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W. Liu et al.
SPECIAL TOPIC
1,3,4-Triphenylisoquinoline (3aa);7e Typical Procedure
15-mL, oven-dried, N2-purged flask was charged with
6-Chloro-1-(4-chlorophenyl)-3,4-diphenylisoquinoline (3da)
This was prepared from hydrazone 1d (120.4 mg, 0.3 mmol),
RhCp*(MeCN)3(SbF6)2 (2.5 mg, 0.009 mmol), PhC≡CPh (64.2 mg,
0.36 mmol), and Cu(OAc)2·H2O (125.7 mg, 0.63 mmol) in toluene
(1.5 mL) for 28 h at 90 °C. Purification by column chromatography
[silica gel, PE–EtOAc (30:1)] gave a colorless solid; yield: 95.9 mg
(75%); mp 179–180 °C.
A
RhCp*(MeCN)3(SbF6)2 (2.5 mg, 0.009 mmol) and Cu(OAc)2·H2O
(125.7 mg, 0.63 mmol) then a soln of hydrazone 1a (99.7 mg, 0.3
mmol) and PhC≡CPh (64.2 mg, 0.36 mmol) in toluene (1.5 mL) was
added. The mixture was stirred at 90 °C for 18 h, cooled to r.t., and
diluted with EtOAc (10 mL) and H2O (30 mL). The aqueous layer
was separated and extracted with EtOAc (3 × 10 mL). The organic
phases were combined, dried (Na2SO4), filtered, and concentrated
in vacuo. The residue was purified by column chromatography [sil-
ica gel, PE–EtOAc (30:1)] to give a colorless solid; yield: 99.7 mg
(93%); mp 195–197 °C.
IR (KBr): 3056, 3027, 1946, 1602, 1538, 1493, 1443, 1403, 1381,
1328, 1090, 981, 839 cm–1.
1H NMR (500 MHz, CDCl3): δ = 8.08 (d, J = 9.0 Hz, 1 H), 7.75 (d,
J = 8.0 Hz, 2 H), 7.70 (d, J = 2.0 Hz, 1 H), 7.54 (d, J = 8.5 Hz, 2
H), 7.32 (dd, J = 9.0 Hz, 2.0 Hz, 1 H), 7.43–7.38 (m, 5 H), 7.28 (d,
J = 2.0 Hz, 1 H), 7.26 (s, 1 H), 7.21–7.19 (m, 3 H).
13C NMR (125 MHz, CDCl3): δ = 158.5, 150.9, 140.3, 138.1, 137.8,
136.7, 136.7, 135.1, 131.6, 131.2, 130.4, 129.3, 129.0, 128.7,
128.7,, 127.8, 127.8, 127.7, 127.4, 125.1, 123.6.
IR (KBr): 3054, 1610, 1540, 1386, 1336, 1073, 1030, 981, 1073,
1030, 981 cm–1.
1H NMR (500 MHz, CDCl3): δ = 8.19 (d, J = 8.5 Hz, 1 H), 7.83 (d,
J = 7.0 Hz, 2 H), 7.73 (d, J = 8.5 Hz, 1 H), 7.62 (t, J = 7.0 Hz, 1 H),
7.58–7.51 (m, 4 H), 7.44–7.37 (m, 5 H), 7.30 (d, J = 6.5 Hz, 2 H),
7.21–7.16 (m, 3 H).
13C NMR (125 MHz, CDCl3): δ = 159.8, 149.6, 140.8, 139.7, 137.5,
137.1, 131.4, 130.5, 130.3, 130.1, 129.9, 128.7, 128.4, 128.4, 127.6,
127.4, 127.1, 126.7, 126.1, 125.5.
MS (EI): m/z (%) 429 (8) [M+ (37Cl)], 428 (20), 427 (42) [M+ (37Cl,
35Cl)], 426 (79), 425 (61) [M+ (35Cl)], 424 (100).
Anal. Calcd for C27H17Cl2N: C, 76.06; H, 4.02; N, 3.29. Found: C,
75.79; H, 4.03; N, 3.04.
