4694
M.J. Mphahlele, M.M. Mphahlele / Tetrahedron 67 (2011) 4689e4695
and column chromatography on silica gel afforded 2d and 3d in
sequence.
3.77 (s, 3H), 5.78 (s, 1H), 6.73e6.77 (m, 4H), 6.93e7.01 (m, 3H),
7.07e7.12 (m, 2H), 7.19 (t, J 7.8 Hz, 2H), 7.26 (d, J 8.7 Hz, 2H), 7.32 (dt,
J 1.2 and 7.5 Hz, 1H), 7.65 (dt, J 1.5 and 7.4 Hz, 1H), 7.75 (dd, J 0.6 and
8.6 Hz, 1H), 8.14 (dd, J 0.6 and 8.7 Hz, 1H); dC (75 MHz, CDCl3) 55.2,
Compound 2d white solid (0.02 g, 15%), mp 160e162 ꢁC
(ethanol); Rf (30% ethyl acetate/hexane) 0.63; nmax (neat) 830, 1028,
1183, 1249, 1382, 1433, 1510, 1577, 3407 cmꢀ1
;
dH (300 MHz, CDCl3)
113.2, 116.1 (d, JCF 21.4 Hz), 118.1, 121.6, 121.7, 124.7, 125.2, 125.4,
2
3.75 (s, 3H), 5.85 (s, 1H), 6.73 (d, J 9.0 Hz, 2H), 6.76 (d, J 9.3 Hz, 2H),
6.95 (t, J 7.8 Hz, 1H), 7.12e7.21 (m, 4H), 7.25e7.33 (m, 6H), 7.64 (t, J
7.8 Hz, 1H), 7.73 (d, J 7.5 Hz, 1H), 8.15 (d, J 9.0 Hz, 1H); dH (75 MHz,
CDCl3) 55.2, 113.1, 118.3, 121.6, 121.7, 125.2, 125.3, 125.6, 127.7, 128.9,
129.2, 129.4, 130.0, 130.6, 131.1, 133.5, 136.1, 144.8, 145.4, 148.5,
158.9, 159.1; m/z (100, MHþ) 403; HRMS (ES): MHþ, 403.1789.
C28H22N2Oþ requires 403.1810.
129.2, 129.5, 130.0, 131.1, 132.0 (d, 4JCF 3.4 Hz), 132.3 (d, 3JCF 8.0 Hz),
133.3, 144.9, 145.2, 148.5, 159.0, 159.2, 162.2 (d, 1JCF 246.2 Hz); m/z
(100, MHþ) 421; HRMS (ES): MHþ, found 421.1722. C28H22N2FOþ
requires 421.1716.
Compound 3f white solid (0.05 g, 54%), mp 185e187 ꢁC
(ethanol); Rf (30% ethyl acetate/hexane) 0.20; nmax (neat) 831, 1251,
1386,1436,1513,1580, 3402 cmꢀ1
; dH (300 MHz, CDCl3) 3.85 (s, 3H),
Compound 3d white solid (0.07g, 52%), mp 185e187 ꢁC
(ethanol); Rf (30% ethyl acetate/hexane) 0.23; nmax (neat) 1026,
6.39 (s, 1H), 6.99 (d, J 8.7 Hz, 2H), 7.05 (t, J 8.4 Hz, 2H), 7.27 (dt, J 1.2
and 7.4 Hz, 1H), 7.33e7.46 (m, 5H), 7.48 (s, 1H), 7.60 (d, J 8.4 Hz, 2H),
7.65 (dt, J 1.2 and 7.5 Hz, 1H), 7.99 (d, J 8.7 Hz, 2H), 8.08 (dd, J 0.6 and
1177, 1249, 1365, 1440, 1604, 3052, 3420 cmꢀ1
; dH (300 MHz, CDCl3)
2
3.86 (s, 3H), 6.46 (s, 1H), 6.99 (d, J 6.6 Hz, 2H), 7.23e7.45 (m, 8H),
7.55 (s, 1H), 7.60 (d, J 7.5 Hz, 2H), 7.65 (d, J 7.8 Hz, 2H), 8.00 (d, J
9.3 Hz, 2H), 8.07 (d, J 9.3 Hz, 1H); dC (75 MHz, CDCl3) 55.3, 99.9,
114.0, 118.9, 119.3, 122.7, 124.5, 124.8, 127.9, 128.5, 128.8, 128.9,
129.0, 129.5, 130.2, 131.2, 132.9, 135.1, 137.2, 138.2, 147.7, 149.3, 157.8,
160.5; m/z (100, MHþ) 403; HRMS (ES): MHþ, found 403.1801.
