M.M. Maluleka, M.J. Mphahlele / Tetrahedron 69 (2013) 699e704
703
3
884.6, 1213.6, 1378.9, 1512.8, 1582.6 cmꢀ1
;
dH (300 MHz, CDCl3)
118.7, 118.8, 128.5 (2ꢂC), 128.6 (d, JCF 8.3 Hz), 129.1, 129.9, 132.2
3 4 4
7.32e7.47 (m, 8H), 7.52 (t, J 7.8 Hz, 2H), 7.65e7.73 (m, 4H), 7.81 (d, J
2.1 Hz, 1H), 7.97 (d, J 2.1 Hz, 1H), 8.37 (s, 1H), 9.26 (s, 1H); dC
(d, JCF 8.0 Hz), 135.8 (d, JCF 3.4 Hz), 135.9, 136.0 (d, JCF 3.4 Hz),
137.3, 139.3, 139.7, 141.6, 142.7, 145.3, 162.5 (d, 1JCF 245.3 Hz), 162.8
(d, 1JCF 246.7 Hz); m/z 470 (37%, C28H17N3F237Clþ), 468.1085 (100%,
C28H17N3F235Clþ); HRMS (ES): MHþ, found C28H17N335ClFþ2 requires
468.1085.
2
(75 MHz, CDCl3) 116.7 (d, JCF 23.0 Hz), 116.8, 118.4, 118.8, 127.0,
3
127.6, 127.9, 128.0, 129.0, 129.2 (d, JCF 8.8 Hz), 129.5, 130.6, 135.6,
3
136.9 (d, JCF 3.0 Hz), 138.3, 139.8 (2ꢂC), 140.2, 142.5, 142.9, 145.2,
1
163.1 (d, JCF 249.3 Hz); m/z 416 (100%, MHþ); HRMS (ES): MHþ,
found 416.1560. C28H19N3Fþ requires 416.1563.
4.1.5.6. 6,8-Bis(4-fluorophenyl)-1-(4-methoxyphenyl)-1H-pyr-
azolo[4,3-c]quinoline (5f). A mixture of 4c (0.50 g, 1.14 mmol), 4-
fluorophenylboronic acid (0.40 g, 2.86 mmol), PdCl2(PPh3)2
(0.041 g, 0.057 mmol), PCy3 (0.032 g, 0.114 mmol), and K2CO3
(0.314 g, 2.308 mmol) in DMFewater (20 mL) afforded 5f as a pink
solid (0.317 g, 60%), mp 256e258 ꢁC (ethanol); nmax (ATR) 802.4,
4.1.5.2. 1-(4-Chlorophenyl)-6,8-diphenyl-1H-pyrazolo[4,3-c]quin-
oline (5b). A mixture of 4b (0.50 g. 1.15 mmol), phenylboronic acid
(0.35 g, 2.87 mmol), PdCl2(PPh3)2 (0.04 g, 0.058 mmol), PCy3
(0.032 g, 0.115 mmol), and K2CO3 (0.317 g, 2.30 mmol) in DMFewater
(20 mL) afforded 5b as an off-white solid (0.320 g, 65%), mp
280e282 ꢁC (ethanol); nmax (ATR) 797.7, 822.3, 833.4, 866.9, 1090.1,
1220.3, 1378.9, 1515.2, 1584.8, 1601.6 cmꢀ1
; dH (300 MHz, CDCl3)
