3478
Y.-L. Liu et al. / Tetrahedron 65 (2009) 3473–3479
7.08–7.14 (m, 2H), 7.23–7.28 (m, 4H), 7.45 (m, 1H); 13C NMR
(75 MHz, CDCl3): 26.6, 35.3, 54.4, 113.8, 118.2, 128.4, 128.9, 129.2,
4.2.14. 2-[(Phenylamino)(phenyl)methyl]cyclohex-2-enone (
Yellow powder, mp: 124–125 ꢀC. FTIR (KBr):
3392, 3052, 3031,
2928, 2875, 1667, 1600, 1500, 1426, 1376, 1315, 1251, 1172, 748, 697,
512 cmꢁ1. 1H NMR (300 MHz, CDCl3):
1.95 (m, 2H), 2.39 (m, 4H),
a-6a)
d
n
133.3, 139.6, 146.4, 146.7, 159.9, 208.0. HRMS (EI): m/z calcd for
C18H16NOCl (Mþ): 297.0920, found: 297.0918.
d
4.21 (br s, 1H), 5.42 (s, 1H), 6.50–5.53 (m, 2H), 6.67 (t, J¼7.3 Hz, 1H),
4.2.9. 2-[(Phenylamino)(4-bromophenyl)methyl]cyclopent-2-
7.02 (t, J¼4.1 Hz, 1H), 7.08–7.04 (m, 2H), 7.19–7.36 (m, 5H); 13C NMR
enone (
Yellow solid, mp: 151–152 ꢀC. FTIR (KBr):
2853,1693,1599,1495,1433,1258,1003, 826, 747, 695, 512 cmꢁ1. 1H
NMR (300 MHz, CDCl3): 2.39–2.47 (m, 2H), 2.60 (m, 2H), 4.55 (br
s, 1H), 5.29 (s, 1H), 6.54 (s, 1H), 6.57 (s, 1H), 6.72 (t, J¼7.3 Hz, 1H),
7.11–7.16 (m, 2H), 7.28–7.31 (m, 2H), 7.44–7.48 (m, 3H). The
value was determined by the 1H NMR absorptions of the product
mixture at 5.29 and 4.89 ppm. 13C NMR (75 MHz, CDCl3):
26.6,
a-3h)
(75 MHz, CDCl3): d 22.8, 38.7, 56.7, 113.5, 117.7, 127.3, 127.4, 128.6,
n
3347, 3051.8, 2915,
129.2, 139.4, 141.8, 146.7, 147.1, 198.5. HRMS (EI): m/z calcd for
C19H19NO (Mþ): 277.1467, found: 277.1469.
d
4.2.15. 2-[(p-Toluidino)(phenyl)methyl]cyclohex-2-enone (
Yellow solid, mp: 139–141 ꢀC. FTIR (KBr):
3388, 3048, 3021,
2923, 2862, 1667, 1598, 1503, 1427, 1374, 1313, 1249, 1171, 810, 750,
693, 510 cmꢁ1 1H NMR (300 MHz, CDCl3):
1.91–2.04 (m, 2H),
a-6b)
a
/g
n
d
.
d
35.3, 54.4, 113.8, 118.2, 121.4, 128.8, 129.2, 131.9, 140.2, 146.3, 146.6,
156.0, 208.0. HRMS (EI): m/z calcd for C18H16NOBr (Mþ): 341.0415
and 343.0395, found: 341.0413 and 343.0392.
2.20 (s, 3H), 2.36–2.46 (m, 4H), 4.08 (br s, 1H), 5.39 (s, 1H), 6.44 (d,
J¼8.3 Hz, 2H), 6.93 (d, J¼8.3 Hz, 2H), 7.03 (t, J¼4.0 Hz, 1H), 7.21–
7.36 (m, 5H); 13C NMR (75 MHz, CDCl3):
d 20.4, 22.8, 26.0, 38.8,
47.2, 113.6, 126.9, 127.3, 128.6, 129.7, 139.6, 142.0, 144.8, 146.6,
198.6. HRMS (EI): m/z calcd for C20H21NO (Mþ): 291.1623, found:
291.1625.
