Chemistry - A European Journal
10.1002/chem.201901782
FULL PAPER
2
,5-Bis(2-benzo[b]furyl)-N,N'-bis(2-(5-hexylthien-2-yl)phenyl)benzen-
124.6, 124.5, 124.5, 123.7, 123.5, 123.2, 123.1, 122.3, 120.2, 116.4,
31.9, 31.8, 30.3, 29.0, 22.8, 14.4.
e-1,4-diamine (3c). Eluent: PE/DCM = 5/1, yield: 60% (0.20 g), light
yellow solid. H NMR (400 MHz, CDCl
1
3
, δ ppm): 7.91 (s, 2H), 7.50 (s, 2H),
7
7
2
.44 (d, J = 8.2 Hz, 2H), 7.34 (d, J = 8.1 Hz, 2H), 7.27 – 7.16 (m, 10H),
General synthetic procedure for the B
solution of diamine (0.25 mmol) and triethylamine (0.10 g, 1.00 mmol) in
o-dichlorobenzene (10 mL) was added BBr (0.19 g, 0.75 mmol). The
reaction mixture was heated at 180 °C under a nitrogen atmosphere for
4 h (BNFS, BNFL, BNBFS, and BNBFL 48 h). After removal of the
2 2
N -embedded PAHs. To a
.13 (d, J = 3.3 Hz, 2H), 7.01 – 6.95 (m, 4H), 6.80 (d, J = 3.1 Hz, 2H),
.82 (t, J = 7.9 Hz, 4H), 1.71 – 1.64 (m, 4H), 1.40 – 1.25 (m, 12H), 0.87 (t,
3
13
J = 6.2 Hz, 6H). C NMR (100 MHz, CDCl
3
, δ ppm): 154.5, 153.7, 147.0,
1
1
2
41.8, 137.8, 135.0, 131.4, 129.0, 126.5, 124.7, 124.7, 123.9, 123.6,
23.2, 121.8, 121.3, 120.5, 116.2, 111.3, 105.2, 31.9, 31.8, 30.4, 29.1,
2.8, 14.3.
2
solvent under reduced pressure, the residue was purified by column
chromatography over silica gel to give the crude product, which was
further recrystallized from CHCl
3
/MeOH to afford the desired product.
2,5-Bis(2-benzo[b]thienyl)-N,N'-bis(2-(5-hexylthien-2-yl)phenyl)benz-
1
ene-1,4-diamine (3d). Eluent: PE/DCM = 6/1, yield: 44% (0.15 g), light
BNFS. Eluent: PE/DCM = 5/1, yield: 24% (44 mg), yellow solid. H NMR
(
1
yellow solid. H NMR (400 MHz, CDCl
3
, δ ppm): 7.78 (d, J = 7.5 Hz, 2H),
2 2
400 MHz, CD Cl , δ ppm): 9.09 (s, 2H), 8.66 (d, J = 8.2 Hz, 2H), 8.01 (d,
J = 8.4 Hz, 2H), 7.81 (s, 2H), 7.63 (s, 2H), 7.48 (t, J = 9.0 Hz, 2H), 7.40 (t,
J = 8.0 Hz, 2H), 7.31 (s, 2H), 3.05 (t, J = 7.4 Hz, 4H), 1.90 – 1.78 (m, 4H),
.49 – 1.34 (m, 12H), 0.93 (t, J = 6.6 Hz, 6H). C NMR (100 MHz,
2
, δ ppm): 158.2, 148.2, 146.3, 143.7, 137.4, 134.1, 127.9, 125.9,
25.5, 124.9, 123.3, 121.8, 116.9, 115.5, 113.6, 32.0, 31.9, 30.6, 29.2,
7
2
2
.71 (d, J = 8.3 Hz, 2H), 7.57 (s, 2H), 7.42 (s, 2H), 7.38 (d, J = 7.2 Hz,
H), 7.35 – 7.28 (m, 4H), 7.21 (d, J = 5.5 Hz, 4H), 6.97 (d, J = 3.4 Hz,
H), 6.92 (t, J = 6.8 Hz, 2H), 6.64 (d, J = 3.4 Hz, 2H), 6.34 (s, 2H), 2.72 (t,
13
1
J = 7.7 Hz, 4H), 1.68 – 1.57 (m, 4H), 1.37 – 1.26 (m, 12H), 0.88 (t, J =
2
CD Cl
1
3
6
1
1
2
3
.7 Hz, 6H). C NMR (100 MHz, CDCl , δ ppm): 146.9, 141.7, 140.5,
1
2
7
40.1, 137.5, 135.2, 131.5, 131.3, 128.9, 128.0, 126.3, 124.6, 124.6,
24.5, 124.3, 123.8, 123.5, 123.1, 122.3, 120.7, 116.6, 31.8, 31.8, 30.3,
9.1, 22.8, 14.3.
+
2.9, 14.1. HRMS (MALDI-TOF/MS, m/z): [M ] calcd for C46
40.2874; found 740.1227.
