Qu et al.
FULL PAPER
1
26.01, 130.33, 131.69, 144.17.
Preparation of 4,8-didodecyloxybenzo[1,2-b:4,5-
(400 MHz, CDCl
7.2 Hz, 6H, CH
3
) δ: 0.28 (s, 18H, SiMe
3
), 1.46 (t, J=
3
), 4.30 (q, J=7.2 Hz, 4H, CH
2H); C NMR (100 MHz, CDCl ) δ: 0.25 (SiMe
14.20 (CH ), 73.25 (OCH ), 97.89 (C≡C), 102.15 (C≡
2
), 7.58 (s,
13
b']dithiophene (3b) The procedure of 3b was similar
to that of 2b. Benzo[1,2-b:4,5-b']dithiophene-4,8-dione
3
3
),
3
2
(
200 mg, 0.91 mmol), zinc power (124 mg, 1.91 mmol),
C), 122.78, 124.90, 130.24, 130.96, 144.17.
n
sodium hydroxide (546 mg, 13.70 mmol), C12
(
water (15 mL). Yield: 356 mg (70%) of a light yellow
solid. H NMR (400 MHz, CDCl
6
4
5
H
25Br
Preparation of 2,6-bis(trimethylsilylethynyl)-4,8-
didodecyloxybenzo[1,2-b:4,5-b']dithiophene (3d)
The procedure of 3d was similar to that of 2d. 2,6-
Dibromo-4,8-didodecyloxybenzo[1,2-b:4,5-b']dithio-
phene (3c) (200 mg, 0.28 mmol), Pd(PPh ) (32 mg,
0.028 mmol), CuI (5 mg, 0.028 mmol), (trimethylsi-
lyl)acetylene (0.36 mL, 2.8 mmol), THF (20 mL), Et N
(15 mL). Yield: 168 mg (80%) of a white solid. H
n
683 mg, 2.73 mmol), Bu
4
NBr (30 mg, 0.091 mmol),
1
3
) δ: 0.88 (t, J=6.8 Hz,
), 1.15-1.40 (m, 36H, CH ), 1.81-1.89 (m,
), 4.28 (q, J=6.4 Hz, 4H, OCH ). 7.36 (d, J=
.6 Hz, 2H, thiophene-H), 7.48 (d, J=5.6 Hz, 2H,
H, CH
H, CH
3
2
3
4
2
2
3
1
3
1
thiophene-H); C NMR (100 MHz, CDCl
CH ), 22.73, 25.98, 29.39, 29.62, 29.65, 30.43, 31.91,
4.15 (OCH ), 114.98, 123.10, 130.87, 131.17, 142.52.
Preparation of 2,6-dibromo-4,8-diethoxybenzo-
1,2-b:4,5-b']dithiophene (2c) To a stirred solution of
,8-diethoxybenzo[1,2-b:4,5-b']dithiophene (2b) (216
mg, 0.78 mmol) in CH Cl (20 mL) under an argon at-
mosphere was added a CH Cl (10 mL) solution of
3
) δ: 14.15
(
7
3
NMR (400 MHz, CDCl ) δ: 0.29 (s, 18H, SiMe ), 0.88
3
3
2
3 2
(t, J=6.8 Hz, 6H, CH ), 1.10-1.42 (m, 32H, CH ),
1.46-1.52 (m, 4H, CH ), 1.82-1.87 (m, 4H, CH ),
2
2
[
4
2
4.21 (q, J=6.8 Hz, 4H, OCH ), 7.57 (s, 2H, thio-
1
3
phene-H); C NMR (100 MHz, CDCl ) δ: 0.25
3
2
2
(SiMe ), 14.14 (CH ), 22.69, 25.94, 29.42, 29.64, 30.45,
3
3
2
2
31.92, 74.14 (OCH ), 97.96 (C≡C), 101.63 (C≡C),
2
bromine (0.078 mL, 1.64 mmol) by a constant pressure
funnel under ice-bath, the mixture was reacted for 1-2
h at room temperature. The reaction mixture was ex-
tracted with diethyl ether three times and washed with
sodium hydrogen sulfite. The combined organic layer
was dried with anhydrous sodium sulfate. The filtrate
was evaporated under reduced pressure and purified by
122.82, 125.96, 130.17, 131.74, 143.81.
Preparation of bimetal ruthenium acetylide com-
plexes 1-3
Preparation of 1 A solution of Cp*(dppe)RuCl
(341 mg, 0.51 mmol), 2,6-bis(trimethylsilylethynyl)-
1,5-dithia-s-indacene-4,8-dione (1b) (100 mg, 0.24
silica gel column chromatography (CH
2
Cl
2
/petroleum
3
mmol), and KF (168 mg, 2.90 mmol) in 20 mL CH OH
ether, V∶V=1∶4) to give a white solid (152 mg, 45%).
and 5 mL THF was heated to reflux under nitrogen at-
mosphere for 24 h. The crude product was collected by
filtration, washed with methanol and hexane. The solid
was dissolved in dichloromethane and precipitated from
slow diffusion with hexane. The solid was filtered and
1
H NMR (400 MHz, CDCl
CH ), 4.28 (q, J=6.8 Hz, 4H, OCH
NMR (100 MHz, CDCl ) δ: 16.04 (CH
15.02, 123.12, 131.04, 131.37, 142.26.
