2090 Chem. Mater., Vol. 22, No. 6, 2010
Kreyes et al.
3
4J(40,R)=0.9 Hz, 1 H, 40-H), 2.76 (t, J(R,β)=7.5 Hz, 2 H,
(d, 3J(400, 300)=3J(30000, 40000)=3.8 Hz, 2 H, 400-H, 30000-H), 6.65
3
R-CH2), 1.69-1.61 (m, 2 H, β-CH2), 1.36-1.28 (m, 24 H, CH2),
0.86 (t, 3J(H,H) = 6.9 Hz, 3 H, CH3), 0.47-0.43 (m, 4 H,
CH2SiCH2), 0.35 (s, 9 H, Sn(CH3)3), -0.08 (s, 6 H, Si(CH3)2).
5-Trimethylstannyl-50-(3-(dimethyltetradecylsilyl)prop-1-yl)-
2,20-bithiophene (23). To a solution of compound 19 (1.80 g, 3.8
mmol) in dry THF (20 mL), n-BuLi (3.3 mL, 5.3 mmol) was
added dropwise at 0 ꢀC. The mixture was allowed to warm to
room temperature and stirred for 1 h. A solution of trimethyltin
chloride (1.06 g, 5.3 mmol) in dry THF (5 mL) was then added.
After stirring for 1 h, the solvent was evaporated to afford crude
23 as a brown solid in quantitative yield determined by 1H
NMR, which was directly used for the coupling step without
further purification. 1H NMR (400 MHz, CDCl3), δ [ppm]: 7.18
(d, 3J(3,4)=3.3 Hz, 1 H, 3-H), 7.04 (d, 3J(4,3)=3.5 Hz, 1 H,
4-H), 6.95 (d, 3J(30,40)=3.6 Hz, 1 H, 30-H), 6.64 (td, 3J(40,30)=
3.5 Hz, 4J(40,R)=0.9 Hz, 1 H, 40-H), 2.77 (t, 3J(R,β)=7.3 Hz, 2
H, R-CH2), 1.68-1.61 (m, 2 H, β-CH2), 1.30-1.24 (m, 24 H,
CH2), 0.86 (t, 3J(H,H)=6.8 Hz, 3 H, CH3), 0.58-0.54 (m, 2 H,
β-CH2CH2Si), 0.49-0.45 (m, 2 H, SiCH2), 0.35 (s, 9 H,
Sn(CH3)3), -0.06 (s, 6 H, Si(CH3)2).
(d, J(4,3)=3.5 Hz, 2 H, 4-H, 4000000-H), 4.03-3.94 (m, 8 H,
CH2 protection groups), 2.76 (t, 3J(R,β)=7.6 Hz, 4 H, R-CH2),
2.16 (s, 4 H, CO2(CH2)2CO2), 1.69-1.61 (m, 4 H, β-CH2),
3
1.38-1.17 (m, 50 H, CH and CH2), 0.87 (t, J(H,H)=6.9 Hz,
6 H, hexyl-CH3), 0.80 (t, J(H,H)=7.3 Hz, 6 H, ethyl-CH3),
3
0.47-0.43 (m, 8 H, CH2SiCH2), -0.06 (s, 12 H, Si(CH3)2). 13
C
NMR (100 MHz, CDCl3), δ [ppm]: 145.6, 145.3, 137.0, 136.8,
135.4, 134.5, 125.3, 124.8, 124.2, 123.5, 123.4, 123.2, 108.5, 35.9,
35.4, 34.7, 33.8, 31.7, 30.2, 29.7, 29.64, 29.60, 29.4, 29.1, 28.9,
24.0, 23.1, 20.1, 16.2, 14.3, 10.8, -2.3. MS (MALDI-TOF) m/z:
1316.3 [MþH]þ, 643.5 [M-C38H59O2S3Si]þ. Elemental analy-
sis: Calcd. for C74H114O4S6Si2 (1316.26): C 67.52, H 8.73;
Found: C 67.31, H 8.65.
