J
Synthesis
K. Skonieczny et al.
Special Topic
3-(Hexyloxy)-2,9,10,13-tetramethoxy-5,6-diphenylimidazo[1,2-
HRMS (ESI): m/z [M + H]+ calcd for C75H75N O : 1095.5788; found:
4
4
f]naphtho[1,2,3,4-lmn]phenanthridine (16)
1095.5798.
Following GP2 using 15 (85 mg, 0.13 mmol, 1 equiv), PIFA (136 mg,
0
.32 mmol, 2.5 equiv), and BF ·Et O (40 μL, 0.32 mmol, 2.5 equiv) in
2,5-Bis[1-(3,4-bis(hexyloxy)phenyl]-4,5-diphenyl-1H-imidazol-2-
yl)thieno[3,2-b]thiophene (19)
3
2
dry toluene (20 mL). The product was isolated by chromatography
silica gel, hexanes/EtOAc, 3:1). Crystallization (EtOAc/hexane) afford-
(
Following GP1 using thieno[3,2-b]thiophene-2,5-dicarbaldehyde (65
mg, 0.33 mmol), 3,4-bis(hexyloxy)aniline (293 mg, 1.00 mmol), ben-
ed a white crystalline solid; yield: 69 mg (82%); mp 77–78 °C.
1
H NMR (500 MHz, CDCl ): δ = 9.30 (d, J = 2.7 Hz, 1 H), 8.50 (d, J = 9.2
zil (140 mg, 0.66 mmol), and NH OAc (256 mg, 3.33 mmol) in
4
3
Hz, 1 H), 8.20 (s, 1 H), 7.73–7.69 (m, 2 H), 7.68–7.61 (m, 4 H), 7.60–
AcOH/toluene (2:1, 30 mL). The product was isolated by chromatogra-
7
2
.56 (m, 1 H), 7.34 (s, 1 H), 7.32 (dd, J = 9.0, 2.7 Hz, 1 H), 7.29–7.24 (m,
H), 7.23–7.19 (m, 1 H), 4.44 (t, J = 6.9 Hz, 2 H), 4.17 (s, 3 H), 4.00 (s, 3
phy (silica gel, hexanes/EtOAc, 6:1). Crystallization (EtOAc/hexane)
afforded a yellow crystalline solid; yield: 110 mg (29%); mp 263–
H), 3.85 (s, 3 H), 3.38 (s, 3 H), 2.26–2.17 (m, 2 H), 1.69–1.62 (m, 2 H),
264 °C.
1
.50–1.36 (m, 4 H), 0.94 (t, J = 7.1 Hz, 3 H).
1
H NMR (400 MHz, CDCl ): δ = 7.58 (d, J = 7.2 Hz, 4 H), 7.25–7.14 (m,
3
13
C NMR (125 MHz, CDCl ): δ = 158.6, 153.0, 150.7, 145.1, 143.8,
16 H), 6.83 (d, J = 6.8 Hz, 4 H), 6.79 (dd, J = 8.4, 2.1 Hz, 2 H), 6.68 (d, J =
1.9 Hz, 2 H), 4.01 (t, J = 6.6 Hz, 4 H), 3.81 (t, J = 5.7 Hz, 4 H), 1.89–1.80
(m, 4 H), 1.73–1.65 (m, 4 H), 1.55–1.45 (m, 4 H), 1.41–1.26 (m, 20 H),
0.93 (t, J = 7.0 Hz, 6 H), 0.89 (t, J = 6.8 Hz, 6 H).
3
141.4, 140.3, 134.8, 134.1, 132.1, 129.9, 129.7, 129.2, 128.6, 127.9,
127.8, 126.8, 125.0, 124.4, 124.3, 124.2, 123.0, 117.2, 117.1, 116.4,
113.4, 110.4, 106.8, 101.3, 73.7, 60.4, 57.0, 55.3, 55.1, 32.0, 30.5, 25.8,
22.8, 14.2.
