A. Tavares, P. H. Schneider, A. A. Merlo
FULL PAPER
Ar) ppm. 13C NMR (CDCl3/[D6]DMSO): δ = 13.8, 22.3, 25.6, 28.8,
28.9, 29.0, 29.1, 31.5, 38.9, 67.8, 77.4, 114.3, 120.6, 128.1, 155.3,
N=CCHHCH), 3.36 (dd, J = 16.8, 10.5 Hz, 1 H, N=CCHHCH),
3.67 (dd, J = 12.0, 4.8 Hz, 1 H, CHCHHOH), 3.86 (dd, J = 12.0,
160.5, 172.2 ppm. IR: ν = 3183, 2925, 2854, 1721, 1608, 1518, 1461, 3.3 Hz, 1 H, CHCHHOH), 3.97 (t, J = 6.6 Hz, 2 H, CH2O), 4.84
˜
1377, 1253, 1182, 1045, 1010, 898, 828, 721, 667 cm–1. C19H27NO4 (m, 1 H), 6.89 (d, J = 9.0 Hz, 2 H, Ar), 7.58 (d, J = 8.7 Hz 2 H,
(333.43): calcd. C 68.44, H 8.16, N 4.20; found C 68.32, H 8.09, N
4.32.
Ar) ppm. 13C NMR (CDCl3): δ = 13.9, 22.5, 25.8, 29.0, 29.1, 29.2,
29.3, 31.7, 36.5, 63.3, 68.0, 80.9, 114.4, 121.5, 128.0, 156.4,
160.5 ppm. IR: ν = 3294, 3189, 2923, 2854, 1611, 1515, 1463, 1377,
˜
3-[4-(Decyloxy)phenyl]-4,5-dihydroisoxazole-5-carboxylic Acid (6d):
Yield 309 mg, 89%; white solid; m.p. 138 °C. 1H NMR (CDCl3): δ
= 0.88 (m, 3 H, CH3), 1.38 [m, 14 H, (CH2)7], 1.79 (m, 2 H,
CH2CH2O), 3.62 (d, J = 9.0 Hz, 2 H, CH2CH), 3.98 (t, J = 6.6 Hz,
2 H, CH2O), 5.12 (t, J = 9.0 Hz, 1 H, CH2CH), 6.90 (d, J = 8.7 Hz,
2 H, Ar), 7.59 (d, J = 8.7 Hz, 2 H, Ar) ppm. 13C NMR (CDCl3/
[D6]DMSO): δ = 13.8, 22.3, 25.6, 28.8, 28.9, 29.0, 29.2, 30.6, 31.5,
1254, 1182, 1048, 876, 820, 721, 666 cm–1. C19H29NO3 (319.44):
calcd. C 71.44, H 9.15, N 4.38; found C 71.65, H 9.25, N 4.50.
{3-[4-(Decyloxy)phenyl]-4,5-dihydroisoxazol-5-yl}methanol
(7d):
1
Yield 273 mg, 41%; white solid; m.p. 95 °C. H NMR (CDCl3): δ
= 0.89 (m, 3 H, CH3), 1.43 [m, 14 H, (CH2)7], 1.79 (m, 2 H,
CH2CH2O), 2.05 (br., 1 H, OH), 3.24 (dd, J = 16.5, 7.8 Hz, 1 H,
N=CCHHCH), 3.37 (dd, J = 16.5, 10.5 Hz, 1 H, N=CCHHCH),
3.67 (dd, J = 12.0, 4.8 Hz, 1 H, CHCHHOH), 3.86 (dd, J = 12.0,
3.3 Hz, 1 H, CHCHHOH), 3.98 (t, J = 6.6 Hz, 2 H, CH2O), 4.84
(m, 1 H), 6.90 (d, J = 9.0 Hz, 2 H, Ar), 7.58 (d, J = 8.7 Hz, 2 H,
Ar) ppm. 13C NMR (CDCl3): δ = 14.0, 22.6, 25.9, 29.1, 29.2, 29.3,
29.4, 29.5, 31.8, 36.5, 63.5, 68.0, 80.9, 114.5, 121.5, 128.1, 156.6,
38.9, 67.7, 77.4, 114.3, 120.5, 128.1, 155.3, 160.5, 172.1 ppm. IR: ν
˜
= 3183, 2925, 2854, 1720, 1610, 1517, 1461, 1377, 1251, 1183, 1042,
1010, 898, 830, 721, 665 cm–1. C20H29NO4 (347.45): calcd. C 69.14,
H 8.41, N 4.03; found C 69.23, H 8.33, N 4.12.
3-(4-Bromophenyl)-4,5-dihydroisoxazole-5-carboxylic Acid (6e):
Yield 127 mg, 47%; brown solid; m.p. 173–175 °C. 1H NMR
(CDCl3): δ = 3.62 (d, J = 9.3 Hz, 2 H, CH2CH), 5.16 (t, J = 9.3 Hz,
1 H, CH2CH), 7.55 (s, 4 H, Ar) ppm. 13C NMR (CDCl3/[D6]-
160.6 ppm. IR: ν = 3294, 3187, 2923, 2854, 1610, 1515, 1463, 1377,
˜
1256, 1182, 1047, 877, 820, 721, 667 cm–1. C20H31NO3 (333.47):
calcd. C 72.04, H 9.37, N 4.20; found C 71.98, H 9.24, N 4.45.
