M
M. A. Hussain, F. A. Khan
Paper
Synthesis
hyde21 (19l; 122 mg, 0.34 mmol) and piperidine (12 mg, 0.14 mmol)
at 80 °C to afford 1m as a yellow solid; yield: 120 mg (61%); mp 99–
101 °C; Rf = 0.50 (50% EtOAc in hexane, silica gel TLC).
(1E,4Z,6E)-1-(2,4-Dimethoxyphenyl)-5-hydroxy-7-(2-methoxy-
naphthalen-1-yl)hepta-1,4,6-trien-3-one (1p)
General procedure C described above was followed when compound
13a (80 mg, 0.30 mmol), B2O3 (41 mg, 0.60 mmol), and B(OMe)3 (62
mg, 0.60 mmol) reacted with 2,4-dimethoxybenzaldehyde (19n; 50
mg, 0.30 mmol) and piperidine (10 mg, 0.12 mmol) at 80 °C to afford
1p as a yellow solid; yield: 62 mg (50%); mp 141–144 °C; Rf = 0.50
(30% EtOAc in hexane, silica gel TLC).
IR (neat): 3482, 3073, 2962, 1627, 1572, 1510, 1432, 1374, 1268,
1204, 1175, 1133, 1029 cm–1
.
1H NMR (400 MHz, CDCl3/DMSO-d6, 3:1): = 15.98 (br s, 1 H), 8.78 (br
s, 1 H), 8.30 (br s, 1 H), 7.94 (d, J = 3.0 Hz, 1 H), 7.82 (d, J = 16.0 Hz, 1
H), 7.68 (dd, J = 16.0, 2.6 Hz, 1 H), 7.56 (d, J = 3.0 Hz, 1H), 7.29 (s, 1 H),
7.11 (d, J = 8.0 Hz, 1 H), 6.71 (d, J = 16.0 Hz, 2 H), 6.06 (s, 1 H), 4.12 (s,
3 H).
IR (neat): 3056, 3004, 2939, 2837, 1599, 1506, 1460, 1269, 1206,
1130, 1033, 968 cm–1
.
1H NMR (400 MHz, CDCl3): = 16.21 (br s, 1 H), 8.31 (d, J = 16.0 Hz, 1
H), 8.24 (d, J = 8.6 Hz, 1 H), 7.93 (d, J = 15.9 Hz, 1 H), 7.85–7.78 (m, 2
H), 7.54–7.48 (m, 2 H), 7.38 (t, J = 7.7 Hz, 1 H), 7.30 (d, J = 9.5 Hz, 1 H),
6.96 (d, J = 16.0 Hz, 1 H), 6.66 (d, J = 16.0 Hz, 1 H), 6.52 (dd, J = 8.8, 2.2
Hz, 1 H), 6.46 (d, J = 2.2 Hz, 1 H), 5.86 (s, 1 H), 4.02 (s, 3 H), 3.88 (s, 3
H), 3.84 (s, 3 H).
13C NMR (100 MHz, CDCl3/DMSO-d6, 3:1): = 186.0, 179.2, 150.7,
149.1, 147.6, 142.0, 137.2, 136.1, 135.1, 132.3, 126.6, 123.2, 121.1,
115.5, 113.1, 112.6, 111.1, 110.1, 102.0, 55.8.
HRMS (ESI-TOF): m/z calcd for C20H16Br3O5 [M + H]+: 572.8542; found:
572.8517.
13C NMR (100 MHz, CDCl3): = 185.0, 182.7, 162.7, 159.9, 156.6,
136.0, 133.0, 132.8, 131.3, 130.2, 129.4, 129.1, 128.6, 127.3, 123.9,
123.5, 122.5, 117.6, 117.2, 112.8, 105.4, 101.7, 98.4, 56.2, 55.52, 55.50.
HRMS (ESI-TOF): m/z calcd for C26H24O5Na [M + Na]+: 439.1516;
found: 439.1516.