C28H22N2Oþ requires 403.1810.
8.4 Hz, 1H); dC (75 MHz, CDCl3) 55.3, 99.8, 114.0, 115.9 (d, JCF
21.3 Hz), 118.8, 119.2, 123.3, 124.8, 124.9, 128.7, 128.8, 129.5, 130.2,
130.6 (d, 3JCF 8.0 Hz), 131.2, 132.9, 134.2 (d, 3JCF 3.5 Hz), 134.4, 137.2,
1
147.8, 149.3, 157.7, 160.6, 162.4 (d, JCF 246.2 Hz); m/z (100, MHþ)
421; HRMS (ES): MHþ, 421.1698. C28H22N2FOþ requires 421.1716.
3.2.7. 2-(4-Fluorophenyl)-4-(phenylamino)-3-(phenylethenyl)quino-
line 2g and 2-(4-fluorophenyl)-4-(20-[(2-phenylethenyl)phenyl-2-yl]
amino)quinoline 3g. A mixture of 1b (0.30 g, 0.68 mmol), trans-2-
vinylphenylboronic acid (0.12 g, 0.82 mmol), Pd(PPh3)4 (0.04 g,
0.03 mmol) and K2CO3 (0.19 g, 1.36 mmol) in DMF (5 mL) was
treated as described above. Workup and column chromatography
on silica gel afforded 2g and 3g in sequence.
3.2.5. 2,3-Bis(4-Fluorophenyl)-4-(phenylamino)quinoline 2e and 2-(4-
fluorophenyl)-4-([40-fluoro(1,10-biphenyl)-2-yl]amino)quinoline 3e. A
mixture of 1b (0.20 g, 0.45 mmol), 4-fluorophenylboronic acid
(0.08 g, 0.55 mmol), Pd(PPh3)4 (0.03 g, 0.02 mmol) and K2CO3 (0.13 g,
0.19 mmol) in DMF (5 mL) was treated as described above. Workup
and column chromatography on silica gel afforded 2e and 3e in
sequence.