3.96 (s, 3H), 7.08 (t, J 8.4 Hz, 2H), 7.16 (d, J 8.7 Hz, 2H), 7.20 (t, J
8.4 Hz, 2H), 7.41 (t, J 8.4 Hz, 2H), 7.58 (d, J 8.7 Hz, 2H), 7.68 (t, J
8.4 Hz, 2H), 7.78 (d, J 2.1 Hz, 1H), 7.87 (d, J 2.1 Hz, 1H), 8.37 (s, 1H),
1223.7, 1379.1, 1507.3, 1582.9 cmꢀ1
; dH (300 MHz, CDCl3) 7.35e7.55
(m, 8H), 7.65 (s, 4H), 7.71 (d, J 8.1 Hz, 2H), 7.83 (d, J 2.1 Hz,1H), 7.98 (d,
J 2.1 Hz,1H), 8.38 (s,1H), 9.26 (s,1H); dC (75 MHz, CDCl3) 116.7,118.6,
118.9 (2ꢂC),127.0,127.6,127.9,128.0,128.5,129.1,129.4,129.9,130.6,
135.7, 135.8, 138.3, 139.3, 139.8, 140.2, 142.5, 142.9, 145.2; m/z 434
(38%, C28H19N335Clþ), 432 (100%, MHþ); HRMS (ES): MHþ, found
432.1266. C28H19N335Clþ requires 432.1266.
2
9.26 (s, 1H); dC (75 MHz, CDCl3) 55.8, 114.8, 114.9 (d, JCF 21.3 Hz),
2
3
115.9 (d, JCF 21.3 Hz), 117.1, 118.3, 119.0, 128.5 (2ꢂC), 128.7 (d, JCF
8.2 Hz), 132.2 (d, 3JCF 8.1 Hz), 133.5, 135.2, 135.9 (d, 3JCF 3.6 Hz), 136.1
(d, JCF 3.5 Hz), 137.0, 139.7, 141.3, 142.6, 145.4, 160.6, 162.4 (d, 1JCF
3
255.1 Hz), 162.7 (d, JCF 246.2 Hz); m/z 464 (100%, MHþ); HRMS
1
(ES): MHþ, found 464.1576. C29H20N3OF2þ requires 464.1574.
4.1.5.3. 1-(4-Methoxyphenyl)-6,8-diphenyl-1H-pyrazolo[4,3-c]
quinoline (5c). A mixture of 4c (0.50 g, 1.154 mmol), phenylboronic
acid (0.35 g, 2.88 mmol), PdCl2(PPh3)2 (0.041 g, 0.057 mmol), PCy3
(0.032 g, 0.115 mmol), and K2CO3 (0.319 g, 2.308 mmol) in
DMFewater (20 mL) afforded 5c as a red solid (0.340 g, 69%), mp
238e240 ꢁC (ethanol); nmax (ATR) 696.6, 758.6, 847.7, 883.5, 1019.0,
4.1.5.7. 1-(4-Fluorophenyl)-6,8-bis[2-(4-fluorophenyl)ethenyl]-
1H-pyrazolo[4,3-c]quinoline (5g). A mixture of 4a (0.50 g,
1.19 mmol), trans-2-(4-fluorophenyl)vinylboronic acid (0.49 g,
2.97 mmol), PdCl2(PPh3)2 (0.04 g, 0.059 mmol), PCy3 (0.033 g,
0.119 mmol), and K2CO3 (0.328 g, 2.380 mmol) in DMFewater
(20 mL) afforded 5g as a light brown solid (0.43 g, 72%), mp
234e236 ꢁC (ethanol); nmax (ATR) 789.0, 813.1, 844.5, 956.6, 1156.1,
1027.4,1177.4,1528.4,1583.5 cmꢀ1
; dH (300 MHz, CDCl3) 3.95 (s, 3H),
7.16 (d, J 9.0 Hz, 2H), 7.31e7.55 (m, 8H), 7.59 (d, J 9.0 Hz, 2H), 7.72 (dd, J
1.5 and 7.8 Hz, 2H), 7.85 (d, J 1.8 Hz,1H), 7.96 (d, J 1.8 Hz, 1H), 8.36 (s,
1H), 9.25 (s, 1H); dC (75 MHz, CDCl3) 55.8, 114.9, 117.0, 118.2, 119.1,
127.1,127.5,127.7,128.0,128.6,128.9,129.2,130.6,133.6,135.2,137.9,
139.8, 139.9, 140.4, 142.3, 142.8, 145.3, 160.6; m/z 428 (100%, MHþ);
HRMS (ES): MHþ, found 428.1758. C29H22N3Oþ requires 428.1763.