(1E,4Z,6E)-1-(2-Bromo-3,4,5-trimethoxyphenyl)-5-hydroxy-7-(2-
methoxynaphthalen-1-yl)hepta-1,4,6-trien-3-one (1n)
General procedure C described above was followed when compound
13a (100 mg, 0.37 mmol), B2O3 (52 mg, 0.75 mmol), and B(OMe)3 (77
mg, 0.75 mmol) reacted with 2-bromo-3,4,5-trimethoxybenzalde-
hyde20 (19h; 102 mg, 0.37 mmol) and piperidine (13 mg, 0.15 mmol)
at 80 °C to afford 1n as a yellow solid; yield: 126 mg (65%); mp 118–
122 °C; Rf = 0.40 (30% EtOAc in hexane, silica gel TLC).
(1E,4Z,6E)-7-(Biphenyl-4-yl)-5-hydroxy-1-(2-methoxynaphthalen-
1-yl)hepta-1,4,6-trien-3-one (1q)
General procedure C described above was followed when compound
13a (85 mg, 0.32 mmol), B2O3 (44 mg, 0.63 mmol), and B(OMe)3 (65
mg, 0.63 mmol) reacted with [1,1′-biphenyl]-4-carbaldehyde (19e; 58
mg, 0.32 mmol) and piperidine (11 mg, 0.13 mmol) at 80 °C to afford
1q as a yellow solid; yield: 68 mg (49%); mp 187–190 °C; Rf = 0.50
(15% EtOAc in hexane, silica gel TLC).
IR (neat): 2939, 2839, 1769, 1620, 1560, 1512, 1473, 1428, 1391,
1344, 1269, 1200, 1105, 1006 cm–1
.
1H NMR (400 MHz, CDCl3): = 15.98 (br s, 1 H), 8.37 (d, J = 16.0 Hz, 1
H), 8.24 (d, J = 8.6 Hz, 1 H), 8.01 (d, J = 15.6 Hz, 1 H), 7.86 (d, J = 9.2 Hz,
1 H), 7.80 (d, J = 8.0 Hz, 1 H), 7.54–7.51 (m, 1 H), 7.39 (t, J = 8.0 Hz, 1
H), 7.31–7.25 (m, 1 H), 7.02–6.97 (m, 2 H), 6.51 (d, J = 15.5 Hz, 1 H),
5.94 (s, 1 H), 4.03 (s, 3 H), 3.89 (s, 9 H).
13C NMR (100 MHz, CDCl3): = 184.6, 182.3, 156.9, 152.8, 151.2,
144.7, 138.6, 134.1, 132.8, 131.7, 130.5, 129.1, 129.0, 128.67, 127.4,
126.2, 123.9, 123,4, 117.2, 113.2, 112.7, 105.9, 101.8, 61.2, 61.0, 56.28,
56.23.
IR (neat): 3035, 2938, 2839, 2160, 1622, 1557, 1510, 1463, 1348,
1267, 1184, 1138, 972 cm–1
.
1H NMR (400 MHz, CDCl3): = 16.0 (br s, 1 H), 8.37 (d, J = 15.9 Hz, 1
H), 8.24 (d, J = 8.5 Hz, 1 H), 7.86 (d, J = 9.0 Hz, 1 H), 7.76 (d, J = 7.6 Hz,
1 H), 7.71 (d, J = 15.9 Hz, 1 H), 7.63–7.61 (m, 6 H), 7.54 (ddd, J = 8.4,
7.0, 1.2 Hz, 1 H), 7.46 (t, J = 7.3 Hz, 2 H), 7.41–7.35 (m, 2 H), 7.30 (d, J =
9.0 Hz, 1 H), 7.01 (d, J = 16.0 Hz, 1 H), 6.68 (d, J = 16.0 Hz, 1 H), 5.91 (s,
1 H), 4.03 (s, 3 H).
HRMS (ESI-TOF): m/z calcd for C27H26BrO6 [M + H]+: 525.0907; found:
525.0901.