Compound 2g white solid (0.05 g, 18%), mp 166e169 ꢁC
(ethanol); Rf (30% ethyl acetate/hexane) 0.74; nmax (neat) 834, 1035,
Compound 2e white solid (0.03 g, 16%), mp 152e153 ꢁC (etha-
nol); Rf (30% ethyl acetate/hexane) 0.82; nmax (neat) 946,1214,1232,
1215, 1270, 1510, 1535, 1556, 3254 cmꢀ1
; dH (300 MHz, CDCl3) 6.35
(s, 1H), 6.69 (d, J 16.8 Hz, 1H), 6.84 (d, J 8.1 Hz, 2H), 6.87 (d, J 8.4 Hz,
1H), 6.92 (d, J 16.8 Hz, 1H), 6.97 (t, J 7.5 Hz, 1H), 7.13 (t, J 8.4 Hz, 2H),
7.24e7.33 (m, 6H), 7.37 (t, J 7.7 Hz, 1H), 7.63e7.71 (d, J 7.5 Hz, 3H),
7.83 (d, J 8.4 Hz, 1H), 8.11 (d, J 8.4 Hz, 1H); dC (75 MHz, CDCl3) 115.1
1491, 1508, 1575, 1598, 3391 cmꢀ1
; dH (300 MHz, CDCl3) 5.80 (s, 1H),
6.77 (d, J 7.8 Hz, 2H), 6.91 (t, J 8.7 Hz, 2H), 6.94e7.02 (m, 3H),
7.06e7.12 (m, 2H), 7.20 (t, J 7.8 Hz, 2H), 7.27e7.33 (m, 2H), 7.34 (dt, J
1.2 and 7.5 Hz, 1H), 7.67 (dt, J 1.5 and 7.4 Hz, 1H), 7.76 (dd, J 0.6 and
8.6 Hz, 1H), 8.14 (dd, J 0.6 and 8.7 Hz, 1H); dC (75 MHz, CDCl3) 114.8
2
(d, JCF 21.3 Hz), 117.7, 121.6, 121.8, 122.6, 123.7, 124.8, 125.8, 126.4,
3
128.3, 129.4, 129.6, 129.9, 131.7 (d, JCF 8.6 Hz), 135.3, 136.6, 137.1
2
2
4
1
(d, JCF 21.4 Hz), 116.2 (d, JCF 21.4 Hz), 118.3, 121.7, 122.0, 124.4,
(d, JCF 3.5 Hz), 134.4, 145.3, 147.9, 147.9, 158.5, 162.9 (d, JCF
246.4 Hz); m/z (100, MHþ) 417; HRMS (ES): MHþ, found 417.1747.
C29H22N2Fþ requires 417.1755.
3
4
125.2, 125.6, 129.3, 129.7, 130.0, 131.5 (d, JCF 8.0 Hz), 131.6 (d, JCF
3.7 Hz), 132.3 (d, JCF 8.0 Hz), 136.8 (d, JCF 3.2 Hz), 145.0, 145.2,
3
4
1
1
148.5, 158.3, 162.3 (d, JCF 247.0 Hz), 162.4 (d, JCF 246.2 Hz); m/z
Compound 3g white solid (0.17 g, 56%), mp 117e121 ꢁC
(ethanol); Rf (30% ethyl acetate/hexane) 0.54; nmax (neat) 833, 962,
(100, MHþ) 409; HRMS (ES): MHþ, found 409.1500. C27H19F2N2
requires 409.1516.
þ
1045, 1156, 1222, 1270, 1510, 1532, 1556, 3244 cmꢀ1
; dH (300 MHz,
Compound 3e white solid (0.10 g, 54%), mp 184e186 ꢁC (etha-
nol); Rf (30% ethyl acetate/hexane) 0.54; nmax (neat) 826, 1154, 1215,
CDCl3) 6.60 (s, 1H), 7.03e7.13 (m, 3H), 7.17e7.32 (m, 5H), 7.30e7.44
(m, 5H), 7.51 (dt, J 1.2 and 7.5 Hz, 1H), 7.73 (dt, J 1.5 and 7.8 Hz, 1H),
7.80 (dd, J 1.8 and 7.1 Hz, 1H), 7.92 (d, J 7.8 Hz, 2H), 7.96 (d, J 8.1 Hz,
1481, 1500, 1587, 3055, 3423 cmꢀ1
; dH (300 MHz, CDCl3) 6.40 (s,
2
1H), 7.06 (t, J 8.4 Hz, 2H), 7.14 (t, J 8.7 Hz, 2H), 7.29 (t, J 7.2 Hz, 1H),
7.36e7.44 (m, 5H), 7.45 (s, 1H), 7.60 (d, J 8.1 Hz, 2H), 7.67 (t, J 8.4 Hz,
1H), 8.01 (dd, J 5.4 and 8.6 Hz, 2H), 8.09 (d, J 8.4 Hz,1H); dC (75 MHz,
CDCl3) 99.8, 115.5 (d, 2JCF 21.4 Hz), 116.0 (d, 2JCF 21.4 Hz), 118.8, 119.2,
1H), 8.13 (d, J 8.1 Hz, 1H); dC (75 MHz, CDCl3) 100.1, 115.4 (d, JCF
21.3 Hz), 118.3, 119.4, 123.6, 125.2, 125.6, 126.3, 126.6, 127.1, 128.0,
3
128.7, 128.8, 129.3 (d, JCF 8.6 Hz), 129.7, 130.4, 131.6, 133.4, 136.5
(d, 4JCF 3.7 Hz),136.9,137.1,148.7,149.1,157.2,163.5 (d, 1JCF 247.1 Hz);
m/z (100, MHþ) 417; HRMS (ES): MHþ, found 417.1755. C29H22N2Fþ
requires 417.1767.
