1440
S. Ushijima et al. / Tetrahedron 68 (2012) 1436e1442
d
2.42 (s, 3H), 7.34e7.42 (m, 2H), 7.46 (d, 2H, J¼8.9 Hz), 7.54 (d, 1H,
J¼8.6 Hz); 13C NMR (125 MHz, CDCl3):
d 128.0, 128.7, 130.6, 134.5,
J¼7.5 Hz), 7.59 (s, 1H), 7.75 (d, 2H, J¼8.9 Hz); 13C NMR (125 MHz,
134.7, 136.4, 138.7, 143.2, 186.9.
CDCl3):
138.3, 138.8, 195.7.
d 21.3, 127.2, 128.2, 128.6, 130.3, 131.4, 133.4, 136.0, 137.3,
4.2.26. 4-Fluoro-40-methoxybenzophenone. Mp 92e94 ꢁC (lit.26 mp
89e91 C); IR (Nujol) 1639 cmꢀ1; 1H NMR (400 MHz, CDCl3)
(s, 3H), 6.97 (d, 2H, J¼8.8 Hz), 7.14 (t, 2H, J¼8.7 Hz), 7.76e7.82 (m,
4H); 13C NMR (100 MHz, CDCl3):
55.4, 113.6, 115.3 (d,
d
3.88
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4.2.16. 4-Chloro-20-methylbenzophenone. Yellow oil. (lit.27 yellow
oil); IR (neat) 1667 cmꢀ1; 1H NMR (500 MHz, CDCl3):
d
2.32 (s, 3H),
d
7.22e7.31 (m, 3H), 7.37e7.44 (m, 3H), 7.73 (d, 2H, J¼8.6 Hz); 13C
JCeF¼22.0 Hz) 123.0, 132.3 (d, JCeF¼9.6 Hz), 132.3, 134.4 (d,
NMR (125 MHz, CDCl3): d 19.9, 125.2, 128.4, 128.7, 130.4, 131.1, 131.4,
JCeF¼2.9 Hz), 163.2, 165.0 (d, JCeF¼253.9 Hz), 194.0.
136.0, 136.7, 138.0, 139.6, 197.2.
4.2.27. 4-Chloro-40-fluorobenzophenone. Mp 116e118 ꢁC (lit.34 mp
4.2.17. 4-Chloro-40-methoxylbenzophenonꢀe.1 Mp 122e123 ꢁC (lit.28
118e119 C); IR (Nujol) 1649 cmꢀ1; 1H NMR (400 MHz, CDCl3)
d
7.17
(t, 2H, J¼8.6 Hz), 7.46 (d, 2H, J¼8.4 Hz), 7.72 (d, 2H, J¼8.4 Hz),
7.78e7.84 (m, 2H); 13C NMR (100 MHz, CDCl3):
115.6 (d,
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;
1H NMR (500 MHz,
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mp 119e120 C); IR (Nujol) 1638 cm
CDCl3):
d
3.89 (s, 3H), 6.97 (d, 2H, J¼8.9 Hz), 7.45 (d, 2H, J¼8.6 Hz),
d
7.71 (d, 2H, J¼8.6 Hz), 7.80 (d, 2H, J¼8.9 Hz); 13C NMR (125 MHz,
JCeF¼22.1 Hz), 128.6, 131.2, 132.5 (d, JCeF¼8.6 Hz), 133.4 (d,
CDCl3):
194.2.
d 55.5, 113.7, 128.5, 129.8, 131.1, 132.4, 136.5, 138.3, 163.4,
JCeF¼2.9 Hz), 135.7, 138.9, 165.4 (d, JCeF¼253.2 Hz), 193.9.
4.2.28. 4-Fluorophenyl 20-naphthyl ketone. Mp 109e110 ꢁC (lit.35
ꢀ1
4.2.18. 4,40-Dichlorlbenzophenone. Mp 144 ꢁC (commercial, mp
144e146 C); IR (Nujol) 1654 cm
mp 110e110.8 C); IR (Nujol) 1651 cm
CDCl3)
7.19 (t, 2H, J¼8.7 Hz), 7.53e7.64 (m, 2H), 7.87e7.96 (m, 6H),
8.23 (s, 1H); 13C NMR (100 MHz, CDCl3)
;
1H NMR (400 MHz,
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ꢀ1
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;
1H NMR (500 MHz, CDCl3):
d
d
7.47 (d, 4H, J¼8.9 Hz), 7.72 (d, 4H, J¼8.6 Hz); 13C NMR (125 MHz,
d
115.5 (d, JCeF¼21.1 Hz),
CDCl3):
d
128.7, 131.3, 135.5, 139.1, 194.2.
123.6, 126.9, 127.8, 128.4, 129.3, 131.6, 132.2, 132.7 (d, JCeF¼9.6 Hz),
132.7, 134.1 (d, JCeF¼3.8 Hz), 134.7, 135.2, 165.4 (d, JCeF¼254.8 Hz),
195.3.