13
C NMR (100 MHz, CDCl ): δ = 149.8, 149.1, 142.2, 139.8, 138.4,
3
HRMS (EI): m/z [M]+ calcd for C43H40N O : 664.2937; found:
135.5, 134.2, 131.7, 130.9, 130.4, 128.8, 128.3, 128.1, 128.0, 127.3,
126.7, 121.3, 117.9, 114.1, 112.8, 69.3, 69.2, 31.6, 31.5, 29.2, 28.9,
2
5
664.2941.
25.7, 25.5, 22.6, 22.5, 14.0 (2 signals).
+
2,2′-(9,9-Dioctyl-9H-fluorene-2,7-diyl)bis(1-(3,4-dimethoxyphe-
HRMS (ESI): m/z [M + H] calcd for C72H81N O S : 1129.5699; found:
4
4 2
nyl)-4,5-diphenyl-1H-imidazole (17)
1129.5707.
Following GP1 using 9,9-dioctyl-9H-fluorene-2,7-dicarbaldehyde
(500 mg, 0.91 mmol), 3,4-dimethoxyaniline (418 mg, 2.73 mmol),
ImPhen 20
benzil (383 mg, 1.82 mmol), and NH OAc (702 mg, 9.11 mmol) in
4
Following GP2 using 19 (26 mg, 0.02 mmol, 1 equiv), PIFA (47 mg,
.11 mmol, 5 equiv), and BF ·Et O (28 μL, 0.22 mmol, 10 equiv) in dry
AcOH/toluene (4:1, 50 mL. The product was isolated by chromatogra-
phy (silica gel, hexanes/EtOAc, 4:1). Crystallization (EtOAc/hexane)
afforded a yellow crystalline solid; yield: 0.72 g (72%); mp 145–
0
3
2
toluene (20 mL). Crystallization (CHCl /hexane) afforded a yellow
3
crystalline solid which is unstable in the presence of strong daylight;
yield: 21 mg (81%); mp 302–304 °C.
146 °C.
1
H NMR (500 MHz, CDCl ): δ = 7.62 (d, J = 7.4 Hz, 4 H), 7.58–7.52 (m, 4
1
3
H NMR (500 MHz, CDCl ): δ = 7.69–7.61 (m, 8 H), 7.61–7.53 (m, 8 H),
3
H), 7.36 (s, 2 H), 7.28–7.18 (m, 12 H), 7.16 (dd, J = 7.7, 1.6 Hz, 4 H),
7.29–7.20 (m, 6 H), 6.97 (s, 2 H), 4.20 (t, J = 6.3 Hz, 4 H), 3.31 (t, J = 6.8
6
2
1
0
.70 (d, J = 8.5 Hz, 2 H), 6.65 (dd, J = 8.5, 2.2 Hz, 2 H), 6.52 (d, J = 2.3 Hz,
H), 3.84 (s, 6 H), 3.56 (s, 6 H), 1.69–1.62 (m, 4 H), 1.24–1.17 (m, 4 H),
.17–1.05 (m, 8 H), 1.01–0.89 (m, 8 H), 0.82 (t, J = 7.2 Hz, 6 H), 0.44–
.36 (m, 4 H).
Hz, 4 H), 1.95–1.87 (m, 4 H), 1.69–1.62 (m, 4 H), 1.62–1.54 (m, 4 H),
1.44–1.33 (m, 20 H), 1.00–0.93 (m, 12 H).
13
C NMR (125 MHz, CDCl ): δ = 148.8, 146.9, 140.1, 134.5, 133.8,
3
133.6, 132.6, 129.5, 129.2, 128.1 (2 signals), 127.8, 127.0, 124.3, 113.7,
13
C NMR (125 MHz, CDCl ): δ = 150.6, 149.0, 148.7, 147.3, 140.6,
3
108.0, 102.2, 69.7, 68.3, 31.8, 31.6, 29.3, 28.9, 25.9, 25.5, 22.7, 14.0.
138.2, 134.5, 131.1, 130.9, 130.2, 129.4, 128.4, 128.2, 127.9, 127.4,
126.6, 123.0, 120.6, 119.7, 111.8, 110.6, 55.9, 55.8, 55.0, 40.3, 31.9,
30.0, 29.4, 29.3, 23.8, 22.6, 14.1.
