The Journal of Organic Chemistry
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+
150.2, 155.5, 158.4; HR-ESI (Q-TOF) m/z: calcd for C21H15N4+ [M +
H]+, 323.1296; found, 323.1305.
154.4, 158.0; HR-ESI (Q-TOF) m/z: calcd for C26H25N4 [M + H]+,
393.2079; found, 393.2088.
6-(1E,3E)-4-(4-(Methoxyphenyl)buta-1,3-dienyl)-N-phenyl-
quinazolin-4-amine (3b). Yield: 70 mg, 13%; mp 245−248 °C
(dec); IR νmax (cm−1): 3029.9, 1939.7, 1599.1, 1568.7 1525.3, 1498.5,
1446.4, 1410.1, 1385.1, 1357.7, 1300.1, 1248.8, 988.5, 806.7, 740.2,
690.7; 1H NMR (500 MHz, DMSO-d6): δ 3.84 (s, 3H), 6.77 (d, 1H, J
= 15.5 Hz), 6.85 (d, 1H, J = 15.5 Hz), 6.95 (d, 2H, J = 8.6 Hz), 7.07
(dd, 1H, J = 15.4, 10.7 Hz), 7.15 (t, 1H, J = 7.3 Hz), 7.29 (dd, 1H, J =
15.5, 10.7 Hz), 7.42 (t, 2H, J = 7.9 Hz), 7.51 (d, 2H, J = 8.5 Hz), 7.73
(d, 1H, J = 8.6 Hz), 7.86 (d, 2H, J = 7.7 Hz), 8.04 (d, 1H, J = 8.6 Hz),
8.54 (s, 1H), 8.59 (s, 1H), 9.84 (s, 1H); 13C NMR (125 MHz, DMSO-
d6): δ 55.6, 114.7, 115.9, 120.4, 122.9, 124.2, 127.5, 128.3, 128.6,
128.9, 130.0, 130.8, 131.3, 131.7, 133.7, 135.9, 139.6, 149.6, 154.6,
158.0, 159.6; HR-ESI (Q-TOF) m/z: calcd for C25H22N3O+ [M +
H]+, 380.1763; found, 380.1766.
N-Phenyl-6-((1E,3E)-4-phenylbuta-1,3-dienyl)quinazolin-4-
amine (3c). Yield: 70 mg, 14%; mp 258−260 °C (dec); IR νmax
(cm−1): 3259.1, 3055.1, 1924.2, 1604.2, 1569.2, 1528.3, 1496.2,
1440.3, 1406.5, 1388.2, 1363.4, 1329.5, 1310.3, 1253.8, 978.0, 901.4,
750.3, 686.5; 1H NMR (500 MHz, DMSO-d6): δ 6.81 (d, 1H, J = 15.2
Hz), 6.91 (d, 1H, J = 15.2 Hz), 7.11 (t, 1H, J = 7.2 Hz), 7.19−7.32 (m,
3H), 7.38 (d, 2H, J = 7.4 Hz), 7.39 (d, 2H, J = 7.4 Hz), 7.56 (d, 2H, J
= 7.6 Hz), 7.68 (d, 1H, J = 8.5 Hz), 7.80 (d, 2H, J = 7.6 Hz), 8.01 (d,
1H, J = 8.5 Hz), 8.47 (s, 1H), 8.58 (s, 1H), 9.84 (s, 1H); 13C NMR
(125 MHz, DMSO-d6): δ 116.1, 121.1, 123.0, 123.8, 126.9, 128.2,
128.4, 128.8, 129.2, 129.8, 131.0, 132.3, 133.7, 135.3, 137.4, 140.7,
149.9, 154.9, 158.1; HR-ESI (Q-TOF) m/z: calcd for C24H20N3+ [M +
H]+, 350.1657; found, 350.1673.