3
123.4, 125.0. 125.3, 128.7, 129.3 (d, JCF 8.6 Hz), 129.7, 130.4, 130.5
3
4
4
(d, JCF 8.3 Hz), 131.3, 134.1 (d, JCF 3.5 Hz), 134.6, 136.5 (d, JCF
3.4 Hz), 137.0, 148.0,149.2, 157.1, 163.6 (d, 1JCF 247.1 Hz), 162.4 (d, 1JCF
246.2 Hz); m/z (100, MHþ) 409; HRMS (ES): MHþ, found 409.1501.
3.2.8. 2-(4-Methoxyphenyl)-4-(phenylamino)-3-(phenylethenyl)
quinoline 2h and 2-(4-methoxyphenyl)-4-(2-[(2-phenylethenyl)phe-
nyl-2-yl]amino)quinoline 3h. A mixture of 1d (0.15 g, 0.33 mmol),
trans-2-vinylphenylboronic acid (0.06 g, 0.40 mmol), Pd(PPh3)4
(0.02 g, 0.02 mmol) and K2CO3 (0.09 g, 0.66 mmol) in DMF (5 mL)
was treated as described above. Workup and column chromatog-
raphy on silica gel afforded 2h and 3h in sequence.
C27H19F2N2þ requires 409.1516.
3.2.6. 3-(4-Fluorophenyl)-2-(4-methoxyphenyl)-4-(phenylamino)
quinoline 2f and 4-([40-fluoro(1,10-biphenyl)-2-yl]amino)-2-(4-me-
thoxyphenyl)quinoline 3f. A mixture of 1d (0.10 g, 0.22 mmol),
4-fluorophenylboronic acid (0.04 g, 0.27 mmol), Pd(PPh3)4 (0.01 g,
0.01 mmol) and K2CO3 (0.06 g, 0.44 mmol) in DMF (5 mL) was
treated as described above. Workup and column chromatography
on silica gel afforded 2f and 3f in sequence.
Compound 2h white solid (0.03 g, 21%), mp 159e161 ꢁC
(ethanol); Rf (30% ethyl acetate/hexane) 0.54; nmax (neat) 837, 1028,
1173, 1249, 1301, 1398, 1483, 1602, 3059, 3320 cmꢀ1
; dH (300 MHz,
Compound 2f white solid (0.02 g, 22%), mp 160e162 ꢁC
(ethanol); Rf (30% ethyl acetate/hexane) 0.50; nmax (neat) 834, 1026,
CDCl3) 3.85 (s, 3H), 6.32 (s, 1H), 6.74 (d, J 16.8 Hz, 1H), 6.83 (d, J
8.4 Hz, 2H), 6.94e6.70 (m, 4H), 7.21e7.30 (m, 7H), 7.35 (dt, J 1.2 and
7.5 Hz, 1H), 7.65 (dt, J 1.5 and 8.7 Hz, 1H), 7.67 (d, J 7.5 Hz, 2H), 7.83
1214, 1243, 1399, 1492, 1508, 1573, 3388 cmꢀ1
; dH (300 MHz, CDCl3)