4.2.10. 2-[(Phenylamino)(p-tolyl)methyl]cyclopent-2-enone (
Yellow solid, mp: 128–129 ꢀC. FTIR (KBr):
3382, 3049, 3021,
2921, 2858, 1695, 1600, 1505, 1434, 1315, 1259, 1185, 746, 694,
516 cmꢁ1. 1H NMR (300 MHz, CDCl3):
2.35 (s, 3H), 2.44–2.48 (m,
a-3i)
n
d
4.2.16. 2-[(4-Fluorophenylamino)(phenyl)methyl]cyclohex-2-
2H), 260 (m, 2H), 4.54 (br s, 1H), 5.32 (s, 1H), 6.57 (s, 1H), 6.60 (s,
enone(
A yellow liquid. FTIR (KBr):
1511, 1377, 1217, 821, 703, 515 cmꢁ1
1.90–2.03 (m, 2H), 2.37–2.49 (m, 4H), 4.16 (br s, 1H), 5.35 (s, 1H),
a-6c)
1H), 6.72 (t, J¼7.3 Hz, 1H), 7.12–7.18 (m, 4H), 7.31 (s, 1H), 7.33 (s, 1H),
n
3383, 3057, 3034, 2938, 2880, 1667,
1H NMR (300 MHz, CDCl3):
7.51 (m, 1H). The
a
/g
value was determined by the 1H NMR ab-
.
sorptions of the product mixture at 5.32 and 4.91 ppm. 13C NMR
(75 MHz, CDCl3): 21.1, 26.6, 35.4, 54.7, 113.7, 117.9, 127.0, 129.2,
d
d
6.42–6.47 (m, 2H), 6.81 (d, J¼233.6 Hz) (t, J¼8.7 Hz, 2H), 6.99 (t,
129.5, 137.3, 138.0, 146.8, 147.0, 159.6, 208.3. HRMS (EI): m/z calcd
J¼4.1 Hz, 1H), 7.27–7.35 (m, 5H); 13C NMR (75 MHz, CDCl3):
d 22.7,
for C19H19NO (Mþ): 277.1467, found: 277.1469.
26.0, 38.7, 57.6, 114.4 (J¼7.3 Hz), 115.5 (J¼22.2 Hz), 127.2, 127.4,
128.6, 139.4, 141.6, 143.4, 146.9, 156.0 (J¼ꢁ233.6 Hz), 198.6. Anal.
Calcd for C19H18FNO: C, 77.27; H, 6.14; N, 4.74. Found: C, 77.32; H,
6.22; N, 4.92.
4.2.11. 2-[(Phenylamino)(cyclohexyl)methyl]cyclopent-2-
enone (
Yellow solid, mp: 78–79 ꢀC. FTIR (KBr):
2361,1690,1597,1502,1441,1251, 746, 686 cmꢁ1.1H NMR (300 MHz,
CDCl3):
a-3j)
n
3382, 3053, 2921, 2850,
4.2.17. 2-[(Phenylamino)(p-tolyl)methyl]cyclohex-2-enone (
Yellow solid, mp: 109–111 ꢀC. FTIR (KBr):
3388, 3026, 2923,
2862,1677, 1614, 1517, 1375, 1308,1248, 1173, 808, 702, 510 cmꢁ1. 1H
NMR (300 MHz, CDCl3): 1.92–2.04 (m, 2H), 2.31 (s, 3H), 2.37–2.49
a-6d)
d
0.90–1.28 (m, 5H), 1.57–1.80 (m, 5H), 1.92 (d, J¼12.8 Hz,
n
1H), 2.40–2.42 (m, 2H), 2.52–2.55 (m, 2H), 4.01 (d, J¼6.8 Hz, 1H),
4.22 (s,1H), 6.50 (d, J¼8.6 Hz, 2H), 6.63 (t, J¼7.3 Hz,1H), 7.10 (m, 2H),
d
7.33 (t, J¼2.4 Hz, 1H); 13C NMR (75 MHz, CDCl3):
d
26.2, 26.4. 29.4,
(m, 4H), 4.17 (br s, 1H), 5.39 (s, 1H), 6.51 (d, J¼7.7 Hz, 2H), 6.68
30.3, 35.4, 41.3, 55.7, 113.2, 117.1, 129.2, 145.7, 147.6, 159.5, 209.3.
(t, J¼7.3 Hz, 1H), 7.04 (t, J¼4.0 Hz, 1H), 7.09–7.15 (m, 4H), 7.22–7.25
HRMS (EI): m/z calcd for C18H23NO (Mþ): 269.1780, found: 269.1783.
(m, 2H); 13C NMR (75 MHz, CDCl3):
d 21.1, 22.8, 25.9, 38.8, 56.7,
113.4, 117.6, 127.2, 129.1, 129.3, 137.0, 138.8, 139.4, 146.4, 147.1, 198.6.
