Full Papers
doi.org/10.1002/ejoc.202001475
1038 m, 1002 m, 858 m, 826 w, 804 m, 720 m, 653 m. MALDI-MS:
order to remove by-products pure ethyl acetate was first used as
eluent before the product was finally eluted from the stationary
phase with 10% methanol in dichloromethane. The residue was
dissolved in dichloromethane and pure product was precipitated
by addition of acetone. and column chromatography (SiO2, toluene:
ethyl acetate=1:0, 40:1, 30:1, 10:1)) to yield 46.4 mg (22.3 μmol=^
24%) of a yellowish solid.
1
2
3
4
5
6
7
8
9
1953.4 calculated for C120H186N6O9S3 +H+; found: 1953.3
2,5,8-Tris(5-(3,4,5-tris(hexyloxy)phenyl)-1,3,4-oxadiazol-2-yl)
benzo[1,2-b:3,4-b’:5,6-b’’]trithiophene (12)
According to the procedure given for 9, 85.9 mg (0.23 mmol,
1.0 eq.) benzo[1,2-b;3,4-b’;5,6-b’’]trithiophene-2,5,8-tricarboxylic and
356.8 mg (0.80 mmol, 3.5 eq.) 5-(3,4,5-tris(hexyloxy)phenyl)-2H-tet-
razole and 0.1 mL (0.75 mmol, 3.3 eq.) 2,4,6-collidine gave, after
1H-NMR (400 MHz, CDCl3): δ [ppm]=8.22 (s, 1H, H3-BTT), 7.28 (s,
3
3
2H, H2-ph, H6-ph), 4.11 (t, J=6.4 Hz, 4H, OCH2), 4.06 (t, J=6.5 Hz,
2H, OCH2), 1.93–1.86 (m, 6H, CH2), 1.57–1.48 (m, 6H, CH2), 1.42–1.25
(m, 36H, CH2), 0.91–0.87 (m, 9H, CH3). 13C-NMR (100 MHz, CDCl3): δ
[ppm]=165.19 (C5-oxa), 160.10 (C2-oxa), 153.79 (C3-ph, C5-ph),
141.84 (C4-ph), 135.28 (C-BTT), 131.39 (C-BTT), 125.70 (C-BTT),
123.82 (C2-BTT), 117.79 (C1-ph), 105.49 (C2-ph, C6-ph), 73.78
(OCH2), 69.53 (OCH2), 32.13, 32.10, 30.58, 29.95, 29.87, 29.82, 29.80,
°
°
stirring for 20 min at 60 C 20 h at 80 C, usual work-up, and column
chromatography (SiO2 (2.5×23 cm), Al2O3 (2.5×1.5 cm, toluene to
toluene/ethyl acetate=10:1). In order to remove further by-
products the obtained mixture was dissolved in dichloromethane
and the product precipitates by addition of ethyl acetate to yield
62.6 mg (0.18 mmol=^ 80%) of a pale yellow solid.
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
~
29.67, 29.59, 29.57, 26.35, 26.29, 22.87, 14.29 (CH3). IR (ATR): u
[cmÀ 1]=2921 ss, 2852 s, 1587 m, 1547 m, 1490 s, 1467 s, 1437 s,
1380 m, 1348 m, 1321 w, 1239 m, 1214 m, 1116 s, 1007 m, 838 m,
723 s, 619 w. MALDI-MS: 2085.4 calculated for C126H198N6O12S3 +H+;
found: 2085.2.