LC/MS (ESI): m/z 358 [M + H]+.
6-Fluoro-1-(4-fluorophenyl)-3,4-diphenylisoquinoline (3ea)
This was prepared hydrazone 1e (110.5 mg, 0.3 mmol),
RhCp*(MeCN)3(SbF6)2 (2.5 mg, 0.009 mmol), PhC≡CPh (64.2 mg,
0.36 mmol), and Cu(OAc)2·H2O (125.7 mg, 0.63 mmol) in toluene
(1.5 mL) for 25 h at 90 °C. Purification by column chromatography
[silica gel, PE–EtOAc (30:1)] gave a colorless solid; yield: 94.4 mg
(80%); mp 171–174 °C.
6-Methyl-3,4-diphenyl-1-(4-tolyl)isoquinoline (3ba)
This was prepared from hydrazone 1b (108.1 mg, 0.3 mmol),
RhCp*(MeCN)3(SbF6)2 (2.5 mg, 0.009 mmol), PhC≡CPh (64.2 mg,
0.36 mmol), and Cu(OAc)2·H2O (125.7 mg, 0.63 mmol) in toluene
(1.5 mL) for 15 h at 90 °C. Purification by column chromatography
[silica gel, PE–EtOAc (30:1)] gave a colorless solid; yield: 102.8
mg (89%); mp 167–169 °C.
IR (KBr): 3070, 1899, 1622, 1601, 1501, 1383, 1332, 1256, 1221,
1180, 1158, 1111, 987, 846 cm–1.
1H NMR (500 MHz, DMSO-d6): δ = 8.20 (dd, J = 9.0, 6.0 Hz, 1 H),
7.87–7.83 (m, 2 H), 7.60 (td, J = 9.0, 2.5 Hz, 1 H), 7.48–7.41 (m, 5
H), 7.40–7.37 (m, 2 H), 7.33–7.31 (m, 2 H), 7.25–7.21 (m, 3 H),
7.17 (dd, J = 11.0, 2.5 Hz, 1 H).
IR (KBr): 3050, 2920, 1915, 1770, 1615, 1541, 1492, 1444, 1377,
1328, 983, 706 cm–1.
1H NMR (500 MHz, CDCl3): δ = 8.14 (d, J = 8.5 Hz, 1 H), 7.76 (d,
J = 8.0 Hz, 2 H), 7.51 (s, 1 H), 7.46–7.36 (m, 8 H), 7.33–7.31 (m, 2
H), 7.23–7.17 (m, 3 H), 2.50 (s, 3 H), 2.46 (s, 3 H).
13C NMR (125 MHz, CDCl3): δ = 159.5, 149.7, 141.0, 140.4, 138.4,
137.8, 137.3, 137.0, 131.5, 130.5, 130.2, 129.2, 129.0, 128.8, 128.3,
127.6, 127.5, 127.2, 127.0, 124.9, 123.9, 22.2, 21.4.
13C NMR (125 MHz, CDCl3): δ = 163.3 (d, 1JF–C = 248 Hz), 163.2
(1JF–C = 252 Hz), 158.6, 150.6, 140.5, 139.1 (3JF–C = 10.0 Hz),
137.0, 135.6, 132.1, 132.0, 131.2, 130.5 (3JF–C = 10.0 Hz), 130.4,
129.7 (4JF–C = 5.0 Hz), 128.7, 127.7, 127.4, 122.7, 117.1 (2JF–C
=
MS (EI): m/z (%) 385 (69) [M+], 384 (100).
25.0 Hz), 115.5 (2JF–C = 21.3 Hz), 109.8 (2JF–C = 21.3 Hz).
HRMS (EI) m/z [M+] calcd for C29H23N: 385.1830; found:
385.1834.
19F NMR (470 MHz, CDCl3): δ = –106.9 (s, Ar-F), –112.7 (s, Ar-F).
MS (EI): m/z (%) 393 (69) [M+], 392 (100).