1230.9, 1523.6, 1600.0 cmꢀ1
; dH (300 MHz, CDCl3) 6.92 (d, J 2.7 Hz,
2H), 7.07 (t, J 8.7 Hz, 2H), 7.09 (t, J 8.7 Hz, 2H), 7.30 (d, J 16.5 Hz, 1H),
7.38 (t, J 8.7 Hz, 2H), 7.45 (t, J 8.7 Hz, 2H), 7.52 (d, J 1.8 Hz,1H), 7.65 (t,
J 8.7 Hz, 2H), 7.66 (t, J 8.7 Hz, 2H), 8.13 (d, J 1.8 Hz, 1H), 8.37 (s, 1H),
8.46 (t, J 16.5 Hz, 1H), 9.24 (s, 1H); dC (75 MHz, CDCl3) 115.6 (d, 2JCF
2
2
21.6 Hz), 115.7 (d, JCF 21.6 Hz), 116.4, 116.6 (d, JCF 22.8 Hz), 118.3,
118.6, 122.8, 125.2, 127.3, 128.1 (d, 3JCF 8.0 Hz), 128.5 (d, 3JCF 8.0 Hz),
128.9, 129.2 (d, 3JCF 8.9 Hz), 129.6, 132.8 (d, 4JCF 3.5 Hz), 133.7 (d, 4JCF
3.2 Hz), 134.5, 135.6, 136.8 (d, 4JCF 3.4 Hz), 137.0, 139.4, 142.8, 144.2,
4.1.5.4. 1,6,8-Tris(4-fluorophenyl)-1H-pyrazolo[4,3-c]quinoline
(5d). A mixture of 4a (0.50 g, 1.19 mmol), 4-fluorophenylboronic
acid (0.42 g, 2.975 mmol), PdCl2(PPh3)2 (0.04 g, 0.059 mmol),
PCy3 (0.033 g, 0.119 mmol), and K2CO3 (0.328 g, 2.38 mmol) in
DMFewater (20 mL) afforded 5d as a light brown solid (0.380 g,
71%), mp 252e254 ꢁC (ethanol); nmax (ATR) 833.2, 858.0, 936.2,
1
1
1
162.5 (d, JCF 246.2 Hz), 162.6 (d, JCF 246.8 Hz), 163.0 (d, JCF
248.8 Hz); m/z 504 (100%, MHþ); HRMS (ES): MHþ, found 504.1688.
C32H21N3F3þ requires 504.1688.
1157.9, 1221.3, 1503.9, 1601.9 cmꢀ1
; dH (300 MHz, CDCl3) 7.11 (t, J
8.1 Hz, 2H), 7.20 (t, J 7.8 Hz, 2H), 7.36 (t, J 8.4 Hz, 2H), 7.37 (m, 4H),
7.39 (d, J 8.4 Hz, 2H), 7.73 (d, J 2.1 Hz, 1H), 7.87 (d, J 2.1 Hz, 1H), 8.38
(d, 1.2 Hz, 1H), 9.26 (d, J 1.2 Hz, 1H); dC (75 MHz, CDCl3) 115.0 (d, 2JCF
21.4 Hz), 116.0 (d, 2JCF 21.4 Hz), 116.8 (d, 2JCF 23.04 Hz), 118.5, 118.8,
128.6 (d, 3JCF 8.0 Hz), 129.0, 129.1, 129.2 (d, 3JCF 8.8 Hz), 132.2 (d, 3JCF
4.1.5.8. 1-(4-Chlorophenyl)-6,8-bis[2-(4-fluorophenyl)ethenyl]-
1H-pyrazolo[4,3-c]quinoline (5h). A mixture of 4a (0.50 g,
1.15 mmol), trans-2-(4-fluorophenyl)vinylboronic acid (0.476 g,
2.87 mmol), PdCl2(PPh3)2 (0.04 g, 0.058 mmol), PCy3 (0.032 g,
0.115 mmol), and K2CO3 (0.320 g, 2.300 mmol) in DMFewater
(20 mL) afforded 5h as a gray solid (0.421 g, 70%), mp 257e259 ꢁC