6-(4-Nitrophenyl)-N-phenylquinazolin-4-amine (1e). Yield:
55 mg, 16%; mp 262−264 °C; IR νmax (cm−1): 3089.6, 1934.3,
1597.5, 1569.0, 1531.1, 1514.6, 1488.0, 1449.5, 1401.4, 1417.5, 1341.8,
1
1271.0, 834.7, 752.1, 693.2; H NMR (500 MHz, DMSO-d6): δ 7.32
(t, 1H, J = 7.4 Hz), 7.57 (t, 2H, J = 8.1 Hz), 7.98 (d, 2H, J = 7.6 Hz),
8.05 (d, 1H, J = 8.6 Hz), 8.33 (d, 2H, J = 8.8 Hz), 8.44 (dd, 1H, J =
8.7, 1.7 Hz), 8.55 (d, 2H, J = 8.8 Hz), 8.76 (s, 1H), 9.14 (d, 1H, J = 1.3
Hz), 10.20 (s, 1H); 13C NMR (125 MHz, DMSO-d6): δ 115.8, 122.3,
123.2, 124.5, 128.6, 128.9, 129.1, 132.1, 135.8, 139.3, 145.9, 147.3,
+
150.3, 155.7, 158.5; HR-ESI (Q-TOF) m/z: calcd for C20H15N4O2
[M + H]+, 343.1195; found, 343.1194.
(E)-6-(4-Dimethylaminostyryl)-N-phenylquinazolin-4-amine
(2a). Yield: 130 mg, 25%; mp 220 °C (dec); IR νmax (cm−1): 3206.0,
2940.8, 1646.0, 1599.4, 1564.6, 1521.6, 1493.6, 1443.9, 1403.9, 1382.3,
1
1363.2, 1254.4, 957.2, 752.1, 691.3; H NMR (400 MHz, DMSO-d6):
δ 2.94 (s, 6H), 6.76 (d, 2H, J = 8.7 Hz), 7.10−7.14 (m, 2H), 7.34−
7.42 (m, 3H), 7.48 (d, 2H, J = 8.7 Hz), 7.73 (d, 1H, J = 8.7 Hz), 7.87
(d, 2H, J = 7.8 Hz), 8.07 (d, 1H, J = 8.7 Hz), 8.52 (s, 1H), 8.60 (s,
1H), 9.78 (s, 1H); 13C NMR (125 MHz, DMSO): δ 112.3, 115.5,
119.1, 122.4, 123.8, 124.6, 127.7, 128.0, 128.5, 130.5, 131.1, 136.2,
139.3, 148.7, 150.3, 153.8, 157.6; HR-ESI (Q-TOF) m/z: calcd for
+
C24H23N4 [M + H]+, 367.1923; found, 367.1929.
(E)-N-Phenyl-6-styrylquinazolin-4-amine (2c). Yield: 74 mg,
16%; mp 248−252 °C (dec); IR νmax (cm−1): 3048.8, 1949.9, 1622.7,
1600.8, 1570.5, 1523.4, 1494.9, 1446.5, 1409.5, 1385.9, 1360.5, 1332.6,
1
1254.5, 827.7, 747.8, 687.8; H NMR (500 MHz, DMSO-d6): δ 7.16
(t, 1H, J = 7.2 Hz), 7.32 (t, 1H, J = 7.2 Hz), 7.38−7.51 (m, 6H), 7.66
(d, 2H, J = 7.4 Hz), 7.78 (d, 1H, J = 8.6 Hz), 7.87 (d, 2H, J = 7.6 Hz),
8.14 (d, 1H, J = 8.3 Hz), 8.56 (s, 1H), 8.72 (s, 1H), 9.81 (s, 1H); 13C
NMR (125 MHz, DMSO-d6): δ 115.8, 120.8, 122.9, 124.2, 127.0,
128.0, 128.4, 128.6, 128.9, 129.3, 130.3, 131.7, 135.6, 137.2, 139.6,
149.8, 154.8, 158.1; HR-ESI (Q-TOF) m/z: calcd for C22H18N3+ [M +
H]+, 324.1500; found, 324.1516.