6-Methoxy-1-(4-methoxyphenyl)-3,4-diphenylisoquinoline
(3ca)
HRMS (EI) m/z [M+] calcd for C27H17F2N: 393.1329; found:
393.1330.
This was prepared from hydrazone 1c (117.7 mg, 0.3 mmol),
RhCp*(MeCN)3(SbF6)2 (2.5 mg, 0.009 mmol), PhC≡CPh (64.2 mg,
0.36 mmol), and Cu(OAc)2·H2O (125.7 mg, 0.63 mmol) in toluene
(1.5 mL) for 14 h at 90 °C. Purification by column chromatography
[silica gel, PE–EtOAc (10:1)] gave a colorless solid; yield: 102.7
mg (82%); mp 168–172 °C.
7-Methyl-3,4-diphenyl-1-(3-tolyl)isoquinoline (3fa)
This was prepared from 1f (108.1 mg, 0.3 mmol),
RhCp*(MeCN)3(SbF6)2 (2.5 mg, 0.009 mmol), PhC≡CPh (64.2 mg,
0.36 mmol), and Cu(OAc)2·H2O (125.7 mg, 0.63 mmol) in toluene
(1.5 mL) for 22 h at 90 °C. Purification by column chromatography
[silica gel, PE–EtOAc (30:1)] gave a colorless solid; yield: 97.1 mg
(84%); mp 161–162 °C.
IR (KBr): 3053, 2837, 2048, 1958, 1609, 1514, 1407, 1251, 1219,
1178, 1032, 840, 706 cm–1.
IR (KBr): 3054, 2917, 1960, 1542, 1504, 1382, 1320, 832 cm–1.
1H NMR (500 MHz, CDCl3): δ = 8.14 (d, J = 9.0 Hz, 1 H), 7.78 (d,
J = 8.5 Hz, 2 H), 7.43–7.41 (m, 2 H), 7.39 (d, J = 7.0 Hz, 2 H), 7.36
(d, J = 7.0 Hz, 1 H), 7.34–7.30 (m, 2 H), 7.21–7.14 (m, 4 H), 7.09
(d, J = 8.5 Hz, 2 H), 6.98 (d, J = 2.0 Hz, 1 H), 3.91 (s, 3 H), 3.74 (s,
3 H).
1H NMR (500 MHz, DMSO-d6): δ = 7.86 (s, 1 H), 7.59 (dd, J1 = 8.5
Hz, J2 = 1.5 Hz, 1 H), 7.56 (s, 1 H), 7.53–7.47 (m, 3 H), 7.45–7.34
(m, 6 H), 7.31 (d, J = 1.5 Hz, 1 H), 7.29 (t, J = 1.5 Hz, 1 H), 7.22–
7.19 (m, 3 H), 2.46 (s, 3 H), 2.45 (s, 3 H).
13C NMR (125 MHz, CDCl3): δ = 138.1, 137.7, 136.6, 135.3, 132.3,
131.4, 130.8, 130.5, 129.7, 129.3, 128.3, 128.1, 127.5, 127.4, 127.3,
126.9, 126.4, 125.9, 125.7, 21.9, 21.6.
13C NMR (125 MHz, CDCl3): δ = 160.6, 160.1, 158.8, 150.1, 139.2,
137.9, 131.6, 131.3, 130.5, 129.6, 128.8, 128.4, 127.5, 127.3, 127.0,
121.2, 118.8, 113.8, 104.3, 55.5, 55.3.
MS (EI): m/z (%) 385 (67) [M+], 384 (100).
MS (EI): m/z (%) 417 (73) [M+], 416 (100).
Anal. Calcd for C29H23N: C, 90.35; H, 6.01; N, 3.63. Found: C,
90.36; H, 5.86; N, 3.49.
Anal. Calcd for C29H23NO2: C, 83.43; H, 5.55; N, 3.35. Found: C,
83.56; H, 5.54; N, 3.42.
Synthesis 2013, 45, 2137–2149
© Georg Thieme Verlag Stuttgart · New York