F
Z. Hassan et al.
Paper
Synthesis
13C NMR (75.5 MHz, CDCl3): δ = 13.7, 13.8 (CH3), 19.1, 19.2 (CH2),
30.5, 30.6 (CH2), 55.8 (OCH3), 65.5, 65.7 (OCH2), 112.1, 120.5, 122.5
(CH), 124.9, 125.3, 125.4, 128.2 (C), 129.6, 130.6 (CH), 130.7, 133.0,
134.2, 136.3, 138.9, 139.8, 155.9, 161.0, 162.0 (C).
GC-MS (EI, 70 eV): m/z (%) = 564 (100) ([M]+, 2 × 35Cl), 491 (24), 477
(36), 463 (11), 421 (31), 381 (37), 325 (24).
2,7-Bis(butoxycarbonyl)-3-chloro-6-(4-chlorophenyl)benzo[1,2-
b:6,5-b′]dithiophene (6e)
Starting with 3a (200 mg, 0.43 mmol), 4-chlorophenylboronic acid
(5e) (1.2 equiv, 78 mg, 0.52 mmol), Pd(PPh3)4 (25 mg, 5 mol%), K3PO4
(2.0 equiv, 185 mg, 0.85 mmol), and 1,4-dioxane (5 mL), following
general procedure B, 6e was isolated as a light green viscous oil (220
mg, 82%).
1H NMR (600 MHz, CDCl3): δ = 0.88 (t, J = 7. 3 Hz, 3 H, CH3), 0.99 (t, J =
7.2 Hz, 3 H, CH3), 1.29–1.49 (m, 2 H), 1.50–1.54 (m, 2 H), 1.55–1.64
(m, 2 H, CH2), 1.75–1.80 (m, 2 H, CH2), 4.19 (t, 2 H, OCH2), 4.37 (t, 2 H,
OCH2), 7.34 (d, J = 8.2 Hz, 2 H), 7.87 (d, J = 8.3 Hz, 2 H), 7.51 (d, J = 8.8
Hz, 1 H), 7.81 (d, J = 8.7 Hz, 1 H).
13C NMR (150 MHz, CDCl3): δ = 13.7, 13.8 (CH3), 19.1, 19.3 (CH2), 31.1,
31.3 (CH2), 65.2, 65.5 (OCH2), 112.8, 120.1, 122.1 (C), 125.1, 125.8
(CH), 127.0, 127.9 (C), 131.3 (CH), 133.1 (C), 134.0 (CH), 135.4, 140.2,
143.6, 148.6, 161.0, 162.2.
HRMS (EI, 70 eV): m/z [M]+ calcd for C27H2635Cl2O5S2: 564.0593;
found: 564.0594.
2,7-Bis(butoxycarbonyl)-3-chloro-6-(2-methoxyphenyl)ben-
zo[1,2-b:6,5-b′]dithiophene (6c)
Starting with 3a (200 mg, 0.43 mmol), 2-methoxyphenylboronic acid
(5c) (1.2 equiv, 78 mg, 0.52 mmol), Pd(PPh3)4 (25 mg, 5 mol%), K3PO4
(2.0 equiv, 185 mg, 0.85 mmol), and 1,4-dioxane (5 mL), following
general procedure B, 6c was isolated as a light green, highly viscous
oil (180 mg, 80%).
IR (KBr): 2957, 2930, 2872, 1716, 1698 (s), 1547, 1531, 1501, 1486,
1462, 1413, 1337, 1311 (m), 1274, 1228, 1175, 1123, 1114, 1071 (s),
2,7-Bis(butoxycarbonyl)-3-chloro-6-(5-formyl-2-thienyl)ben-
zo[1,2-b:6,5-b′]dithiophene (6f)
906, 875, 727 (s) cm–1
.
Starting with 3a (200 mg, 0.43 mmol), 5-formyl-2-thienylboronic
acid (5f) (1.2 equiv, 80 mg, 0.51 mmol), Pd(PPh3)4 (25 mg, 5 mol%),
K3PO4 (2.0 equiv, 185 mg, 0.85 mmol), and 1,4-dioxane (5 mL), follow-
ing general procedure B, 6f was isolated as a yellowish oil (170 mg,
72%).
1H NMR (600 MHz, CDCl3): δ = 0.90 (t, J = 7.4 Hz, 3 H), 0.99 (t, J = 7.3
Hz, 3 H), 1.31–1.34 (m, 2 H), 1.49–1.53 (m, 2 H), 1.58–1.63 (m, 2 H),
1.76–1.81 (m, 2 H), 4.25 (t, J = 6.5 Hz, 2 H), 4.39 (t, J = 6.7 Hz, 2 H), 7.29
(d, J = 3.8 Hz, 1 H), 7.66 (d, J = 8.8 Hz, 1 H), 7.86 (d, J = 3.8 Hz, 1 H), 7.90
(d, J = 8.8 Hz, 1 H), 9.98 (s, 1 H).
13C NMR (150 MHz, CDCl3): δ = 13.6, 13.7 (CH3), 19.1, 19.2 (CH2), 30.4,
30.6 (CH2), 65.8, 65.9 (OCH2), 121.2, 122.1, 126.1, 128.2 (C), 130.3
(CH), 131.8, 132.9, 134.1, 134.6 (C), 135.9 (CH), 136.7, 139.6, 143.7,
145.0, 160.8, 161.3 (C), 182.8 (CH).