4.2.19. 4-Bromo-40-chlorobenzopheꢀn1one. Mp 145e146 ꢁC (lit.19 mp
;
1H NMR (500 MHz, CDCl3):
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146e148 C); IR (Nujol) 1644 cm
d
7.47 (d, 2H, J¼8.6 Hz), 7.62e7.66 (m, 4H), 7.72 (d, 2H, J¼8.3 Hz); 13
C
4.2.29. 2-Benzofuryl 40-fluorophenyl ketone. Mp 133e135 ꢁC; IR
ꢀ1
; d 7.21 (t, 2H,
1H NMR (400 MHz, CDCl3)
€
(Nujol) 1648 cm
NMR (125 MHz, CDCl3):
135.9, 139.1, 194.3.
d
127.7, 128.7, 131.2, 131.3, 131.7, 135.4,
J¼8.6 Hz), 7.33 (t, 1H, J¼7.5 Hz), 7.49 (t, 1H, J¼8.4 Hz), 7.54 (s, 1H),
7.62 (d, 1H, J¼8.4 Hz), 7.72 (d, 1H, J¼7.7 Hz), 8.08e8.14 (m, 2H); 13C
4.2.20. 4-Chloro-20,40-dimethoxybenzophenone. Mp 95e97 ꢁC (lit.29
mp 99 C); IR (Nujol) 1655 cm
NMR (100 MHz, CDCl3)
d
112.4, 115.7 (d, JCeF¼22.0 Hz), 116.2, 123.2,
ꢀ1
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;
1H NMR (500 MHz, CDCl3):
124.0, 126.8, 128.4, 132.1 (d, JCeF¼8.6 Hz), 133.3 (d, JCeF¼2.9 Hz),
152.1, 155.9, 165.6 (d, JCeF¼255.8 Hz), 182.6; HRMS(APCI)[MþH]þ,
calcd for C15H10FO2¼241.0659, observed¼241.0656.
d
3.69 (s, 3H), 3.87 (s, 3H), 6.50 (s, 1H), 6.56 (d, 1H, J¼8.3 Hz),
7.35e7.43 (m, 3H), 7.70 (d, 2H, J¼8.3 Hz); 13C NMR (125 MHz,
CDCl3):
d 55.4, 55.5, 98.7, 104.8, 121.0, 128.3, 131.0, 132.2, 137.3,
138.5, 159.5, 163.6, 194.2.
4.2.30. 4-Fluorophenyl 20-pyridyl ketone. Mp 82e83 ꢁC (lit.36 mp
68e69 C); IR (Nujol) 1654 cmꢀ1; 1H NMR (400 MHz, CDCl3)
d 7.16
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4.2.21. 4-Chloro-20,40,60-trimethylbenzophenone. Mp 67e69 ꢁC
(t, 2H, J¼8.7 Hz), 7.50 (ddd, 1H, J1¼7.7 Hz, J2¼4.8 Hz, J3¼1.1 Hz), 7.91
(td, 1H, J1¼7.7 Hz, J2¼1.8 Hz), 8.06 (dt, 1H, J1¼7.7 Hz, J2¼1.1 Hz),
8.14e8.19 (m, 2H), 8.72 (ddd, 1H, J1¼4.8 Hz, J2¼1.8 Hz, J3¼0.9 Hz);
(lit.30 mp 68e69.5 C); IR (Nujol) 1663 cm
;
1H NMR (500 MHz,
ꢀ1
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CDCl3):
d
2.07 (s, 6H), 2.33 (s, 3H), 6.90 (s, 2H), 7.41 (d, 2H, J¼8.9 Hz),
7.74 (d, 2H, J¼8.6 Hz); 13C NMR (125 MHz, CDCl3):
d
19.3, 21.1, 128.4,
13C NMR (100 MHz, CDCl3):
d
115.3 (d, JCeF¼22.0 Hz), 124.6, 126.3,
129.1, 130.8, 134.1, 135.7, 136.3, 138.8, 140.1, 199.4.
132.5 (d, JCeF¼2.9 Hz), 133.8 (d, JCeF¼9.6 Hz), 137.1, 148.4, 154.9,
165.7 (d, JCeF¼255.8 Hz), 192.0; HRMS (ESI) [M]þ, calcd for
C12H8FNO¼201.0590, observed¼201.0593.
