V
D. Hermann et al.
Paper
Synthesis
1
Ar2
1H NMR (400 MHz, CDCl3): δ = 7.90 (AA′BB′, 2 H, 2Ar2-H), 7.79 (AA′BB′,
2 H, 2Ar1-H), 7.45 (s, 1 H, 4-H), 7.08 (AA′BB′, 2 H, 3Ar1-H), 6.96 (AA′BB′,
2 H, 3Ar2-H), 5.97 (s, 1 H, 1′-H), 3.85 (s, 3 H, OCH3).
13C NMR (126 MHz, CDCl3): δ = 168.58 (C-2), 163.64 (d, JC-4
=
,F
251.1 Hz, C-4Ar2), 147.45 (C-5), 135.79 (d, 6JC-4,F = 1.7 Hz, C-4), 135.28
(C-4Ar1), 131.87 (C-2Ar1), 131.81 (C-1Ar1), 129.30 (C-3Ar1), 129.28 (d, 3JC-
,F = 8.5 Hz, C-2Ar2), 128.26 (C-3), 125.66 (d, 4JC-1 ,F = 3.4 Hz, C-1Ar2),
Ar2
Ar2
1
Ar1
13C NMR (101 MHz, CDCl3): δ = 169.06 (C-2), 162.97 (d, JC-4
=
2
,F
Ar2
116.19 (d, 2JC-3 ,F = 21.8 Hz, C-3Ar2), 112.60 (C-1′).
251.3 Hz, C-4Ar1), 160.92 (C-4Ar2), 147.19 (d, JC-5,F = 2.8 Hz, C-5),
6
Ar11
Ar1
134.09 (C-4), 132.47 (d, 3JC-2 ,F = 8.2 Hz, C-2Ar1), 129.90 (d, 4JC-1
=
HRMS (APCI+): m/z [M + H]+ calcd for C17H11ClFO2: 301.0426; found:
,F
3.6 Hz, C-1Ar1), 128.75 (C-2Ar2), 128.53 (d, 8JC-3,F = 1.2 Hz, C-3), 122.21
301.0426.
2
Ar1
(C-1Ar2), 116.11 (d, JC-3
= 21.8 Hz, C-3Ar1), 114.48 (C-3Ar2), 111.61
,F
(d, 5JC-1′,F = 1.5 Hz, C-1′), 55.50 (OCH3).
(Z)-3-(4-Fluorophenyl)-5-(4-methoxybenzylidene)furan-2(5H)-
HRMS (APCI+): m/z [M + H]+ calcd for C18H14FO3: 297.0922; found:
one (65)
297.0921.
Yield: 0.189 g (82%, 2 steps); yellow solid; mp 156–158 °C.
IR (NaCl, CDCl3): 3350, 2925, 1740, 1605, 1510, 1450, 1360, 1300,
1170, 1105, 1035, 960, 900, 830, 810 cm–1
.
(Z)-5-Benzylidene-3-(4-fluorophenyl)furan-2(5H)-one (62)
[CAS Reg. No.: 208194-70-1]
1H NMR (300 MHz, CDCl3): δ = 7.94 (AA′BB′, 2 H, 2Ar2-H), 7.79 (AA′BB′,
2 H, 2Ar1-H), 7.55 (s, 1 H, 4-H), 7.13 (AA′BB′, 2 H, 3Ar2-H), 6.94 (AA′BB′,
2 H, 3Ar1-H), 6.05 (s, 1 H, 1′-H), 3.86 (s, 3 H, OCH3).
Yield: 0.038–0.050 g (92–95%, 1 step); yellow solid; mp 180–181 °C.
IR (NaCl, CDCl3): 3370, 3115, 2920, 2850, 1750, 1645, 1605, 1585,
1450, 1360, 1320, 1300, 1235, 1160, 1105, 970, 935, 865, 835, 730,
1
Ar2
13C NMR (101 MHz, CDCl3): δ = 169.06 (C-2), 163.41 (d, JC-4
=
,F
690 cm–1
.
