H
Y.-l. Zheng et al.
Paper
Synthesis
HRMS (ESI): m/z calcd for C18H18
O
[M + H]+: 251.1430; found:
HRMS (ESI): m/z calcd for C21H24O2 [M + H]+: 309.1849; found:
251.1425.
309.1841.
4-(3,4-Dimethylphenyl)-4-phenylbut-3-en-2-one (3ap)
4-(4-Fluorophenyl)-4-(4-methoxyphenyl)but-3-en-2-one (3bd)
Yellow oil; yield: 292 mg (78%); mixture of geometric isomers
(~1:0.7).
Yellow oil; yield: 231 mg (57%); mixture of geometric isomers
(~1:0.4).
1H NMR (400 MHz, CDCl3): δ = 7.39 (d, J = 4.6 Hz, 3.4 H), 7.32–7.29 (m,
3.4 H), 7.20 (d, J = 4.7 Hz, 2 H), 7.15 (d, J = 7.5 Hz, 0.7 H), 7.10–7.05 (m,
2 H), 6.96 (dd, J = 13.1, 8.5 Hz, 2.1 H), 6.58 (s, 1 H, major CH), 6.52 (s,
0.7 H, minor CH), 2.30 (s, 2.1 H, minor CH3), 2.25 (s, 5.1 H, CH3), 2.21
(s, 3 H, major CH3), 1.88 (s, 2.1 H, minor CH3), 1.84 (s, 3 H, major CH3).
1H NMR (400 MHz, CDCl3): δ = 7.32–7.25 (m, 2.4 H), 7.24–7.18 (m, 1.4
H), 7.14–7.08 (m, 2.6 H), 7.02 (t, J = 7.7 Hz, 2 H), 6.94 (d, J = 7.7 Hz, 2
H), 6.86 (d, J = 7.9 Hz, 0.8 H, minor ArH), 6.56 (s, 0.4 H, minor CH),
6.45 (s, 1 H, major CH), 3.86 (s, 3 H, major OCH3), 3.82 (s, 1.2 H, minor
OCH3), 1.93–1.90 (m, 4.2 H).
13C NMR (151 MHz, CDCl3): δ = 200.6, 200.2, 154.5, 154.4, 141.3,
139.4, 138.6, 138.5, 137.6, 136.8, 136.6, 130.9, 129.9, 129.8, 129.8,
129.6, 129.5, 128.8, 128.7, 128.5, 127.7, 127.5, 127.0, 126.3, 30.4, 30.4,
20.0, 19.9, 19.8, 19.8.
13C NMR (151 MHz, CDCl3): δ = 200.3, 199.4, 163.6 (d, J = 251 Hz),
163.0 (d, J = 249 Hz), 161.0, 160.4, 152.9, 152.9, 137.4 (d, J = 3 Hz),
135.1 (d, J = 2 Hz), 133.0, 131.5 (d, J = 7 Hz), 131.3, 130.9, 130.5 (d, J =
9 Hz), 129.9, 127.2, 125.7, 115.5, 115.5, 115.4, 115.3, 113.9, 55.4, 55.3,
30.6, 30.2.
HRMS (ESI): m/z calcd for
C18H18O
[M + H]+: 251.1430; found:
251.1423.
HRMS (ESI): m/z calcd for C17H15FO2 [M + H]+: 271.1129; found:
271.1134.
4-(4-Methoxyphenyl)-4-(p-tolyl)but-3-en-2-one (3ba)
4-(4-Fluorophenyl)-4-(p-tolyl)but-3-en-2-one (3ca)
Yellow oil; yield: 338 mg (85%); mixture of geometric isomers
(~1:0.9).
Yellow oil; yield: 230 mg (60%); mixture of geometric isomers
(~1:0.4).
1H NMR (400 MHz, CDCl3): δ = 7.25–7.18 (m, 5.8 H), 7.14 (d, J = 3.5 Hz,
1.8 H, minor ArH), 7.12 (d, J = 3.0 Hz, 1.8 H, minor ArH), 7.09 (d, J = 7.7
Hz, 2 H, major ArH), 6.92 (d, J = 8.4 Hz, 1.8 H, minor ArH), 6.84 (d,
J = 8.7 Hz, 2 H, major ArH), 6.51 (s, 1 H, major CH), 6.49 (s, 0.9 H, mi-
nor CH), 3.84 (s, 2.7 H, minor OCH3), 3.80 (s, 3 H, major OCH3), 2.40 (s,
3 H, major CH3), 2.35 (s, 2.7 H, minor CH3), 1.89 (s, 2.7 H, minor CH3),
1.85 (s, 3 H, major CH3).
13C NMR (151 MHz, CDCl3): δ = 200.5, 200.3, 161.0, 160.4, 154.3,
154.3, 139.8, 138.9, 138.6, 136.4, 133.5, 131.4, 131.4, 130.1, 129.8,
129.2, 128.7, 126.8, 126.0, 113.9, 113.9, 55.5, 55.4, 30.4, 21.5, 21.4.
1H NMR (400 MHz, CDCl3): δ = 7.27 (dd, J = 8.8, 5.5 Hz, 0.8 H, minor
ArH), 7.24–7.06 (m, 9.6 H), 7.00 (t, J = 8.6 Hz, 0.8 H, minor ArH), 6.58
(s, 1 H, major CH), 6.49 (s, 0.4 H, minor CH), 2.41 (s, 1.2 H, minor CH3),
2.36 (s, 3 H, major CH3), 1.94 (s, 3 H, major CH3), 1.89 (s, 1.2 H, minor
CH3).