13C NMR (100 MHz, CDCl3): = 184.5, 182.8, 156.8, 142.7, 140.2,
139.7, 134.1, 133.9,132.8, 131.6, 129.2, 129.0, 128.9, 128.66, 128.60,
127.8, 127.5, 127.4, 127.0, 124.1, 123.9, 123.4, 117.3, 112.7, 102.1,
56.2.
HRMS (ESI-TOF): m/z calcd for C30H25O3 [M + H]+: 433.1798; found:
433.1796.
(1E,4Z,6E)-5-Hydroxy-7-(2-methoxynaphthalen-yl)-1-(3,4,5-tri-
methoxyphenyl)hepta-1,4,6-trien-3-one (1o)
General procedure C described above was followed when compound
13a (100 mg, 0.37 mmol) B2O3 (52 mg, 0.75 mmol), and B(OMe)3 (77
mg, 0.75 mmol) reacted with 3,4,5-trimethoxybenzaldehyde (19m;
72 mg, 0.37 mmol) and piperidine (13 mg, 0.15 mmol) at 80 °C to af-
ford 1o as a yellow solid; yield: 81 mg (49%); mp 145–148 °C; Rf = 0.50
(30% EtOAc in hexane, silica gel TLC).
(1E,4Z,6E)-7-[3-(But-3-en-2-yl)-4-hydroxy-5-methoxyphenyl]-5-
hydroxy-1-(4-hydroxy-3-methoxyphenyl)hepta-1,4,6-trien-3-one
(1r)
IR (neat): 2938, 2837, 2312, 2270, 2188, 2168, 1985, 1625, 1582,
1504, 1460, 1263, 1129 cm–1
.
General procedure C described above was followed when compound
13 (50 mg, 0.21 mmol), B2O3 (30 mg, 0.43 mmol), and B(OMe)3 (44
mg, 0.43 mmol) reacted with 3-(but-3-en-2-yl)-4-hydroxy-5-me-
thoxybenzaldehyde (11; 43 mg, 0.21 mmol) and piperidine (7.0 mg,
0.08 mmol) at 80 °C to afford 1r as a yellow solid; yield: 52 mg (59%);
mp 179–181 °C; Rf = 0.50 (30% EtOAc in hexane, silica gel TLC).
1H NMR (400 MHz, CDCl3): = 16.08 (br s, 1 H), 8.35 (d, J = 15.9 Hz, 1
H), 8.22 (d, J = 8.6 Hz, 1 H), 7.84 (d, J = 9.0 Hz, 1 H), 7.78 (d, J = 8.0 Hz,
1 H), 7.58 (d, J = 15.8 Hz, 1 H), 7.53–7.50 (m, 1 H), 7.40–7.36 (m, 1 H),
7.29–7.25 (m, 1 H), 6.98 (d, J = 16.0 Hz, 1 H), 6.77 (s, 2 H), 6.55 (d, J =
15.6 Hz, 1 H), 5.89 (s, 1 H), 4.01 (s, 3 H), 3.89 (s, 9H).
13C NMR (100 MHz, CDCl3): = 184.2, 182.9, 156.8, 153.4, 140.2,
139.9, 133.8, 132.8, 131.6, 130.6, 129.1, 129.0, 128.6, 127.4, 123.9,
123.6, 123.4, 117.2, 112.7, 105.1, 102.0, 61.0, 56.2, 56.1.
IR (neat): 3417, 2961, 1578, 1503, 1442, 1278, 1205, 1136, 965, 837
cm–1
.
1H NMR (400 MHz, DMSO-d6): = 16.37 (br s, 1 H), 9.69 (s, 1 H), 9.25
(s, 1 H), 7.56 (dd, J = 16.1, 2.2 Hz, 2 H), 7.33 (d, J = 1.5 Hz, 1 H), 7.24 (d,
J = 1.5 Hz, 1 H), 7.16 (dd, J = 8.4, 1.8 Hz, 1 H), 7.07 (d, J = 2.2 Hz, 1 H),
HRMS (ESI-TOF): m/z calcd for C27H27O6 [M + H]+: 447.1802; found:
447.1799.
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