4.2.22. 4-Chlorophenyl 40-biphenyl ketone.ꢀ1Mp 169e170 ꢁC (lit.31
;
1H NMR (500 MHz,
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mp 169.5e170.5 C); IR (Nujol) 1642 cm
CDCl3):
d
7.38e7.42 (m, 1H), 7.44e7.49 (m, 4H), 7.63 (d, 2H,
4.2.31. Ethyl 4-methoxyphenyl ketone. Colorless oil (commercial,
J¼8.6 Hz), 7.69 (d, 2H, J¼8.6 Hz), 7.77 (d, 2H, J¼8.6 Hz), 7.85 (d, 2H,
mp 25e27 ꢁC); IR (neat) 1681 cmꢀ1 1H NMR (500 MHz, CDCl3)
;
J¼8.6 Hz); 13C NMR (125 MHz, CDCl3):
d
127.0, 127.2, 128.2, 128.6,
d
1.21 (t, 3H, J¼7.2 Hz), 2.95 (q, 2H, J¼7.2 Hz), 3.87 (s, 3H), 6.94 (d,
128.9, 130.5, 131.3, 135.8, 136.0, 138.8, 139.8, 145.4, 194.9.
2H, J¼8.8 Hz), 7.95 (d, 2H, J¼8.9 Hz); 13C NMR (125 MHz, CDCl3)
d
8.4, 31.4, 55.4, 113.6, 130.0, 130.2, 163.3, 199.4.
4.2.23. 4-Chlorophenyl 20-naphthyl ketone. Mp 125e126 ꢁC (lit.32
mp 125.6e126 C); IR (Nujol) 1655 cm
ꢀ1
;
1H NMR (500 MHz,
4.2.32. Cyclohexyl 4-methoxyphenylꢀ1ketone. Mp 63e65 ꢁC (lit.37
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;
1H NMR (500 MHz, CDCl3)
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CDCl3):
d
7.48 (d, 2H, J¼8.6 Hz), 7.53e7.63 (m, 2H), 7.80 (d, 2H,
mp 62e64 C); IR (Nujol) 1682 cm
J¼8.9 Hz), 7.89e7.95 (m, 4H), 8.22 (s, 1H); 13C NMR (125 MHz,
d 1.22e1.31 (m, 1H), 1.34e1.44 (m, 2H), 1.46e1.54 (m, 2H),
CDCl3):
d
125.6, 125.8, 126.9, 127.8, 128.4, 128.7, 129.4, 131.5, 131.7,
1.70e1.76 (m, 1H), 1.81e1.90 (m, 4H), 3.18e3.26 (m, 1H), 3.86 (s,
132.2, 134.5, 135.3, 136.2, 138.8, 195.5.
3H), 6.93 (d, 2H, J¼9.2 Hz), 7.94 (d, 2H, J¼8.9 Hz); 13C NMR
(125 MHz, CDCl3)
163.2, 202.4.
d 25.9, 26.0, 29.5, 45.3, 55.4, 113.7, 129.3, 130.5,
4.2.24. 4-Chlorophenyl 20-pyridyl ꢀk1etone. Mp 64e67 ꢁC (lit.33 mp
66e69 C); IR (Nujol) 1659 cm
;
1H NMR (500 MHz, CDCl3):
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d
7.44e7.52 (m, 3H), 7.91 (td, 1H, J1¼7.7 Hz, J2¼1.4 Hz), 8.05e8.08
4.2.33. tert-Butyl 4-methoxypheny ketone. Colorless oil (lit.38 oil);
(m, 3H), 8.72 (d, 1H, J¼4.9 Hz); 13C NMR (125 MHz, CDCl3):
d
124.7,
IR (neat) 1666 cmꢀ1; 1H NMR (400 MHz, CDCl3)
d 1.37 (s, 9H), 3.85
126.4, 128.4, 132.5, 134.6, 137.2, 139.4, 148.5, 154.7, 192.4.
(s, 3H), 6.90 (d, 2H, J¼9.0 Hz), 7.85 (d, 2H, J¼9.1 Hz); 13C NMR
(100 MHz, CDCl3) d 28.3, 43.8, 55.3, 113.2, 130.0, 130.9, 161.9, 206.2.
4.2.25. 4-Chlorophenyl 20-thienyl ketone. Mp 97e101 ꢁC (lit.26 mp
93e95 C); IR (Nujol) 1630 cmꢀ1; 1H NMR (500 MHz, CDCl3):
d
7.17
4.2.34. Ethyl 4-methylphenyl ketone. Colorless oil (commercial, oil);
IR (neat) 1685 cmꢀ1 1H NMR (400 MHz, CDCl3)
1.21 (t, 3H,
J¼7.3 Hz), 2.39 (s, 3H), 2.95 (q, 2H, J¼7.2 Hz), 7.23 (d, 2H, J¼8.6 Hz),
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(dd, 1H, J1¼4.9 Hz, J2¼3.7 Hz), 7.48 (d, 2H, J¼8.6 Hz), 7.62 (dd, 1H,
;
d
J1¼3.7 Hz, J2¼1.2 Hz), 7.74 (dd, 1H, J1¼4.9 Hz, J2¼1.2 Hz), 7.82 (d, 2H,