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Journal of Materials Chemistry A
Page 5 of 18
PAPER
DOI: 10.1039/C6TA07639D
Journal Name
4-butylbenzene-1,2-diol (3a). Yield 91%; white solid; δH(200 MHz, 6-ethylbenzo[b]thieno[3,4-e][1,4]dioxine (PhEDOT-C2). Yield 9%;
MeOD): 6.63 (2 H, m), 6.47 (1 H, d, J 8.0), 2.45 (2 H, t, J 7.5), 1.53 (2 colorless liquid; δH(200 MHz, CDCl3): 6.79 (3 H, m), 6.42 (2 H, s),
H, quin, J 7.6), 1.32 (2 H, q, J 7.4), 0.92 (3 H, t, J 7.2).
2.56 (2 H, q, J 7.4), 1.21 (3 H, t, J 7.5); δC(200 MHz, CDCl3): 140.45,
140.04, 139.27, 138.68, 122.84, 116.39, 115.94, 100.76, 100.64,
28.02, 15.46; FTIR (KBr): νmax/cm-1 3114, 2963, 2928, 2870, 1600,
1491, 1433, 1274, 760 cm-1; MS (70 eV): m/z 218 (M+ 65), 203
(C11H8O2S+ 100).
4-hexylbenzene-1,2-diol (3b). Yield 82%; yellow oil; δH(200 MHz,
MeOD): 6.62 (2 H, m), 6.46 (1 H, d, J 8.0), 2.43 (2 H, t, J 7.6), 1.54 (2
H, br), 1.30 (6 H, s), 0.89 (3 H, m).
4-octylbenzene-1,2-diol (3c). Yield 83%; light yellow solid; δH(200
MHz, MeOD): 6.62 (2 H, m), 6.46 (1 H, m), 2.44 (2 H, t, J 7.5), 1.54 (2
H, br), 1.29 (10 H, s), 0.89 (3 H, m).
6-butylbenzo[b]thieno[3,4-e][1,4]dioxine (PhEDOT-C4). Yield 9%;
Colorless crystalline solid; m.p. 27.0°C; δH(200 MHz, CDCl3): 6.84 (1
H, m), 6.73 (2 H, m), 6.41 (2 H, s), 2.52 (2 H, t, J 7.5), 1.56 (2 H, m),
1.34 (2 H, sex, J 7.2), 0.92 (3 H, t, J 7.2); δC(200 MHz, CDCl3): 140.38,
139.28, 139.18, 138.69, 123.41, 116.45, 116.31, 100.74, 100.63,
34.74, 33.43, 22.18, 13.91; FTIR (KBr): νmax/cm-1 3115, 2955, 2928,
2854, 1600, 1491, 1433, 1274, 760 cm-1; MS (70 eV): m/z 246 (M+,
52), 203 (C11H8O2S+ 100).
4-decylbenzene-1,2-diol (3d). Yield 65%; white solid; δH(200 MHz,
MeOD): 6.62 (2 H, m), 6.46 (1 H, d, J 8.0), 2.46 (2 H, t, J 3.7), 1.53 (2
H, br), 1.28 (14 H, s), 0.90 (3 H, m)
4-dodecylbenzene-1,2-diol (3e). Yield 97%; light brown powder;
δH(200 MHz, MeOD): 6.62 (2 H, t, J 7.4), 6.46 (1 H, dd, J 8.0 2.0),
2.43 (2 H, t, J 7.5), 1.53 (2 H, br), 1.28 (19 H, s), 0.89 (3 H, m).
6-hexylbenzo[b]thieno[3,4-e][1,4]dioxine (PhEDOT-C6). Yield 7%;
Colorless liquid; m.p. 34.3°C; δH(200 MHz, CDCl3): 6.82 (1 H, m),
6.77 (2 H, m), 6.41 (2 H, s), 2.51 (2 H, t, J 7.5), 1.57 (2 H, br), 1.30 (6
H, s), 0.88 (3 H, m); δC(200 MHz, CDCl3): 140.38, 139.28, 139.19,
138.74, 138.67, 123.40, 116.44, 116.31, 100.74, 100.63, 35.06,
31.67, 31.25, 28.80, 22.58, 14.08; FTIR (KBr): νmax/cm-1 3114, 2955,
2920, 2850, 1594, 1493, 1433, 1274, 758 cm-1; MS (70 eV): m/z 274
(M+ 64), 203 (C11H8O2S+ 100).
4-(3,3-dimethylbutyl)benzene-1,2-diol (3f). Yield 82%; White
crystalline solid; δH(200 MHz, MeOD): 6.63 (2 H, t, J 8.0), 6.46 (1 H,
d, J 7.8), 2.41 (2 H, m), 1.43 (2 H, m), 0.95 (9 H, s).
4-(3,5,5-trimethylhexyl)benzene-1,2-diol (3g). Yield 80%; light
yellow crystal; δH(200 MHz, MeOD): 6.63 (2 H, m), 6.47 (1 H, d, J
7.4), 2.47 (2 H, br), 1.38 (5 H, m), 0.96 (3 H, d, J 6.0), 0.88 (9 H, s).