1H NMR (300 MHz, CDCl3): δ = 0.79 (t, J = 7.3 Hz, 3 H, CH3), 0.92 (t, J =
7.3 Hz, 3 H, CH3), 1.11–1.20 (m, 2 H), 1.40–1.46 (m, 4 H), 1.66–1.74
(m, 2 H), 3.61 (s, 3 H, OCH3), 4.10 (t, J = 6.3 Hz, 2 H), 4.31 (t, J = 6.5 Hz,
2 H), 6.95 (d, J = 8.3 Hz, 1 H), 7.01 (td, J = 7.4, 1.2 Hz, 1 H), 7.17 (dd, J =
7.4, 1.7 Hz, 1 H), 7.34–7.39 (m, 2 H), 7.71 (d, J = 8.8 Hz, 1 H).
13C NMR (75.5 MHz, CDCl3): δ = 13.7, 13.8 (CH3), 19.1, 19.2 (CH2),
30.5, 30.6 (CH2), 55.8 (OCH3), 65.5, 65.7 (OCH2), 110.9, 120.2, 120.5
(CH), 123.2, 125.2 (CH), 128.2 (C), 129.9 (CH), 130.1 (C), 130.9 (CH),
133.0, 134.1, 136.1, 140.2, 140.7, 157.1, 161.0, 162.2.
GC-MS (EI, 70 eV): m/z (%) = 530 (100) ([M]+, 35Cl), 457 (49), 443 (33),
381 (37), 325 (21).
HRMS (EI, 70 eV): m/z [M]+ calcd for C27H2735ClO5S2: 530.0982; found:
530.0981.
2,7-Bis(butoxycarbonyl)-3-chloro-6-(4-methoxyphenyl)ben-
zo[1,2-b:6,5-b′]dithiophene (6d)
2,7-Bis(butoxycarbonyl)-3,6-bis(4-methoxyphenyl)benzo[1,2-
b:6,5-b′]dithiophene (7a)
Starting with 3a (200 mg, 0.43 mmol), 4-methoxyphenylboronic acid
(5d) (1.2 equiv, 78 mg, 0.52 mmol), Pd(PPh3)4 (25 mg, 5 mol%), K3PO4
(2.0 equiv, 185 mg, 0.85 mmol), and 1,4-dioxane (5 mL), following
general procedure B, 6d was isolated as a light greenish oil (170 mg,
74%).
Starting with 3a (100 mg, 0.21 mmol), 4-methoxyphenylboronic acid
(5d) (2.5 equiv, 80 mg, 0.53 mmol), NiCl2(dppe) (6.0 mg, 5 mol%), K3-
PO4 (4.0 equiv, 185 mg, 0.87 mmol), and toluene (5 mL), following the
general procedure B, 7a was isolated as a yellowish viscous solid (115
mg, 88%).
IR (KBr): 2930, 2872, 1716 (s), 1531, 1501, 1486, 1413, 1337, 1311
1H NMR (600 MHz, CDCl3): δ = 0.89 (t, J = 7.4 Hz, 6 H, CH3), 1.26–1.32
(m, 4 H), 1.56–1.60 (m, 4 H), 3.86 (s, 6 H, OCH3), 4.20 (t, J = 6.5 Hz, 4 H,
OCH2), 7.01 (d, J = 8.4 Hz, 4 H), 7.32 (d, J = 8.4 Hz, 4 H), 7.41 (s, 2 H).
13C NMR (150 MHz, CDCl3): δ = 13.7 (CH3), 19.1 (CH2), 30.5 (CH2), 55.2
(OCH3), 65.3 (OCH2), 113.5, 122.1, 126.5 (CH), 128.0, 131.0, 134.3,
139.5, 144.5, 159.6, 162.4 (C).
(m), 1274, 1175, 1114, 1071 (s), 906, 875 (s) cm–1
.
1H NMR (600 MHz, CDCl3): δ = 0.88 (t, J = 7.3 Hz, 3 H), 0.99 (t, J = 7.1
Hz, 3 H), 1.50–1.54 (m, 2 H), 1.50–1.54 (m, 2 H), 1.55–1.64 (m, 2 H),
1.75–1.80 (m, 2 H), 3.87 (s, 3 H, OCH3), 4.19 (t, J = 6.3 Hz, 2 H), 4.37 (t,
J = 6.2 Hz, 2 H), 7.02 (d, J = 8.5 Hz, 2 H), 7.33 (d, J = 8.5 Hz, 2 H), 7.53 (d,
J = 8.8 Hz, 1 H), 7.77 (d, J = 8.8 Hz, 1 H).
13C NMR (150 MHz, CDCl3): δ = 13.6, 13.7 (CH3), 19.1, 19.2 (CH2), 30.4,
30.5 (CH2), 55.2 (OCH3), 65.3, 65.6 (OCH2), 113.5, 120.3, 122.8 (C),
125.3, 126.1 (CH), 128.1, 128.6 (C), 130.9 (CH), 132.8 (C), 134.1 (CH),
136.2, 140.2, 144.3, 159.6, 160.9, 162.1.
HRMS (EI, 70 eV): m/z [M]+ calcd for C34H34O6S2: 602.1764; found:
602.1764.
2,7-Bis(butoxycarbonyl)-3,6-bis(5-chloro-2-methoxyphenyl)ben-
zo[1,2-b:6,5-b′]dithiophene (7b)
Starting with 3a (100 mg, 0.21 mmol), 5-chloro-2-methoxyphenylbo-
ronic acid (2.5 equiv, 99 mg, 0.53 mmol), NiCl2(dppe) (6.0 mg, 5
mol%), K3PO4 (4.0 equiv, 185 mg, 0.87 mmol), and toluene (5 mL), fol-
lowing the general procedure B, 7b was isolated as a light greenish
solid (107 mg, 74%).
© Georg Thieme Verlag Stuttgart · New York — Synthesis 2016, 48, A–H