R. Grigg et al. / Tetrahedron 63 (2007) 7213–7228
7219
afforded 10 (17%) as a colourless viscous oil. (Found: C,
74.05; H, 5.60; N, 4.30. C19H17NO3 requires: C, 74.25; H,
5.50; N, 4.55%.) dH (500 MHz, CDCl3) 3.80 (3H, s, OMe),
4.50 (2H, s, OCH2), 5.35 (1H, s, 4-isoxazolone–H), 5.31
and 5.41 (2ꢁ1H, 2ꢁs, ]CH2), 6.78 (2H, d, J 8.7 Hz, 3-H
and 5-H), 7.13 (2H, d, J 8.7 Hz, 2-H and 6-H), 7.35 (2H,
d, J 7.9 Hz, 20-H and 60-H), 7.45 (2H, dd J 7.9 and 7.2 Hz,
30-H and 50-H) and 7.52 (1H, m, 40-H); dC (75 MHz,
CDCl3) 55.7, 57.3, 91.7, 113.9, 116.8, 127.5, 129.6, 131.3,
131.9, 140.9, 159.9 and 169.2; m/z % (ES) 308 (M++H,
100); nmax/cmꢂ1 (film) 3060, 2980 and 1680.
2ꢁOMe), 5.11 and 5.18 (2ꢁ2H, 2ꢁs, 2ꢁ]CH2), 7.09
(4H, d, J 8.1 Hz, 2ꢁ2-H and 2ꢁ6-H), 7.11–7.14 (2H, m,
30-H and 50-H), 7.28 (1H, m, 40-H), 7.32 (2H, d, J 7.7 Hz,
20-H and 60-H) and 7.71 (4H, d, J 8.1 Hz, 2ꢁ3-H and 2ꢁ
5-H); dC (75 MHz, CDCl3) 42.3 (CH2), 52.4 (OMe), 57.2,
120.9 (]CH2), 126.5, 127.2, 128.3, 128.8, 129.6, 131.6,
142.2, 144.9, 167.0 (CO) and 179.6 (CO); m/z % (ES) 510
(M++H, 85); nmax/cmꢂ1 (film) 3054, 2988, 1793 and 1634.
3.2.4. 4,4-Bis{2-[3,5-bis(trifluoromethyl)phenyl]prop-2-
en-1-yl}-3-phenylisoxazol-5(4H)-one (16).
CF3
F3C
3.2.2. Methyl 4-(1-{[5-({2-[4-(methoxycarbonyl)phenyl]-
prop-2-en-1-yl}oxy)-3-phenylisoxazol-4-yl]methyl}vi-
nyl)benzoate (11).
CF3
5'
4'
6
4
3'
6'
CF3
2'
CO2Me
3
5
2
5'
4'
2'
N
6
O
6'
O
3'
16
2
N
2''
Prepared from 3-phenyl-5-isoxazolone and 3,5-bis(trifluoro-
methyl)iodobenzene by general procedure A. Column chro-
matography eluting with 4:1 v/v hexane–Et2O (Rf 0.06)
afforded 16 (63%) as colourless plates, mp 55–57 ꢀC.
(Found: C, 55.95; H, 2.90; N, 1.90. C31F12H19NO2 requires:
C, 55.95; H, 2.85; N, 2.10%.) dH (500 MHz, CDCl3) 3.33
and 3.31 (2ꢁ2H, 2ꢁd, J 13.9 Hz, 2ꢁCH2), 5.25 and 5.32
(2ꢁ2H, 2ꢁs, 2ꢁ]CH2), 7.00–7.04 (2H, dd, J 8.1 and
7.7 Hz, 30-H and 50-H), 7.16–7.19 (3H, m, 20-H, 60-H and
40-H), 7.40 (4H, s, 2ꢁ2-H and 2ꢁ6-H) and 7.46 (2H, s,
2ꢁ4-H); dC (75 MHz, CDCl3) 41.9, 57.6, 117.4, 121.0,
121.4, 125.3, 126.0, 127.1, 128.3, 128.5, 128.9, 131.9 (q,
JC–F 33.3 Hz, C–CF3), 140.4, 142.2, 164.6 and 179.0
(CO); m/z % (ES) 666 (M++H, 40); nmax/cmꢂ1 (film) 3054,
2987, 1795 and 1265.