6-octylbenzo[b]thieno[3,4-e][1,4]dioxine (PhEDOT-C8). Yield 9%;
white crystalline solid; m.p. 47.3°C; δH(200 MHz, CDCl3): 6.77 (3 H,
m), 6.41 (2 H, s), 2.51 (2 H, t, J 7.5), 1.56 (2 H, br), 1.27 (10 H, s),
0.88 (3 H, m); δC(200 MHz, CDCl3): 140.39, 139.29, 139.19, 138.75,
138.67, 123.40, 116.44, 116.31, 100.74, 100.63, 35.07, 31.86, 31.30,
29.43, 29.24, 29.14, 22.66, 14.10; FTIR (KBr): νmax/cm-1 3115, 2955,
2920, 2850, 1594, 1492, 1429, 1268, 756 cm-1; MS (70 eV): m/z 302
(M+ 86), 203 (C11H8O2S+ 100).
4-benzylbenzene-1,2-diol (3h). Yield 98%; off-white powder; δH(200
MHz, MeOD): 7.17 (5 H, m), 6.58 (3 H, m), 3.78 (2 H, s).
4-([1,1'-biphenyl]-4-ylmethyl)benzene-1,2-diol (3i). Yield 83%;
colorless powder; δH(200 MHz, MeOD): 7.54 (4 H, m), 7.32 (5 H, m),
6.62 (3 H, m), 3.84 (2 H, s).
4-(naphthalen-2-ylmethyl)benzene-1,2-diol (3j). Yield 88%; white
powder; δH(200 MHz, MeOD): 7.75 (3 H, m), 7.60 (1 H, s), 7.35 (3 H,
m), 6.64 (3 H, m), 3.96 (2 H, s).
6-decylbenzo[b]thieno[3,4-e][1,4]dioxine (PhEDOT-C10). Yield 8%;
colorless crystalline solid; m.p. 50.0°C; δH(200 MHz, CDCl3): 6.77 (3
H, m), 6.41 (2 H, s), 2.51 (2 H, t, J 7.6), 1.57 (2 H, br), 1.26 (15 H, s),
0.88 (3 H, t, J 6.0); δC(200 MHz, CDCl3): 140.38, 139.29, 139.19,
138.75, 138.67, 123.41, 116.44, 116.31, 100.74, 100.63, 35.06,
31.89, 31.29, 29.60, 29.57, 29.47, 29.32, 29.13, 22.68, 14.11; FTIR
(KBr): νmax/cm-1 3110, 2955, 2920, 2850, 1598, 1497, 1437, 1282,
760 cm-1; MS (70 eV): m/z 331 (M+ 85), 203 (C11H8O2S+ 100).
Synthesis of the monomers. 1 eq of 3a-3j and 2.5 g of 3,4-
dimethoxy thiophene (117 mmol, 4 eq) are dissolved in 120 mL of
toluene. 0.5 g of p-toluenesulfonic acid (2.9 mmol, ~1 eq) is added
to the solution, which is then refluxed at 120°C for 24 h. After 24 h,
0.5 g of p-toluenesulfonic acid is added again and the solution is
refluxed again at 120°C for 24 h. The resulting product is purified
first on silica gel with dichloromethane/cyclohexane (1:1) as eluent
and then on silica gel with cyclohexane as eluent.
6-dodecylbenzo[b]thieno[3,4-e][1,4]dioxine (PhEDOT-C12). Yield
6%; light green powder; m.p. 55.8°C; δH(200 MHz, CDCl3): 6.77 (3 H,
m), 6.41 (2 H, m), 2.51 (2 H, t, J 7.6), 1.26 (20 H, s), 0.88 (3 H, m);
δC(200 MHz, CDCl3): 140.38, 139.29, 139.19, 138.75, 138.67, 123.40,
116.44, 116.31, 100.74, 100.63, 35.07, 31.92, 31.29, 29.64, 29.57,
29.47, 29.35, 29.13, 22.69, 14.12; FTIR (KBr): νmax/cm-1 3111, 2955,
2916, 2850, 1598, 1496, 1437, 1282, 762 cm-1; MS (70 eV): m/z 358
(M+ 100), 203 (C11H8O2S+ 94).
6-methylbenzo[b]thieno[3,4-e][1,4]dioxine (PhEDOT-C1). Yield 9%;
colorless crystalline solid; m.p. 77.5°C; δH(200 MHz, CDCl3): 6.76 (3
H, m), 6.42 (2 H, s), 2.27 (3 H, s); δC(200 MHz, CDCl3): 140.34,
139.26, 139.14, 138.55, 124.03, 117.13, 116.32, 100.78, 100.63,
20.63; FTIR (KBr): νmax/cm-1 3106, 2955, 2916, 2854, 1600, 1495,
1433, 1276, 764 cm-1; MS (70 eV): m/z 204 (M+ 100), 203 (C11H8O2S+
33).
6-(tert-butyl)benzo[b]thieno[3,4-e][1,4]dioxine
(PhEDOT-tBu).
Yield 7%; white crystalline solid; m.p. 91.4°C; δH(200 MHz, CDCl3):
4 | J. Name., 2012, 00, 1-3
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