1,2-Bis(2-(5-(6-(dimethylundecylsilyl)hex-1-yl)-2,20:50,200-ter-
thien-500-yl)-1,3-dioxolan-2-yl)ethane (26). Crude compound 22
(3.9 mmol) and brominated precursor 37 (0.97 g, 1.95 mmol)
were dissolved in dry THF (50 mL). The solution was degassed
for 1 h. Pd(PPh3)4 (0.16 g, 0.14 mmol) then was added and the
mixture was stirred under reflux for 20 h. After cooling to room
temperature, methanol (60 mL) was added and the resulting
precipitate was filtered. The orange crude product was recrys-
tallized from acetone and 26 was obtained as a yellow powder
1,2-Bis(2-(5-(11-(hexyldimethylsilyl)undec-1-yl)-2,20:50,200-
terthien-500-yl)-1,3-dioxolan-2-yl)ethane (24). Crude compound
20 (3.2 mmol) and brominated precursor 37 (794 mg, 1.6 mmol)
were dissolved in dry THF (35 mL). The solution was degassed
for 1 h. Pd(PPh3)4 (130 mg, 0.1 mmol) then was added and the
mixture was refluxed for 18 h. After cooling to room tempera-
ture, methanol was added and the resulting precipitate was
filtered off. The orange crude product was recrystallized from
acetone and 24 was obtained as a yellow powder (1.1 g, 55%). 1H
NMR (400 MHz, CDCl3), δ [ppm]: 6.97 (d, 3J(H,H)=3.8 Hz,
1
(0.80 g, 33%). H NMR (400 MHz, CDCl3), δ [ppm]: 6.97 (d,
3J(H,H)=3.8 Hz, 2 H, 30-H, 40000-H or 40-H, 300000-H), 6.96 (d,
3J(300, 400)=3J(40000, 30000)=3.8 Hz, 2 H, 300-H, 4000000000-H), 6.94 (d,
3J(H,H)=3.8 Hz, 2 H, 30-H, 400000-H or 40-H, 3000000 -H), 6.94 (d,
3J(3,4)=3J(3000000, 4000000)=3.6 Hz, 2 H, 3-H, 3 -H), 6.87 (d,
3J(400, 300)=3J(30000, 40000)=3.8 Hz, 2 H, 400-H, 30000-H), 6.65 (d,
3J(4,3)=3.8 Hz, 2 H, 4-H, 4000000-H), 4.03-3.94 (m, 8 H, CH2
protection group), 2.76 (t, 3J(R,β)=7.6 Hz, 4 H, R-CH2), 2.16 (s,
4 H, CO2(CH2)2CO2), 1.69-1.61 (m, 4 H, β-CH2), 1.35-1.24
(m, 48 H, CH2), 0.86 (t, 3J(H,H)=6.9 Hz, 6 H, CH3), 0.48-0.44
(m, 8 H, CH2SiCH2), -0.08 (s, 12 H, Si(CH3)3). 13C NMR (100
MHz, CDCl3) δ [ppm]: 145.6, 145.3, 137.0, 136.8, 135.4, 134.5,
125.3, 124.8, 124.1, 123.5, 123.4, 123.2, 108.5, 65.1, 34.7,
33.8, 33.4, 32.0, 31.6, 30.2, 29.8, 29.68, 29.66, 29.42, 29.40,
28.8, 23.9, 23.8, 22.7, 15.31, 15.29, 14.2, -3.3. MS (MALDI-
TOF) m/z (%): 1259.8 [MþH]þ, 715.4 [M-C31H47S3Si]þ, 615.4
3
2 H, 30-H, 40000-H or 40-H, 30000-H), 6.96 (d, J(300, 400) =
3J(40000, 30000)=3.5 Hz, 2 H, 300-H, 40000-H), 6.94 (d, 3J(H,H)=3.8
3
Hz, 2 H, 30-H, 400000-H or 40-H, 300000-H), 6.94 (d, J(3,4)=
3J(3000000, 4000000)=3.6 Hz, 2 H, 3-H, 3000000-H), 6.87 (d, 3J(400, 300)=
3J(30000, 40000)=3.5 Hz, 2 H, 400-H, 30000-H), 6.65 (td, 3J(4,3)=3.5
Hz, 4J(4,R)=4J(4000000,R)=1.0 Hz, 2 H, 4-H, 4000000-H), 4.03-3.94
(m, 8 H, CH2 protection groups), 2.76 (t, 3J(R,β)=7.4 Hz, 4 H,
R-CH2), 2.16 (s, 4 H, CO2(CH2)2CO2), 1.69-1.62 (m, 4 H,
[M-C36H55OS3Si]þ. Elemental analysis: Calcd. for C70H106
-
3
β-CH2), 1.38-1.25 (m, 48 H, CH2), 0.86 (t, J(H,H)=6.9 Hz,
O4S6Si2 (1260.15): C 66.72, H 8.48; Found: C 66.34, H 8.48.