4-((1E,3E-4-(4-(Phenylamino)quinazolin-6-yl)buta-1,3-
dienyl)benzonitrile (3d). Yield: 134 mg, 25%; mp 242−245 °C
(dec); IR νmax (cm−1): 3365.8, 3028.7, 2224.5, 1598.1, 1568.6, 1525.6,
1496.8, 1443.5, 1402.4, 1387.6, 1361.7, 1252.8, 983.0, 746.2, 848.0,
1
687.4; H NMR (500 MHz, DMSO-d6): δ 7.02 (d, 1H, J = 15.2 Hz),
7.16 (d, 1H, J = 15.1 Hz), 7.30 (t, 1H, J = 7.4 Hz), 7.46−7.60 (m, 4H),
7.90 (d, 3H, J = 8.5 Hz), 7.96 (d, 2H, J = 8.35 Hz), 8.00 (d, 2H, J =
7.65 Hz), 8.22 (dd, 1H, J = 8.7, 1.0 Hz), 8.69 (s, 1H), 8.79 (s, 1H),
9.98 (s, 1H); 13C NMR (125 MHz, DMSO-d6): δ 109.9, 115.8, 119.4,
121.4, 122.9, 124.2, 127.5, 128.7, 128.9, 130.6, 131.3, 131.8, 133.0,
133.5, 134.4, 135.2, 139.5, 142.1, 150.1, 154.9, 158.1; HR-ESI (Q-
4-((E-2-(4-(Phenylamino)quinazoline-6-yl)vinyl)benzonitrile
(2d). Yield: 98 mg, 20%; mp 250−254 °C; IR νmax (cm−1): 3071.4,
2221.6, 1599.8, 1571.8, 1498.4, 1441.7, 1403.6, 1362.3, 964.8, 838.4,
1
752.4, 693.8; H NMR (500 MHz, DMSO-d6): δ 7.15 (t, 1H, J = 7.4
+
Hz), 7.42 (t, 2 H, J = 8.3 Hz), 7.56 (d, 1H, J = 16.4 Hz), 7.59 (d, 1H, J
= 16.4 Hz), 7.79−7. 89 (br m, 7H), 8.17 (dd, 1H, J = 8.7, 1.7 Hz), 8.57
(s, 1H), 8.76 (s, 1H), 9.88 (s, 1H); 13C NMR (125 MHz, DMSO-d6):
δ 110.2, 115.8, 119.3, 121.8, 122.9, 124.2, 127.5, 128.5, 129.1, 129.2,
131.9 133.1, 134.7, 139.5, 141.9, 150.2, 155.1, 158.2; HR-ESI (Q-
TOF) m/z: calcd for C25H19N4 [M + H]+, 375.1609; found,
375.1610.
6-((1E,3E)-4-(4-Nitrophenyl)buta-1,3-dienyl)-N-phenylquina-
zolin-4-amine (3e). Yield: 113 mg, 20%; mp 273−275 °C (dec); IR
νmax (cm−1): 3421.3, 3020.7, 1927.9, 1603.3, 1585.6, 1571.5, 1557.7,
1535.3, 1494.4, 1444.3, 1331.5, 1253.8, 1109.3, 987.1, 743.6, 804.3; 1H
NMR (500 MHz, DMSO-d6): δ 6.92 (d, 1H, J = 15.4 Hz), 7.03 (d,
1H, J = 15.3 Hz), 7.13 (t, 1H, J = 7.2 Hz), 7.32−7.41 (m, 3H), 7.48
(dd, 1H, J = 15.4, 10.7 Hz), 7.73 (d, 1H, J = 8.6 Hz), 7.81 (d, 2H, J =
8.8 Hz), 7.83 (d, 2H, J = 8.8 Hz), 8.08 (d, 1H, J = 8.6 Hz), 8.20 (d,
2H, J = 8.6 Hz), 8.53 (s, 1H), 8.64 (s, 1H), 9.86 (s, 1H); 13C NMR
(125 MHz, DMSO-d6): δ 115.8, 121.5, 123.0, 124.3, 124.4, 127.6,
128.7, 128.9, 130.6, 131.4, 132.0, 134.5, 135.1, 135.2, 139.5, 144.2,
146.6, 150.1, 155.0, 158.1; HR-ESI (Q-TOF) m/z: calcd for
+
TOF) m/z: calcd for C23H17N4 [M + H]+, 349.1453; found,
349.1453.
