(4-(dodecyloxy)-
phenyl)-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-
10H-phenothiazin-7-yl)vinyl)-7-(4,4,5,5-tetramethyl-1,3,2-
dioxaborolan-2-yl)-10H-phenothiazine (5b)
To a solution of compound 4b (1.0 g, 0.91 mmol) in anhy-
drous THF (60 mL) at ꢁ78 ꢂC was added 1.12 mL (2.54
mmol) of n-butyllithium (2.3 M in hexane) by syringe. The
ꢂ
3-Bromo-7-((E)-2-(3-bromo-10-(4-methoxyphenyl)-
10H-phenothiazin-7-yl)vinyl)-10-(4-methoxyphenyl)-
10H-phenothiazine (4a)
Compound 3a (2.0 g, 3.53 mmol) and Zn powder (2.31 g,
35.3 mmol) was suspended in anhydrous THF (90 mL)
mixture was stirred at ꢁ78 C for 2 h. 2-Isopropoxy-4,4,5,5,-
tetramethyl-1,3,2-dioxaborolane (0.62 mL, 2.99 mmol) was
added to the solution, and the resulting mixture was stirred
ꢂ
at ꢁ78 C for 1 h, warmed to room temperature, and stirred
for a further 12 h. The mixture was poured into water,
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