250.5 Hz, C-4Ar2), 160.69 (C-4Ar1), 145.88 (C-5), 136.13 (d, JC-4,F = 2.2
6
3
Ar2
Hz, C-4), 132.57 (C-2Ar1), 129.07 (d, JC-2
= 8.3 Hz, C-2Ar2), 126.74
1H NMR (500 MHz, CDCl3): δ = 7.95 (AA′BB′, 2 H, 2Ar2-H), 7.82–7.80
(m, 2 H, 2Ar1-H), 7.56 (s, 1 H, 4-H), 7.43–7.39 (m, 2 H, 3Ar1-H), 7.36–
7.32 (m, 1 H, 4Ar1-H), 7.14 (AA′BB′, 2 H, 3Ar2-H), 6.09 (s, 1 H, 1′-H).
,F
4
Ar2
(C-3), 126.26 (C-1Ar1), 126.12 (d, JC-1
= 3.5 Hz, C-1Ar2), 116.06 (d,
,F
2JC-3 ,F = 21.8 Hz, C-3Ar2), 114.64 (C-3Ar1), 114.14 (C-1′), 55.54 (OCH3).
Ar2
HRMS (APCI+): m/z [M + H]+ calcd for C18H14FO3: 297.0922; found:
297.0923.
Ar2
13C NMR (126 MHz, CDCl3): δ = 168.84 (C-2), 163.55 (d, 1JC-4 ,F 250.9
6
Hz, C-4Ar2), 147.20 (C-5), 136.08 (d, JC-4,F = 1.7 Hz, C-4), 133.30 (C-
3
Ar2
1Ar1), 130.80 (C-2Ar1), 129.36 (C-4Ar1), 129.22 (d, JC-2
= 8.1 Hz, C-
,F
2Ar2), 129.02 (C-3Ar1), 127.89 (C-3), 125.81 (d, 4JC-1 ,F = 3.6 Hz, C-1Ar2),
Ar2
(Z)-5-(4-Fluorobenzylidene)-3-(4-fluorophenyl)furan-2(5H)-one
(66)
Ar2
116.12 (d, 2JC-3 ,F = 21.8 Hz, C-3Ar2), 114.12 (C-1′).
HRMS (APCI+): m/z [M + H]+ calcd for C17H12 FO2: 267.0816; found:
Yield: 0.165 g (74%, 2 steps); yellow solid; mp 211–212 °C.
267.0817.
IR (NaCl, CDCl3): 3350, 2925, 1745, 1605, 1505, 1445, 1365, 1245,
1160, 1105, 1040, 960, 900, 865, 830 cm–1
.
1H NMR (500 MHz, 323 K, CDCl3): δ = 7.94 (AA′BB′, 2 H, 2Ar2-H), 7.80
(AA′BB′, 2 H, 2Ar1-H), 7.53 (s, 1 H, 4-H), 7.13 (AA′BB′, 2 H, 3Ar2-H), 7.10
(AA′BB′, 2 H, 3Ar1-H), 6.03 (s, 1 H, 1′′-H).
(Z)-3-(4-Fluorophenyl)-5-(4-methylbenzylidene)furan-2(5H)-one
(63)
Yield: 0.130 g (59%, 2 steps); yellow solid; mp 178–181 °C.
Ar2
IR (NaCl, CDCl3): 3375, 2920, 2850, 1740, 1685, 1580, 1505, 1450,
13C NMR (126 MHz, 323 K, CDCl3): δ = 168.63 (C-2), 163.71 (d, 1JC-4
=
,F
1
Ar1
1295, 1235, 1160, 1105, 960, 915, 860, 835, 810 cm–1
.