DMSO):
δ = 38.5, 77.8, 124.4, 127.4, 128.1, 131.7, 155.0,
171.8 ppm. IR: ν = 3200–3100, 2924, 2854, 1726, 1592, 1462, 1377,
˜
Butyl 3-[4-(Heptyloxy)phenyl]-4,5-dihydroisoxazole-5-carboxylate
(8a): Yield 112 mg, 31%; yellow solid; m.p. 34 °C. 1H NMR
(CDCl3): δ = 0.91 [m, 6 H, (CH3)2], 1.38 [m, 10 H, (CH2)5], 1.67
(m, 2 H, CH2CH2OCO), 1.79 (m, 2 H, CH2CH2O), 3.60 (d, J =
10.2 Hz, 1 H, CHHCH), 3.61 (d, J = 8.4 Hz, 1 H, CHHCH), 3.98
(t, J = 6.6 Hz, 2 H, CH2O), 4.20 (t, J = 6.6 Hz, 2 H, CH2OCO),
1225, 899, 824 cm–1. C10H8BrNO3 (270.08): calcd. C 44.47, H 2.29,
N 5.19; found C 44.56, H 2.41, N 5.25.
3-(4-Nitrophenyl)-4,5-dihydroisoxazole-5-carboxylic Acid (6g): Yield
118 mg, 25%; white solid; m.p. 130 °C. 1H NMR (CDCl3/[D6]-
DMSO): δ = 3.69 (d, J = 9.3 Hz, 2 H, CH2CH), 5.25 (m, 1 H,
CH2CH), 7.45 (br., 1 H, OH), 7.87 (d, J = 8.4 Hz, 2 H, Ar), 8.27 5.13 (dd, J = 8.4, 10.2 Hz, 1 H, CHHCH), 6.90 (d, J = 9.0 Hz, 2
(d, J = 8.4 Hz, 2 H, Ar) ppm. C10H8N2O5 (236.18): calcd. C 50.85,
H, Ar), 7.60 (d, J = 9.0 Hz, 2 H, Ar) ppm. 13C NMR (CDCl3): δ
H 3.41, N 11.86; found C 50.78, H 3.49, N 12.01.
= 13.5, 13.9, 18.9, 22.4, 25.8, 28.9, 29.0, 30.3, 31.6, 39.0, 65.6, 68.0,
77.7, 114.5, 120.7, 128.3, 155.5, 160.8, 170.3 ppm. IR: ν = 2923,
˜
{3-[4-(Heptyloxy)phenyl]-4,5-dihydroisoxazol-5-yl}methanol
(7a):
2854, 1737, 1610, 1519, 1456, 1377, 1264, 1210, 1017, 879, 828,
722, 664 cm–1. C21H31NO4 (361.48): calcd. C 69.78, H 8.64, N 3.87;
found C 69.58, H 8.59, N 3.98.
1
Yield 419 mg, 36%; white solid; m.p. 96 °C. H NMR (CDCl3): δ
= 0.89 (m, 3 H, CH3), 1.41 [m, 8 H, (CH2)4], 1.79 (m, 2 H,
CH2CH2O), 2.10 (br., 1 H, OH), 3.24 (dd, J = 16.5, 7.8 Hz, 1 H,
N=CCHHCH), 3.36 (dd, J = 16.5, 10.5 Hz, 1 H, N=CCHHCH),
3.67 (dd, J = 12.0, 4.8 Hz, 1 H, CHCHHOH), 3.85 (dd, J = 12.0,
3.3 Hz, 1 H, CHCHHOH), 3.97 (t, J = 6.6 Hz, 2 H, CH2O), 4.83
(m, 1 H), 6.89 (d, J = 9.0 Hz, 2 H, Ar), 7.58 (d, J = 8.7 Hz, 2 H,
Ar) ppm. 13C NMR (CDCl3): δ = 13.9, 22.5, 25.8, 28.9, 29.0, 31.6,
Butyl
3-[4-(Octyloxy)phenyl]-4,5-dihydroisoxazole-5-carboxylate
(8b): Yield 244 mg, 65%; yellow solid; m.p. 35 °C. 1H NMR
(CDCl3): δ = 0.91 [m, 6 H, (CH3)2], 1.38 [m, 12 H, (CH2)6], 1.67
(m, 2 H, CH2CH2OCO), 1.79 (m, 2 H, CH2CH2O), 3.60 (d, J =
9.9 Hz, 1 H, CHHCH), 3.61 (d, J = 8.1 Hz, 1 H, CHHCH), 3.98
(t, J = 6.6 Hz, 2 H, CH2O), 4.20 (t, J = 6.6 Hz, 2 H, CH2OCO),
5.13 (dd, J = 8.1, 9.9 Hz, 1 H, CHHCH), 6.90 (d, J = 9.0 Hz, 2 H,
Ar), 7.60 (d, J = 9.0 Hz, 2 H, Ar) ppm. 13C NMR (CDCl3): δ =
13.5, 14.0, 18.9, 22.5, 25.9, 29.0, 29.1, 29.2, 30.3, 31.7, 39.0, 65.6,
36.5, 63.4, 68.0, 80.9, 114.5, 121.5, 128.1, 156.5, 160.5 ppm. IR: ν
˜
= 3294, 3187, 2923, 2854, 1610, 1517, 1463, 1377, 1253, 1181, 1049,
875, 820, 721, 665 cm–1. C17H25NO3 (291.39): calcd. C 70.07, H
8.65, N 4.81; found C 70.12, H 8.71, N 4.89.