4.2.12. 2-[(p-Toluidino)(4-fluorophenyl)methyl]cyclopent-2-
HRMS (EI): calcd for C20H21NO (Mþ): 291.1623, found: 291.1626.
enone (
Yellow solid, mp: 111–112 ꢀC. FTIR (KBr):
1668, 1511, 1377, 1312, 1217, 1165, 821, 774, 703, 515 cmꢁ1. 1H NMR
(300 MHz, CDCl3): 2.20 (s, 3H), 2.40–2.44 (m, 2H), 2.55–2.58 (m,
2H), 4.37 (br s, 1H), 5.26 (s, 1H), 6.45 (d, J¼8.4 Hz, 2H), 6.91–7.01 (m,
4H), 7.33–7.37 (m, 2H), 7.45 (t, J¼2.6 Hz, 1H). The value was
determined by the 1H NMR absorptions of the product mixture at
5.26 and 4.85 ppm. 13C NMR (75 MHz, CDCl3):
20.4, 26.6, 35.4,
a-3k)
n
3385, 3031, 2924,
4.2.18. 2-[(Phenylamino)(4-methoxyphenyl)methyl]cyclohex-2-
enone (
A yellow liquid. FTIR (KBr):
1505, 1374, 1247, 1173, 1032, 817, 749, 694 cmꢁ1. 1H NMR (300 MHz,
CDCl3): 1.92–2.04 (m, 2H), 2.35–2.44 (m, 4H), 3.76 (s, 3H), 4.16 (br
a-6e)
d
n 3389, 3043, 2922, 2862, 1666, 1602,
a
/g
d
s, 1H), 5.37 (s, 1H), 6.50 (d, J¼8.2 Hz, 2H), 6.67 (t, J¼7.3 Hz, 1H), 6.83
d
(d, J¼8.7 Hz, 2H), 7.03 (t, J¼4.1 Hz, 1H), 7.11 (t, J¼7.7 Hz, 2H), 7.26 (d,
54.6, 113.9, 115.5 (d, J¼21.4 Hz), 127.4, 128.7 (d, J¼8.0 Hz), 129.7,
137.0,144.5,146.8,159.7,162.2 (d, J¼244.2 Hz). HRMS (EI): m/z calcd
for C19H18NOF (Mþ): 295.1372, found: 295.1375.
J¼8.7 Hz, 2H); 13C NMR (75 MHz, CDCl3):
d 22.8, 25.9, 38.8, 55.3,
56.4, 113.4, 114.0, 117.6, 128.4, 129.1, 133.9, 139.4. 146.3, 147.1, 158.9,
198.6. HRMS (EI): m/z calcd for C20H21NO2 (Mþ): 307.1572, found:
307.1574.
4.2.13. 2-[(4-Fluorophenylamino)(4-chlorophenyl)methyl]-
cyclopent-2-enone (
Yellow solid, mp: 107–111 ꢀC. FTIR (KBr):
2862, 1696, 1618, 1512, 1220, 1093, 1008, 818, 514 cmꢁ1
(300 MHz, CDCl3): 2.43 (m, 2H), 2.58 (m, 2H), 4.47 (br s, 1H), 5.21
(s, 1H), 6.44–6.49 (m, 2H), 6.81 (t, J¼8.7 Hz, 2H), 7.26–7.34 (m, 4H),
7.43 (t, J¼2.6 Hz, 1H). The
value was determined by the 1H NMR
absorptions of the product mixture at 5.21 and 4.82 ppm. 13C NMR
(75 MHz, CDCl3):
a
-3l)
4.2.19. 2-[(Phenylamino)(4-fluorophenyl)methyl]cyclopent-2-
n
3378, 3048, 2922,
1H NMR
enone (
White solid, mp: 104–106 ꢀC. FTIR (KBr):
1664, 1604, 1503, 1425, 1375, 1314, 1224, 1163, 822, 749,
694, 519 cmꢁ1 1H NMR (300 MHz, CDCl3):
1.68–2.04 (m, 2H),
a-6f)
.
n 3394, 3061, 2929,
d
.
d
a/g
2.36–2.44 (m, 2H), 4.18 (br s, 1H), 5.29 (s, 1H), 6.51 (d, J¼7.7 Hz, 2H),
6.69 (t, J¼7.3 Hz, 1H), 6.95–7.15 (m, 5H), 7.29–7.34 (m, 2H); 13C NMR
d
26.6, 35.2, 55.1, 114.8 (J¼7.4 Hz), 115.6
(75 MHz, CDCl3):
d
22.7, 25.9, 38.7, 56.5, 113.5, 115.4 (J¼ꢁ21.4 Hz),
(J¼ꢁ22.3 Hz), 128.3, 128.9, 133.4, 139.5, 143.0, 146.3, 156.2 (d,
J¼234.8 Hz), 159.9, 207.9. HRMS (EI): m/z calcd for C18H15NOFCl
(Mþ): 315.0826, found: 315.0829.
117.9, 128.8 (J¼8.0 Hz), 129.2, 137.5, 139.4, 146.9, 162.1 (J¼244.0 Hz),
198.5. HRMS (EI): m/z calcd for C19H18NOF (Mþ): 295.1372, found:
295.1375.