250.9 Hz, C-4Ar2), 163.26 (d, JC-4
= 251.8 Hz, C-4Ar1), 146.97 (d,
,F
3
Ar1
6JC-5,F = 2.8 Hz, C-5), 135.88 (C-4), 132.69 (d, JC-2
= 8.5 Hz, C-2Ar1),
1H NMR (500 MHz, CDCl3): δ = 7.94 (AA′BB′, 2 H, 2Ar2-H), 7.71 (AA′BB′,
2 H, 2Ar1-H), 7.54 (s, 1 H, 4-H), 7.22 (AA′BB′, 2 H, 3Ar1-H), 7.13 (AA′BB′,
2 H, 3Ar2-H), 6.06 (s, 1 H, 1′-H), 2.38 (s, 3 H, CH3).
,F
Ar2
129.74 (d, 4JC-1 ,F = 3.3 Hz, C-1Ar1), 129.30 (d, 3JC-2 ,F = 8.4 Hz, C-2Ar2),
Ar1
4
Ar2
2
Ar1
128.07 (C-3), 125.88 (d, JC-1
= 3.7 Hz, C-1Ar2), 116.23 (d, JC-3
=
,F
Ar2
,F
21.9 Hz, C-3Ar1)*, 116.17 (d, 2JC-3 ,F = 21.9 Hz, C-3Ar2)*, 112.65 (C-1′′). *
1
Ar2
13C NMR (126 MHz, CDCl3): δ = 168.96 (C-2), 163.46 (d, JC-4
=
,F
Assignment interchangeable.
250.7 Hz, C-4Ar2), 146.66 (C-5), 139.85 (C-4Ar1), 136.14 (C-4), 130.81
HRMS (APCI+): m/z [M + H]+ calcd for C17H11 F2O2: 285.0722; found:
Ar2
(C-2Ar1), 130.58 (C-1Ar1), 129.81 (C-3Ar1), 129.14 (d, 3JC-2 ,F = 8.1 Hz, C-
285.0723.
4
Ar2
2Ar2), 127.37 (C-3), 125.95 (d, JC-1
= 3.3 Hz, C-1Ar2), 116.08 (d,
,F
Ar2
2JC-3 ,F = 21.8 Hz, C-3Ar2), 114.35 (C-1′), 21.67 (C-4Ar1).
(Z)-5-(4-Iodobenzylidene)-3-phenylfuran-2(5H)-one (67)
HRMS (APCI+): m/z [M + H]+ calcd for C18H14FO2: 281.0972; found:
281.0974.
Yield: 0.120 g (64%, 2 steps); yellow solid; mp 194–195 °C.
IR (NaCl, CDCl3): 3375, 3110, 2920, 1750, 1645, 1445, 1400, 1355,
1315, 1295, 1180, 1095, 1005, 955, 905, 860, 805, 785, 745, 730, 690,
(Z)-5-(4-Chlorobenzylidene)-3-(4-fluorophenyl)furan-2(5H)-one
(64)
660 cm–1
.
Yield: 0.036 g (62%, 2 steps); yellow solid; mp 187–188 °C.
1H NMR (300 MHz, CDCl3): δ = 7.95–7.92 (m, 2 H, 2Ar2-H), 7.74
(AA′BB′, 2 H, 2Ar1-H), 7.59 (s, 1 H, 4-H), 7.54 (AA′BB′, 2 H, 3Ar1-H), 7.48–
7.43 (m, 2 H, 3Ar2-H), 7.43–7.38 (m, 1 H, 4Ar2-H), 5.99 (s, 1 H, 1′-H).
IR (NaCl, CDCl3): 3380, 2920, 2850, 1750, 1605, 1510, 1490, 1465,
1295, 1250, 1165, 1095, 1015, 960, 855, 835 cm–1
.
13C NMR (126 MHz, CDCl3): δ =168.58 (C-2), 147.92 (C-5), 138.21 (C-
2Ar1), 136.23 (C-4), 132.82 (C-1Ar1), 132.12 (C-3Ar1), 129.91 (C-4Ar2),
129.49 (C-3)*, 129.43 (C-1Ar2)*, 129.03 (C-3Ar2), 127.28 (C-2Ar2), 112.60
(C-1′), 95.56 (C-4Ar1). * Assignment interchangeable.
1H NMR (300 MHz, CDCl3): δ = 7.95 (AA′BB′, 2 H, 2Ar2-H), 7.75 (AA′BB′,
2 H, 2Ar1-H), 7.56 (s, 1 H, 4-H), 7.38 (AA′BB′, 2 H, 3Ar1-H), 7.14 (AA′BB′,
2 H, 3Ar2-H), 6.03 (s, 1 H, 1′-H).
Anal. Calcd for C17H11IO2: C, 54.57; H, 2.96. Found: C, 54.58; H, 3.08.
© Georg Thieme Verlag Stuttgart · New York — Synthesis 2016, 48, A–AA