+
HRMS (ESI): m/z [M + H] calcd for C72H77N O S : 1125.5386; found:
4
4 2
1125.5393.
HRMS (ESI): m/z [M + H]+ calcd for C75H79N O : 1099.6101; found:
4
4
2
-(4,7-Dimethoxynaphthalen-1-yl)-1-(3,4-dimethoxyphenyl)-4,5-
1099.6108.
diphenyl-1H-imidazole (21)
Following GP1 using 4,7-dimethoxy-1-naphthaldehyde (108 mg, 0.5
mmol), 3,4-dimethoxyaniline (115 mg, 0.75 mmol), benzil (105 mg,
ImPhen 18
Following GP2 using 17 (100 mg, 0.09 mmol, 1 equiv), PIFA (195 mg,
.45 mmol, 5 equiv), and BF ·Et O (115 μL, 0.90 mmol, 10 equiv) in
0
.5 mmol), and NH OAc (193 mg, 2.5 mmol) in AcOH (30 mL). The
4
0
3
2
product was isolated by chromatography (silica gel, hexanes/EtOAc,
:1). Crystallization (EtOAc/pentane) afforded a white crystalline sol-
dry toluene (20 mL). The product was isolated by chromatography
silica gel, hexanes/EtOAc, 3:1 to 2:1). Crystallization (hexane) afford-
3
(
id; yield: 153 mg (73%); mp 181–182 °C.
ed a white crystalline solid; yield: 88 mg (88%); mp 337–339 °C.
1
H NMR (600 MHz, CDCl ): δ = 8.16 (d, J = 9.2 Hz, 1 H), 7.69–7.66 (m, 2
3
1
H NMR (500 MHz, CDCl ): δ = 8.92 (s, 2 H), 8.79 (s, 2 H), 8.06 (s, 2 H),
3
H), 7.52 (d, J = 1.7 Hz, 1 H), 7.29–7.22 (m, 8 H), 7.19 (t, J = 7.3 Hz, 1 H),
7.69–7.65 (m, 4 H), 7.65–7.57 (m, 8 H), 7.57–7.52 (m, 2 H), 7.29 (t, J =
7.10 (dd, J = 9.2, 2.5 Hz, 1 H), 6.54 (d, J = 8.0 Hz, 1 H), 6.49 (d, J = 8.6 Hz,
1 H), 6.41 (dd, J = 8.5, 2.4 Hz, 1 H), 6.36 (d, J = 2.3 Hz, 1 H), 3.94 (s, 3 H),
3.83 (s, 3 H), 3.72 (s, 3 H), 3.37 (s, 3 H).
7.4 Hz, 4 H), 7.25–7.20 (m, 2 H), 7.02 (s, 2 H), 4.12 (s, 6 H), 3.31 (s, 6
H), 2.39–2.31 (m, 4 H), 1.13–0.99 (m, 16 H), 0.98–0.91 (m, 4 H), 0.74
(t, J = 7.1 Hz, 6 H), 0.72–0.65 (m, 4 H).
13
C NMR (150 MHz, CDCl ): δ = 158.6, 156.3, 148.3, 148.0, 146.5,
3
13
C NMR (125 MHz, CDCl ): δ = 151.3, 149.3, 146.4, 142.9, 141.5,
3
135.2, 131.1, 130.6, 129.5, 128.5, 128.1, 127.9, 127.3, 126.5, 123.8,
20.7, 119.9, 117.0, 111.2, 110.2, 105.1, 101.2, 55.7, 55.6, 55.4, 55.3.
HRMS (EI): m/z [M] calcd for C35H30N O : 542.2206; found: 542.2210.
134.6, 133.6, 132.3, 129.5, 129.2, 128.2 (2 signals), 128.0, 127.2, 127.0,
124.6, 123.2, 118.9, 116.3, 112.7, 106.5, 101.1, 56.9, 55.8, 55.0, 41.4,
31.8, 30.1, 29.5, 29.2, 24.2, 22.5, 14.0.
1
2
4
©
Georg Thieme Verlag Stuttgart · New York — Synthesis 2017, 49, A–L