(ethanol); nmax (ATR) 788.8, 811.4, 836.0, 955.6, 1091.5, 1156.9,
4
4
8.0 Hz), 135.6, 135.9 (d, JCF 3.2 Hz), 136.0 (d, JCF 3.2 Hz), 136.9 (d,
4JCF 3.2 Hz), 137.3, 139.7, 141.5, 142.7, 145.3, 162.5 (d, 1JCF 245.2 Hz),
1
1
162.7 (d, JCF 246.7 Hz), 163.1 (d, JCF 249.6 Hz); m/z 452 (100%,
1229.2, 1522.9, 1599.8 cmꢀ1
; dH (300 MHz, CDCl3) 6.94 (s, 2H), 7.08
þ
MHþ); HRMS (ES): MHþ, found 452.1372. C28H17N3F3 requires
(t, J 8.7 Hz, 2H), 7.09 (t, J 8.7 Hz, 2H), 7.30 (d, J 16.5 Hz, 1H), 7.47
(t, 8.7 H, 2H), 7.59 (d, J 1.5 Hz, 1H), 7.608e7.69 (m, 6H), 8.13 (d, J
1.5 Hz, 1H), 8.38 (s, 1H), 8.46 (d, J 16.5 Hz, 1H), 9.23 (s, 1H); dC
(75 MHz, CDCl3) 115.6 (d, 2JCF 21.3 Hz), 115.8 (d, 2JCF 21.3 Hz), 116.5,
118.3, 118.8, 123.1, 125.3, 127.3, 128.2 (d, 3JCF 8.0 Hz), 128.5, 128.6 (d,
3JCF 8.0 Hz), 129.1, 129.7, 132.8 (d, 4JCF 3.4 Hz), 133.8 (d, 4JCF 3.4 Hz),
452.1375.
4.1.5.5. 1-(4-Chlorophenyl)-6,8-bis(4-fluorophenyl)-1H-pyrazolo
[4,3-c]quinoline (5e). A mixture of 4b (0.50 g, 1.15 mmol), 4-
fluorophenylboronic acid (0.402 g, 2.875 mmol), PdCl2(PPh3)2
(0.04 g, 0.0575 mmol), PCy3 (0.032 g, 0.115 mmol), and K2CO3
(0.318 g, 2.30 mmol) in DMFewater (20 mL) afforded 5e as an off-
white solid (0.366 g, 68%), mp 260e262 ꢁC (ethanol); nmax (ATR)
1
134.7, 135.6, 135.9, 137.2, 139.3, 139.4, 142.9, 144.2, 162.5 (d, JCF
1
246.7 Hz), 162.6 (d, JCF 246.7 Hz); m/z 522 (41%,C32H21N335ClF2þ),
520 (100%, C32H21N335ClF2þ); HRMS (ES): MHþ, found 520.1392.
C32H21N335ClF2þ requires 520.1396.
799.5, 857.1, 935.9, 1090.1, 1223.7, 1507.3, 1600.4 cmꢀ1
; dH
(300 MHz, CDCl3) 7.12 (t, J 8.4 Hz, 2H), 7.20 (t, J 8.4 Hz, 2H), 7.40 (t, J
8.4 Hz, 2H), 7.64 (s, 4H), 7.68 (t, J 8.4 Hz, 2H), 7.75 (d, J 1.8 Hz, 1H),
7.88 (d, J 1.8 Hz, 1H), 8.40 (d, J 1.2 Hz, 1H), 9.26 (d, J 1.2 Hz, 1H); dC
(75 MHz, CDCl3) 115.0 (d, 2JCF 21.4 Hz), 116.0 (d, 2JCF 21.4 Hz), 116.8,
4.1.5.9. 6,8-Bis[2-(4-fluorophenyl)ethenyl]-1-(4-methoxyphenyl)-
1H-pyrazolo[4,3-c]quinoline (5i). A mixture of 4a (0.50 g,
1.14 mmol), trans-2-(4-fluorophenyl)vinylboronic acid (0.472 g,