68.0, 77.7, 114.5, 120.6, 128.3, 155.5, 160.8, 170.4 ppm. IR: ν =
˜
{3-[4-(Octyloxy)phenyl]-4,5-dihydroisoxazol-5-yl}methanol
(7b):
1
2923, 2854, 1738, 1612, 1519, 1458, 1377, 1264, 1210, 1019, 881,
827, 722, 666 cm–1. C22H33NO4 (375.51): calcd. C 70.37, H 8.86, N
3.73; found C 70.18, H 8.69, N 3.90.
Yield 219 mg, 36%; white solid; m.p. 94 °C. H NMR (CDCl3): δ
= 0.89 (m, 3 H, CH3), 1.41 [m, 10 H, (CH2)5], 1.78 (m, 2 H,
CH2CH2O), 2.99 (br., 1 H, OH), 3.24 (dd, J = 16.8, 8.1 Hz, 1 H,
N=CCHHCH), 3.34 (dd, J = 16.8, 10.5 Hz, 1 H, N=CCHHCH),
3.67 (dd, J = 12.0, 4.8 Hz, 1 H, CHCHHOH), 3.83 (dd, J = 12.0,
3.3 Hz, 1 H, CHCHHOH), 3.96 (t, J = 6.6 Hz, 2 H, CH2O), 4.81
(m, 1 H), 6.87 (d, J = 9.0 Hz, 2 H, Ar), 7.56 (d, J = 8.7 Hz, 2 H,
Ar) ppm. 13C NMR (CDCl3): δ = 13.9, 22.5, 25.8, 29.0, 29.1, 29.2,
31.7, 36.5, 63.4, 68.0, 80.9, 114.5, 121.4, 128.1, 156.5, 160.5 ppm.
Butyl
3-[4-(Nonyloxy)phenyl]-4,5-dihydroisoxazole-5-carboxylate
(8c): Yield 151 mg, 38%; yellow solid; m.p. 40 °C. 1H NMR
(CDCl3): δ = 0.91 [m, 6 H, (CH3)2], 1.38 [m, 14 H, (CH2)7], 1.67
(m, 2 H, CH2CH2OCO), 1.79 (m, 2 H, CH2CH2O), 3.60 (d, J =
9.9 Hz, 1 H, CHHCH), 3.61 (d, J = 8.4 Hz, 1 H, CHHCH), 3.98
(t, J = 6.6 Hz, 2 H, CH2O), 4.20 (t, J = 6.6 Hz, 2 H, CH2OCO),
5.13 (dd, J = 8.4, 9.9 Hz, 1 H, CHHCH), 6.91 (d, J = 9.0 Hz, 2 H,
Ar), 7.60 (d, J = 9.0 Hz, 2 H, Ar) ppm. 13C NMR (CDCl3): δ =
13.5, 14.0, 18.9, 22.5, 25.8, 29.0, 29.1, 29.2, 29.4, 30.3, 31.7, 39.0,
IR: ν = 3294, 3189, 2923, 2854, 1608, 1517, 1463, 1377, 1254, 1181,
˜
1049, 876, 820, 721, 668 cm–1. C18H27NO3 (305.42): calcd. C 70.79,
H 8.91, N 4.59; found C 70.65, H 8.86, N 4.80.
{3-[4-(Nonyloxy)phenyl]-4,5-dihydroisoxazol-5-yl}methanol
(7c): 65.6, 68.0, 77.7, 114.5, 120.7, 128.3, 155.5, 160.8, 170.4 ppm. IR: ν
˜
1
Yield 122 mg, 38%; white solid; m.p. 98 °C. H NMR (CDCl3): δ
= 2923, 2854, 1737, 1610, 1517, 1456, 1377, 1264, 1210, 1017, 880,
= 0.89 (m, 3 H, CH3), 1.43 [m, 12 H, (CH2)6], 1.79 (m, 2 H, 828, 722, 667 cm–1. C23H35NO4 (389.54): calcd. C 70.92, H 9.06, N
CH2CH2O), 2.10 (br., 1 H, OH), 3.24 (dd, J = 16.8, 8.1 Hz, 1 H, 3.60; found C 70.98, H 9.12, N 3.69.
894
www.eurjoc.org
© 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Org. Chem. 2009, 889–897