(E)-6-(4-Nitrostyryl)-N-phenylquinazolin-4-amine (2e). Yield:
128 mg, 24%; mp 240 °C (dec); IR νmax(cm−1): 3085.1, 1932.2,
1602.1, 1591.5, 1571.4, 1527.7, 1501.7, 1328.8, 1404.1, 1443.2, 1365.5,
1255.4, 1105.2, 968.0, 749.5, 684.1, 694.9; 1H NMR (500 MHz,
DMSO-d6): δ 7.30 (t, 1H, J = 7.3 Hz), 7.56 (t, 2H, J = 7.8 Hz), 7.72
(d, 1H, J = 16.5 Hz), 7.76 (d, 1H, J = 16.5 Hz), 7.93 (d, 1H, J = 8.6
Hz), 8.01 (t, 4H, J = 7.8 Hz), 8.30, (d, 1H, J = 8.6 Hz), 8.40 (d, 2H, J
= 8.4 Hz), 8.71 (s, 1H), 8.91(s, 1H), 9.98 (s, 1H); 13C NMR (125
MHz, DMSO-d6): δ 115.8, 122.1, 122.9, 124.3, 124.6, 127.8, 128.1,
128.7, 128.9, 131.9, 132.7, 134.7, 139.4, 144.1, 146.8, 150.3, 155.2,
+
C24H19N4O2 [M + H]+, 395.1508; found, 395.1503.
ASSOCIATED CONTENT
■
+
158.2; HR-ESI (Q-TOF) m/z: calcd for C22H17N4O2 [M + H]+,
S
* Supporting Information
1H and 13C NMR spectra, emission spectra in toluene and
acetonitrile, frontier molecular orbitals, and Cartesian coor-
dinates of optimized geometries. This material is available free
369.1351; found, 369.1346.
6-(1E,3E)-(4-(4-Dimethylaminophenyl)buta-1,3-dienyl)-N-
phenylquinazolin-4-amine (3a). Yield: 90 mg, 16%; mp 255−258
°C (dec); IR νmax (cm−1): 2980.6, 1596.3, 1570.0, 1521.7, 1496.4,
1
1445.6, 1409.3, 1385.4, 1354.0, 1186.4, 987.4, 801.0, 746.0, 689.8; H
NMR (500 MHz, DMSO-d6): δ 2.94 (s, 6H), 6.71 (d, 2H, J = 8.7 Hz),
6.77 (d, 2H, J = 15.6 Hz), 6.95 (dd, 1H, J = 15.2, 11.7 Hz), 7.15 (t,
1H, J = 7.0 Hz), 7.27 (dd, 1H, J = 15.0, 11.1 Hz), 7.38−7.43 (m, 4H),
7.72 (d, 1H, J = 8.4 Hz), 7.87 (d, 2H, J = 7.3 Hz), 8.00 (d, 1H, J = 8.3
Hz), 8.54 (d, 2H, J = 15.6 Hz), 9.8 (s, 1H); 13C NMR (125 MHz,
DMSO-d6): δ 112.6, 115.9, 119.9, 122.9, 124.2, 125.0, 125.2, 128.1,
128.5, 128.9, 129.2, 131.2, 132.2, 134.7, 136.2, 139.6, 149.5, 150.5,
AUTHOR INFORMATION
■
Corresponding Author
Notes
The authors declare no competing financial interest.
4946
dx.doi.org/10.1021/jo500520x | J. Org. Chem. 2014, 79, 4940−4947