O
O
3''
11
6''
CO2Me
5''
Prepared from 3-phenyl-5-isoxazolone and methyl 4-iodo-
benzoate by general procedure A at 100 ꢀC for 16 h. Column
chromatography eluting with 1:1 v/v hexane–ethyl acetate
(Rf 0.25) afforded 11 (55%) as colourless needles, mp 130–
132 ꢀC. (Found: C, 72.95; H, 5.30; N, 2.85. C31H27NO6 re-
quires: C, 73.05; H, 5.30; N, 2.75%.) dH (500 MHz,
CDCl3) 3.39 (2H, s, CCH2), 3.90 and 3.92 (2ꢁ3H, 2ꢁs,
2ꢁOMe), 4.40 (2H, s, OCH2), 4.98, 5.40, 5.42 and 5.53
(4ꢁ1H, 4ꢁs, 2ꢁ]CH2), 7.20 (2H, d, J 7.3 Hz, 20-H and
60-H), 7.22 (2H, d, J 8.1 Hz, 200-H and 600-H), 7.34 (2H, d, J
8.1 Hz, 2-H and 6-H), 7.42 (2H, dd, J 7.7 and 7.3 Hz, 30-H
and 50-H), 7.50–7.52 (1H, m, 40-H), 7.91 and 7.92 (2ꢁ2H,
2ꢁd, J 8.1 Hz, 3-H, 5-H, 300-H and 500-H); dC (75 MHz,
CDCl3) 28.4, 52.4, 57.2, 117.2, 120.7, 126.4, 126.8, 128.5,
129.6, 129.9, 130.1, 131.6, 142.2, 144.9 and 179.6 (CO);
m/z % (ES) 527 (M+NH+4, 100); nmax/cmꢂ1 (film) 3054,
2987, 1742 and 1632.
3.2.5. 4,4-Bis[2-(3-chloro-4-fluorophenyl)prop-2-en-1-
yl]-3-phenylisoxazol-5(4H)-one (17).
F
Cl
F
5
5'
4'
3'
6
Cl
3.2.3. Dimethyl 4,40-[(5-oxo-3-phenyl-4,5-dihydroisox-
azole-4,4-diyl)diprop-1-ene-3,2-diyl]dibenzoate (12).
6'
2
2'
N
O
O
17
MeO2C
Prepared from 3-phenyl-5-isoxazolone and 3-chloro-4-fluo-
roiodobenzene by general procedure A. Column chromato-
graphy eluting with 4:1 v/v hexane–Et2O (Rf 0.1) afforded
17 (54%) as colourless plates, mp 34–36 ꢀC. (Found: C,
65.25; H, 3.80; Cl, 14.10; N, 2.75. C27Cl2F2H19NO2 re-
quires: C, 65.05; H, 3.80; Cl, 14.25; N, 2.80%.) dH
(500 MHz, C6D6) 2.58 and 2.80 (2ꢁ2H, 2ꢁd, J 14.0 Hz,
2ꢁCH2), 4.80 and 5.06 (2ꢁ2H, 2ꢁs, 2ꢁ]CH2), 6.33 (2H,
dd, JH–F 8.9 and 8.5 Hz, 2ꢁ5-H), 6.47 (2H, ddd, J 8.5,
JH–F 6.8 and 2.1 Hz, 2ꢁ6-H), 6.76 (2H, dd, J 8.1 and
7.6 Hz, 30-H and 50-H), 6.80 (1H, m, 40-H), 6.81 (2H, dd,
JH–F 6.8 and 2.1 Hz, 2ꢁ2-H) and 7.00 (2H, d, J 8.1 Hz,
20-H and 60-H); dC (75 MHz, CDCl3) 42.7 (CH2), 57.5,
116.5, 120.8 (]CH2), 126.2, 127.7, 128.1, 128.8, 129.6,
131.9, 137.4, 141.0, 165.5 and 179.6 (CO); m/z % (ES) 501
5
CO2Me
3
5'
4'
3'
6
6'
2
2'
N
O
O
12
Prepared from 3-phenyl-5-isoxazolone and methyl 4-iodo-
benzoate by general procedure A. Column chromatography
eluting with 1:1 v/v hexane–ethyl acetate (Rf 0.35) afforded
12 (61%) as a colourless solid, which crystallized from hex-
ane–ethyl acetate as colourless plates, mp 105–107 ꢀC.
(Found: C, 72.90; H, 5.10; N, 2.60. C31H27NO6 requires: C,
73.05; H, 5.30; N, 2.75%.) dH (500 MHz, CDCl3) 3.29 and
3.30 (2ꢁ2H, 2ꢁd, J 14.2 Hz, 2ꢁCH2), 3.86 (6H, s,