Preparation of 2,6-dibromo-4,8-didodecyloxy-
3
) δ: 1.46 (t, J=7.2 Hz, 6H,
1
3
3
2
), 7.44 (s, 2H); C
), 69.68 (OCH ),
3
3
2
1
1
dried to give 1 as an atrovirens solid (216 mg, 55%). H
benzo[1,2-b:4,5-b']dithiophene (3c) The procedure
of 3c was similar to that of 2c. 4,8-Didodecyloxy-
benzo[1,2-b:4,5-b']dithiophene (3b) (2.20 g, 3.9 mmol),
3 5 3 5
NMR (400 MHz, CDCl ) δ: 1.54 (s, 30H, 2C (CH ) ),
2.07 (br, 4H, CH2/dppe), 2.63 (br, 4H, CH2/dppe), 6.65 (s,
2H), 7.20 - 7.37 (m, 32H, HAr/dppe), 7.66 (br, 8H,
1
3
Br
2
(8.2 mmol, 0.4 mL), CH
2
Cl
2
(100 mL). Yield 1.69 g
) δ:
), 1.16-1.44 (m, 36H, CH ),
), 4.17 (q, J=6.4 Hz, 4H,
H
Ar/dppe); C NMR (100 MHz, CDCl
3
) δ: 9.90 (CH
Me
3
),
),
1
(
60%) of a white solid. H NMR (400 MHz, CDCl
3
29.34 (t, J=22.90 Hz, CH2/dppe), 93.61 (C/C
5
5
0
1
.88 (t, J=6.8 Hz, 6H, CH
.46-1.61 (m, 4H, CH
). 7.42 (s, 2H, thiophene-H); C NMR (100 MHz,
) δ: 14.16 (CH ), 22.70, 25.95, 29.37, 29.60,
9.64, 30.40, 31.92, 74.16 (OCH ), 114.95, 123.09,
30.85, 131.13, 142.49.
Preparation of 2,6-bis(trimethylsilylethynyl)-4,8-
3
2
106.71 (s, thiophene-C ≡ C), 123.59(Ru-C ≡ CH),
127.57, 129.21, 129.34, 133.19, 135.82, 136.31, 137.84,
2
13
31
OCH
CDCl
2
1
2
138.18, 140.80, 145.03, 159.00, 174.28 (C=O);
NMR (160 MHz, CDCl
Ru : C 67.96, H 6.08; found C 67.91,
P
3
) δ: 79.09 (dppe). Anal. calcd
3
3
for C92
H
98
O
2
P
4
2 2
S
2
H 6.12.
Preparation of 2 The procedure of 2 was similar
to that of 1. Cp*(dppe)RuCl (388 mg, 0.58 mmol), 2,6-
bis(trimethylsilylethynyl)-4,8-diethoxybenzo[1,2-b:4,5-
b']dithiophene (2d) (130 mg, 0.28 mmol), KF (192 mg,
diethoxybenzo[1,2-b:4,5-b']dithiophene (2d) To a
stirred solution of 2,6-dibromo-4,8-diethoxybenzo-
[
(
1,2-b:4,5-b']dithiophene (2c) (370 mg, 0.85 mmol), CuI
16 mg, 0.085 mmol), and Pd(PPh (98 mg, 0.085
)
4
3.31 mmol), CH
mg (60%) of a brown solid. H NMR (400 MHz, CDCl
δ: 1.46 (t, J=7.2 Hz, 6H, CH CH ), 1.56 (s, 30H,
2C (CH ), 2.06 (br, 4H, CH2/dppe), 2.69 (br, 4H,
CH2/dppe), 4.17 (q, J=6.4 Hz, 4H, OCH ), 6.50 (s, 2H),
7.23-7.38 (m, 32H, HAr/dppe), 7.77 (br, 8H, HAr/dppe);
3
OH (20 mL), THF (5 mL). Yield: 279
3
1
mmol) in triethylamine (15 mL) and THF (25 mL) un-
der an argon atmosphere was added (trimethylsilyl)-
acetylene (0.48 mL, 3.39 mmol), and the mixture was
refluxed at 60 ℃ for 24 h. The cold solution was fil-
tered through a bed of Celite. The filtrate was evapo-
rated under reduced pressure and purified by silica gel
3
)
2
3
5
3 5
)
2
1
3
*
C NMR (100 MHz, CDCl
(m, CH2/dppe), 68.46 (OCH
(s, thiophene-C ≡ C), 116.32 (Ru-C ≡ CH), 127.41,
3
) δ: 10.04 (Cp -CH
3
), 29.50
column chromatography (CH
2
Cl
2
/petroleum ether, V∶V
2
), 92.90 (C/C Me ), 103.29
5
5
1
=
1∶2) to give a white solid (180 mg, 45%). H NMR
1172
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Chin. J. Chem. 2017, 35, 1170—1178