1H-NMR (400 MHz, CDCl3): δ [ppm]=8.08 (s, 1H, H3-BTT), 7.20 (s,
2H, H2-ph,H6-ph), 4.09–4.03 (m, Hz, 6H, OCH2), 1.92–1.75 (m, 6H,
CH2), 1.59–1.49 (m, 6H, CH2), 1.43–1.34 (m, 12H, CH2), 0.97–0.92 (m,
9H, CH3). 13C-NMR (100 MHz, CDCl3): δ [ppm]=165.07, 159.96,
153.72, 141.78, 135.04, 131.20, 125.63, 123.55, 117.65, 105.34, 73.72,
69.47, 31.95, 31.83, 30.54, 29.53, 26.00, 25.93, 22.87, 22.84, 14.26 (d,
2,5,8-Tris(5-(3,4,5-tris(dodecyloxy)
phenyl)-1,3,4-oxadiazol-2-yl)benzo[1,2-b:3,4-b’:5,6-b’’]
trithiophene 15
J=2.2 Hz). IR (ATR): u [cmÀ 1]=2956 s, 2927 s, 2871 m, 2857 m,
~
1587 s, 1547 m, 1488 ss, 1467 s, 1435 ss, 1379 m, 1348 s, 1321 m,
1240 s, 1214 s, 1112 ss, 1046 m, 1006 s, 909 m, 874 m, 839 s, 723 ss,
673 m. MALDI-MS: 1580.9 calculated for C90H126N6O12S3 +H+; found:
1580.9.
Following the procedure given for 9, 34.9 mg (0.092 mmol, 1.0 eq.)
benzo[1,2-b;3,4-b’;5,6-b’’]trithiophene-2,5,8-tricarboxylic
and
227.8 mg (0.33 mmol, 3.7 eq.) 5-(3,4,5-tris(dodecyloxy)phenyl)-2H-
tetrazole and 0.1 mL (0.75 mmol, 8.3 eq.) 2,4,6-collidine gave, after
2,5,8-Tris(5-(3,4,5-tris(octyloxy)phenyl)-1,3,4-oxadiazol-2-yl)
benzo[1,2-b:3,4-b’:5,6-b’’]trithiophene 13
°
stirring 20 h at 80 C, usual work-up, a crude material. This was
purified by column chromatography (Al2O3 (neutral) topped with
bas. Al2O3). In order to remove by-products pure ethyl acetate was
first used as eluent before the pure product was eluted from the
stationary phase with chloroform to yield 0.127 g (0.054 mmol=^
According to the procedure given for 9, 33.3 mg (88.0 μmol, 1.0 eq.)
benzo[1,2-b;3,4-b’;5,6-b’’]trithiophene-2,5,8-tricarboxylic
and
159.2 mg (0.3 mmol, 3.4 eq.) 5-(3,4,5-tris(octyloxy)phenyl)-2H-tetra-
zole and 0.1 mL (0.75 mmol, 8.6 eq.) 2,4,6-collidine gave, after
°
59%) of a pale yellow solid with m. p.=À 7 C (onset, DSC).
1H-NMR (300 MHz, CDCl3): δ [ppm]=8.14 (s, 1H, H3-BTT), 7.24 (s,
2H, H2-ph, H6-ph), 4.11–4.04 (m, 6H, OCH2), 1.94–1.74 (m, 6H, CH2),
1.58–1.50 (m, 6H, CH2), 1.44–1.26 (m, 48H, CH2), 0.91–0.85 (m, 9H,
CH3). 13C-NMR (75 MHz, CDCl3): δ [ppm]=165.15, 160.02, 153.76,
141.82, 135.14, 131.30, 125.68, 123.67, 117.71, 105.43, 73.75, 69.50,
32.11, 30.61, 29.96, 29.93, 29.90, 29.83, 29.71, 29.58, 29.57, 26.37,
°
stirring for 24 h at 80 C, and usual work-up a crude product that
was dissolved in dichloromethane and adsorbed on neutral
aluminium oxide. The crude product was obtained by column
chromatography (neutral
(1×3 cm)). In order to remove by-
Al2O3
products pure ethyl acetate was used as eluent and the product
was eluted with 10% methanol in dichloromethane. In order to
remove remaining by-products the obtained mixture was dissolved
in dichloromethane and the product precipitates by addition of
ethyl acetate. Yield: 43.3 mg (23.6 μmol=^ 27%) of an off-white solid
26.32, 22.86, 14.28. IR (ATR): u [cmÀ 1]=2951 m, 2920 ss, 2851 ss,
~
1588 s, 1547 m, 1490 s, 1466 s, 1437 s, 1379 m, 1348 s, 1321 m,
1239 m, 1214 m, 1116 ss, 1051 m, 1006 s, 966 m, 838 m, 723 s.