13C NMR (151 MHz, CDCl3): δ = 200.2, 199.5, 163.6 (d, J = 251 Hz),
163.1 (d, J = 249 Hz), 153.2, 153.1, 140.1, 139.2, 138.0, 137.3 (d, J = 2
Hz), 135.9, 135.1 (d, J = 3 Hz), 131.6 (d, J = 8 Hz), 130.6 (d, J = 9 Hz),
129.7, 129.4, 128.5, 127.5, 126.8, 115.6, 115.6, 115.5, 115.4, 30.7, 30.4,
21.5, 21.4.
MS (ESI): m/z = 267.2 [M + H]+.
HRMS (ESI): m/z calcd for C17H15FO [M + H]+: 255.1180; found:
4,4-Bis(4-methoxyphenyl)but-3-en-2-one (3bb)6
255.1177.
Yellow oil; yield: 236 mg (56%).
4-(4-Chlorophenyl)-4-(4-fluorophenyl)but-3-en-2-one (3cb)
1H NMR (400 MHz, CDCl3): δ = 7.25 (d, J = 8.5 Hz, 2 H), 7.14 (d, J = 8.2
Hz, 2 H), 6.93 (d, J = 8.3 Hz, 2 H), 6.85 (d, J = 8.5 Hz, 2 H), 6.47 (s, 1 H),
3.86 (s, 3 H), 3.82 (s, 3 H), 1.87 (s, 3 H).
13C NMR (151 MHz, CDCl3): δ = 200.3, 160.9, 160.3, 154.0, 133.6,
131.3, 130.1, 125.8, 113.8, 55.4, 55.3, 30.2.
Yellow oil; yield: 99 mg (24%); mixture of geometric isomers (~1:0.3).
1H NMR (400 MHz, CDCl3): δ = 7.39 (d, J = 8.2 Hz, 0.6 H, minor ArH),
7.31 (d, J = 8.5 Hz, 2 H, major ArH), 7.27 (d, J = 3.7 Hz, 0.3 H, minor
ArH), 7.24–7.15 (m, 4.6 H), 7.11 (t, J = 8.7 Hz, 2.3 H), 7.03 (t, J = 8.5 Hz,
0.6 H, minor ArH), 6.55 (s, 1.3 H), 1.99 (s, 0.9 H, minor CH3), 1.97 (s, 3
H, major CH3).
MS (ESI): m/z = 283.1 [M + H]+.
13C NMR (151 MHz, CDCl3): δ = 199.5, 199.2, 163.8 (d, J = 251 Hz),
163.3 (d, J = 251 Hz), 151.7, 151.7, 139.4, 137.3, 136.8 (d, J = 3 Hz),
135.9, 135.2, 134.5 (d, J = 3 Hz), 131.6 (d, J = 8 Hz), 131.1, 130.4 (d, J =
8 Hz), 129.8, 128.9, 127.8, 127.3, 115.9, 115.8, 115.7, 115.7, 30.9, 30.8.
HRMS (ESI): m/z calcd for C16H12ClFO [M + H]+: 275.0633; found:
275.0626.
4-(4-(tert-Butyl)phenyl)-4-(4-methoxyphenyl)but-3-en-2-one
(3bc)
Yellow oil; yield: 297 mg (64%); mixture of geometric isomers
(~1:0.6).
1H NMR (400 MHz, CDCl3): δ = 7.42 (d, J = 7.9 Hz, 1.2 H, minor ArH),
7.35 (d, J = 7.8 Hz, 2 H, major ArH), 7.25 (t, J = 7.0 Hz, 3.2 H), 7.15 (t,
J = 7.5 Hz, 3.2 H), 6.94 (d, J = 8.5 Hz, 2 H, major ArH), 6.86 (d, J = 8.6 Hz,
1.2 H, minor ArH), 6.52 (s, 1.6 H), 3.86 (s, 3 H, major OCH3), 3.82 (s, 1.8
H, minor OCH3), 1.89 (s, 3 H, major CH3), 1.83 (s, 1.8 H, minor CH3),
1.36 (s, 5.4 H, minor tBu), 1.32 (s, 9 H, major tBu).
4-(4-Chlorophenyl)-4-(p-tolyl)but-3-en-2-one (3c′a)
Yellow oil; yield: 224 mg (55%); mixture of geometric isomers
(~1:0.6).
1H NMR (400 MHz, CDCl3): δ = 7.37 (d, J = 8.1 Hz, 2 H, major ArH),
7.28 (d, J = 8.4 Hz, 1.2 H, minor ArH), 7.21 (d, J = 8.3 Hz, 2 H, major
ArH), 7.19–7.11 (m, 6.4 H), 7.07 (d, J = 7.6 Hz, 1.2 H, minor ArH), 6.58
(s, 1 H, major CH), 6.49 (s, 0.6 H, minor CH), 2.40 (s, 1.8 H, minor CH3),
2.35 (s, 3 H, major CH3), 1.97 (s, 3 H, major CH3), 1.88 (s, 1.8 H, minor
CH3).
13C NMR (151 MHz, CDCl3): δ = 200.6, 200.5, 160.9, 160.3, 154.3,
154.1, 153.0, 152.2, 138.3, 136.2, 133.5, 131.4, 130.1, 129.6, 128.5,
126.9, 126.1, 125.5, 125.4, 113.9, 55.5, 55.4, 34.8, 31.5, 31.3, 30.4,
30.3.
© Georg Thieme Verlag Stuttgart · New York — Synthesis 2018, 50, A–K