1,2-Bis(2-(5-(3-(dimethyltetradecylsilyl)prop-1-yl)-2,20:50,200-
terthien-500-yl)-1,3-dioxolan-2-yl)ethane (27). Crude product
(23) (3.6 mmol) and brominated precursor 37 (0.89 g, 1.79
mmol) were dissolved in dry THF (30 mL). The solution was
degassed for 1 h. Pd(PPh3)4 (0.15 g, 0.13 mmol) then was added
and the mixture was stirred under reflux for 18 h. After cooling
to room temperature, methanol was added and the resulting
precipitate was filtered. The crude product then was dissolved in
THF, charcoal was added, and the mixture was refluxed for 30
min. After filtration, the product was precipitated by the addi-
tion of methanol. 27 was obtained as a yellow solid (0.72 g,
32%). 1H NMR (400 MHz, CDCl3), δ [ppm]: 6.98-6.94 (m, 8 H,
3-H, 30-H, 40-H, 300-H, 40000-H, 300000-H, 400000-H, 3000000-H),
6.87 (d, 3J(400, 300)=3J(30000, 40000)=3.5 Hz, 2 H, 400-H, 30000-H),
6.65 (d, 3J(4,3)=3J(4000000,3000000)=3.5 Hz, 2 H, 4-H, 4000000-H),
4.03-3.94 (m, 8 H, CH2 protection group), 2.78 (t, 3J(R,β)=7.3
Hz, 4 H, R-CH2), 2.17 (s, 4 H, CO2(CH2)2CO2), 1.69-1.61 (m, 4
H, β-CH2), 1.28-1.24 (m, 48 H, CH2), 0.86 (t, 3J(H,H)=7.0 Hz,
6 H, CH3), 0.58-0.54 (m, 4 H, β-CH2CH2Si), 0.49-0.45 (m, 4
H, SiCH2), -0.05 (s, 12 H, Si(CH3)2). 13C NMR (100 MHz,
CDCl3) δ [ppm]: 145.4, 137.0, 136.9, 135.5, 134.6, 125.2, 125.0,
124.1, 123.5, 123.4, 123.2, 108.5, 65.1, 34.7, 34.1, 33.7, 31.9,
29.74, 29.72, 29.70, 29.67, 29.6, 29.39, 29.37, 26.4, 23.9, 22.7,
6 H, CH3), 0.47-0.43 (m, 8 H, CH2SiCH2), -0.08 (s, 12 H,
Si(CH3)2). 13C NMR (100 MHz, CDCl3), δ [ppm]: 145.9, 145.5,
136.9, 135.4, 134.3, 125.5, 125.1, 124.4, 123.7, 123.6, 123.4,
108.5, 65.3, 34.7, 33.9, 33.5, 31.7, 30.3, 29.83, 29.76, 29.7,
29.52, 29.51, 29.3, 24.03, 23.99, 22.8, 15.4, 14.4, -3.1. MS
(MALDI-TOF) m/z: 1215.1 [M-C2H4O]þ, 1170.1 [M-C4H8-
O2]þ, 671.6 [M-C33H51OS3Si]þ, 615.6 [M-C36H55O2S3Si]þ.
Elemental analysis: Calcd. for C70H106O4S6Si2 (1260.15): C
66.72, H 8.48; Found: C 66.61, H 8.56.
1,2-Bis(2-(5-(11-((2-ethylhexyl)dimethylsilyl)undec-1-yl)-2,20:
50,200-terthien-500-yl)-1,3-dioxolan-2-yl)ethane (25). Crude com-
pound 21 (3.0 mmol) and brominated precursor 37 (0.74 g, 1.5
mmol) were dissolved in dry THF (30 mL). The solution was
degassed for 1 h. Pd(PPh3)4 (0.12 g, 0.11 mmol) then was added
and the mixture was refluxed for 20 h. After cooling to room
temperature, methanol was added and the resulting precipitate
was filtered off. The orange crude product was recrystallized
from acetone and 25 was obtained as a yellow powder (0.86 g,
44%). 1H NMR (400 MHz, CDCl3), δ [ppm]: 6.97 (d, 3J(H,H)=
3
3.8 Hz, 2 H, 30-H, 400000-H or 40-H, 300000-H), 6.96 (d, J(300,
400) = 3J(40000, 30000) = 3.5 Hz, 2 H, 300-H, 40000-H), 6.94 (d,
3J(H,H)=3.8 Hz, 2 H, 30-H, 400000-H or 40-H, 300000-H), 6.94
(d, 3J(3,4)=3J(3000000, 4000000)=3.5 Hz, 2 H, 3-H, 3000000-H), 6.87