42 2 2 2 2
H B N O S
1
BNTS. Eluent: PE/DCM = 5/1, yield: 61% (0.11 g), yellow solid. H NMR
400 MHz, CDCl , δ ppm): 8.82 (s, 2H), 8.57 (d, J = 8.5 Hz, 2H), 7.98 (t, J
7.2 Hz, 4H), 7.66 (s, 2H), 7.46 (d, J = 4.9 Hz, 2H), 7.41 (t, J = 7.5 Hz,
H), 7.34 (t, J = 7.3 Hz, 2H), 3.00 (t, J = 7.6 Hz, 4H), 1.86 – 1.77 (m, 4H),
N,N'-Bis(2-(furan-2-yl)phenyl)-2,5-bis(5-hexylthien-2-yl)benzene-1,4-
(
3
diamine (3e). Chromatography (silica gel, PE/DCM = 3/1), yield: 65%
=
2
1
1
(
0.19 g), white solid. H NMR (400 MHz, CDCl
3
, δ ppm): 7.57 (d, J = 7.7
Hz, 2H), 7.48 (s, 2H), 7.42 (s, 2H), 7.18 (d, J = 3.7 Hz, 4H), 7.05 (d, J =
13
.49 – 1.43 (m, 4H), 1.41 – 1.35 (m, 8H), 0.92 (t, J = 6.7 Hz, 6H).
C
3
6
1
.6 Hz, 2H), 6.95 – 6.87 (m, 2H), 6.82 (s, 2H), 6.68 (d, J = 3.5 Hz, 2H),
NMR (100 MHz, CDCl
3
, δ ppm): 149.5, 149.1, 146.3, 137.3, 133.3, 132.1,
.61 (d, J = 3.3 Hz, 2H), 6.47 – 6.46 (m, 2H), 2.75 (t, J = 7.6 Hz, 4H),
1
28.3, 126.1, 125.8, 125.1, 125.1, 123.6, 122.7, 121.7, 119.3, 32.0, 31.9,
13
.65 – 1.58 (m, 4H), 1.34 – 1.26 (m, 12H), 0.87 (t, J = 6.6 Hz, 6H).
, δ ppm): 153.1, 147.1, 141.8, 141.6, 137.1, 134.5,
29.0, 128.4, 128.0, 126.1, 124.5, 123.5, 120.1, 119.4, 116.9, 111.6,
C
+
30.7, 29.2, 22.9, 14.4. HRMS (MALDI-TOF/MS, m/z): [M ] calcd for
NMR (100 MHz, CDCl
3
46 42 2 2 4
C H B N S 772.2417; found 772.0995.
1
1
07.4, 31.8, 31.8, 30.3, 29.0, 22.8, 14.3.
1
BNBFS. Eluent: PE/DCM = 4/1, yield: 21% (43 mg), yellow solid.
NMR (400 MHz, CDCl , δ ppm): 9.08 (s, 2H), 8.45 (d, J = 8.4 Hz, 2H),
.20 (d, J = 7.5 Hz, 2H), 7.87 (d, J = 7.7 Hz, 2H), 7.77 (s, 2H), 7.69 (d, J
7.8 Hz, 2H), 7.42 – 7.27 (m, 8H), 3.03 (d, J = 7.6 Hz, 4H), 1.91 – 1.84
H
3
2,5-Bis(5-hexylthien-2-yl)-N,N-'bis(2-(thien-2-yl)phenyl)benzene-1,4-
8
=
diamine (3f). Eluent: PE/DCM = 8/1, yield: 52% (0.16 g), green yellow
1
solid. H NMR (400 MHz, CDCl
3
, δ ppm): 7.38 (d, J = 7.1 Hz, 4H), 7.32 (d,
13
(
m, 4H), 1.56 – 1.42 (m, 12H), 0.98 (t, J = 6.9 Hz, 6H). C NMR (100
MHz, CDCl , δ ppm): 160.2, 156.6, 148.6, 145.8, 137.3, 135.4, 130.6,
29.4, 126.1, 125.6, 125.0, 123.7, 123.6, 123.6, 122.1, 117.6, 116.5,
11.9, 109.9, 32.4, 32.3, 31.0, 29.7, 23.5, 14.8. HRMS (MALDI-TOF/MS,
J = 5.1 Hz, 2H), 7.22 - 9.19 (m, 4H), 7.11 (d, J = 8.7 Hz, 2H), 7.06 – 7.04
3
(m, 2H), 6.94 – 6.88 (m, 4H), 6.64 (d, J = 3.4 Hz, 2H), 6.14 (s, 2H), 2.74
1
1
(
t, J = 7.6 Hz, 4H), 1.66 – 1.58 (m, 7.5 Hz, 4H), 1.34 – 1.25 (m, 12H),
13
0
1
1
.88 (t, J = 6.7 Hz, 6H). C NMR (100 MHz, CDCl
3
, δ ppm): 147.1, 142.4,
+
46 2 2 2 2
m/z): [M ] calcd for C54H B N O S 840.3187; found 840.3161.
40.6, 136.9, 134.5, 131.3, 129.2, 128.0, 127.6, 126.5, 126.0, 125.7,
24.5, 123.3, 120.2, 116.4, 109.9, 31.8, 31.8, 30.3, 29.0, 22.8, 14.4.