MALDI-MS: 2445.6 calculated for
C
144H234N6O12S3 +Ag+; found:
1H-NMR (300 MHz, CDCl3): δ [ppm]=8.24 (s, 1H, H3-BTT), 7.30 (s,
2H, H2-ph, H6-ph), 4.13-4.05 (m, 6H, OCH2), 1.94-1.75 (m, 6H, CH2),
1.58–1.25 (m, 30H, CH2), 0.93–0.88 (m, 9H, CH3). 13C-NMR (100 MHz,
CDCl3): δ [ppm]=165.14, 160.02, 153.76, 141.85, 135.13, 131.30,
125.68, 123.70, 117.72, 105.45, 73.76, 69.52, 32.11, 32.05, 30.60,
2445.5.
2,5,8-Tris(5-(3,4,5-tris(tetradecyloxy)
phenyl)-1,3,4-oxadiazol-2-yl)benzo[1,2-b:3,4-b’:5,6-b’’]
trithiophene 16
~
29.75, 29.64, 29.59, 29.52, 26.36, 26.29, 22.87, 14.29. IR (ATR): u
[cmÀ 1]=2960 s, 2919 ss, 2851 s, 1697 w, 1587 s, 1547 m, 1490 s,
1467 s, 1437 s, 1383 m, 1348 m, 1321 m, 1239 m, 1216 s, 1115 ss,
1008 s, 965 w, 838 m, 772 s, 743 w, 724 s, 626 w. MALDI-MS: 1833.2
calculated for C108H162N6O12S3 +H+; found: 1832.9.
According to the procedure given for 9, 34.6 mg (91.4 μmol, 1.0 eq.)
benzo[1,2-b;3,4-b’;5,6-b’’]trithiophene-2,5,8-tricarboxylic
and
233.4 mg (0.30 mmol, 3.0 eq.) 5-(3,4,5-tris(tetradecyloxy)phenyl)-2H-
tetrazole and 0.1 mL (0.75 mmol, 8.3 eq.) 2,4,6-collidine gave, after
°
stirring for 18 h at 80 C, and usual work-up a crude product. This
2,5,8-Tris(5-(3,4,5-tris(decyloxy)phenyl)-1,3,4-oxadiazol-2-yl)
benzo[1,2-b:3,4-b’:5,6-b’’]trithiophene 14
was purified by column chromatography (Al2O3 (neutral)) topped
with bas. Al2O3). In order to remove by-products, pure ethyl acetate
was first used as eluent before the product was finally eluted from
the stationary phase with chloroform. The residue was dissolved in
chloroform and the pure product was precipitated by addition of
acetone to yield 80.5 mg (31.1 μmol=^ 34%) of a slightly yellow
Following the procedure given for 9, 35.1 mg (92.6 μmol, 1.0 eq.)
benzo[1,2-b;3,4-b’;5,6-b’’]trithiophene-2,5,8-tricarboxylic
and
193.96 mg (0.3 mmol, 3.4 eq.) 5-(3,4,5-tris(decyloxy)phenyl)-2H-tet-
razole and 0.1 mL (0.75 mmol, 8.1 eq.) 2,4,6-collidine gave, after
°
solid with m. p.=20 C (onset, DSC).
°
stirring 24 h at 80 C, usual work-up, a crude material. This was
purified by column chromatography (Al2O3 (neutral) 1×3 cm). In
Eur. J. Org. Chem. 2021, 798–809
807
© 2021 The Authors. European Journal of Organic Chemistry published
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