1
BNBTS. Eluent: PE/DCM = 5/1, yield: 43% (94 mg), yellow solid.
NMR (400 MHz, CDCl , δ ppm): 8.88 (s, 2H), 8.60 (d, J = 8.3 Hz, 2H),
.51 (d, J = 8.6 Hz, 2H), 8.06 (d, J = 8.4 Hz, 2H), 7.93 (d, J = 7.5 Hz, 2H),
H
3
N,N'-Bis(2-(2-benzo[b]furyl)phenyl)-2,5-bis(5-hexylthien-2-yl)benzen-
8
7
4
e-1,4-diamine (3g). Eluent: PE/DCM = 5/1), yield: 74% (0.24 g), gray
.74 (s, 2H), 7.50 – 7.38 (m, 8H), 2.98 (t, J = 7.3 Hz, 4H), 1.82 – 1.75 (m,
H), 1.42 – 1.31 (m, 12H), 0.89 (d, J = 6.6 Hz, 6H). C NMR (100 MHz,
1
solid. H NMR (400 MHz, CDCl
3
, δ ppm): 7.71 (d, J = 7.2 Hz, 2H), 7.62 –
13
7
3
=
.47 (m, 4H), 7.36 (d, J = 8.1 Hz, 2H), 7.31 – 7.20 (m, 8H), 7.09 (d, J =
CDCl
3
, δ ppm): 150.1, 148.5, 145.7, 143.4, 140.5, 136.7, 134.9, 133.9,
29.7, 126.1, 125.9, 125.3, 125.3, 124.9, 123.9, 123.0, 122.7, 122.3,
18.9, 31.9, 30.6, 30.0, 29.0, 22.9, 14.4. HRMS (MALDI-TOF/MS, m/z):
.5 Hz, 2H), 6.97 (s, 2H), 6.94 (s, 2H), 6.69 (d, J = 3.3 Hz, 2H), 2.73 (t, J
6.7 Hz, 4H), 1.62 – 1.55 (m, 4H), 1.32 – 1.20 (m, 12H), 0.84 (t, J = 6.7
1
1
[
13
Hz, 6H). C NMR (100 MHz, CDCl
3
, δ ppm): 155.5, 154.6, 147.3, 137.0,
+
46 2 2 4
M ] calcd for C54H B N S 872.2730; found 872.0784.
1
1
1
34.5, 130.1, 129.4, 129.1, 128.1, 126.3, 124.7, 124.3, 123.5, 123.4,
23.3, 121.1, 120.3, 116.9, 111.3, 103.9, 31.9, 31.8, 30.4, 29.1, 22.8,
4.4.
1
BNFL. Eluent: PE/DCM = 4/1, yield: 21% (39 mg), yellow solid. H NMR
400 MHz, CD Cl , δ ppm): 8.83 (s, 2H), 8.71 (d, J = 8.5 Hz, 2H), 8.30 (d,
J = 8.2 Hz, 2H), 7.84 (s, 2H), 7.61 (s, 2H), 7.58 – 7.52 (m, 2H), 7.48 (t, J
(
2
2
N,N'-Bis(2-(2-benzo[b]thienyl)phenyl)-2,5-bis(5-hexylthien-2-yl)benz-
=
1
CD
7.5 Hz, 2H), 7.31 (s, 2H), 3.01 (t, J = 7.6 Hz, 4H), 1.85 – 1.77 (m, 4H),
.45 – 1.35 (m, 12H), 0.92 (t, J = 6.8 Hz, 6H). C NMR (100 MHz,
ene-1,4-diamine (3h). Eluent: PE/DCM = 3/1), yield: 33% (0.12 g), gray
13
1
solid. H NMR (400 MHz, CDCl
3
, δ ppm): 7.82 (d, J = 7.6 Hz, 2H), 7.74 (d,
2
Cl
2
, δ ppm): 159.0, 147.4, 146.8, 143.7, 139.0, 133.1, 128.3, 126.2,
J = 7.6 Hz, 2H), 7.48 – 7.42 (m, 6H), 7.36 – 7.32 (m, 4H), 7.23 (d, J = 7.5
Hz, 2H), 7.14 (d, J = 8.0 Hz, 2H), 6.95 (t, J = 8.0 Hz,, 4H), 6.59 (s, 2H),
1
2
7
23.3, 122.5, 122.5, 121.5, 119.4, 119.1, 113.2, 32.0, 31.8, 30.6, 29.1,
+
2.8, 14.1. HRMS (MALDI-TOF/MS, m/z): [M ] calcd for C46
42 2 2 2 2
H B N O S
6
1
1
.29 (s, 2H), 2.69 (t, J = 7.6 Hz, 4H), 1.59 - 1.56 (m, 4H), 1.34 – 1.24 (m,
40.2874; found 740.1241.
13
2H), 0.88 (t, J = 5.9 Hz, 6H). C NMR (100 MHz, CDCl
3
, δ ppm): 147.2,
42.5, 141.2, 140.42, 140.4, 136.8, 134.5, 131.5, 129.8, 128.1, 126.1,
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