The Journal of Organic Chemistry
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(ESI) m/z: calcd for C18H24N2O2 [M+Na]+ 323.1735, found: 323.1735. IR (neat, ν, cm-1) = 3360, 2958, 1702, 1637 cm-1.
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(Z)-4-((tert-butylamino)methylene)-3-(4-methoxyphenyl)isoxazol-5(4H)-one (3e) Yield: 37% (20.3 mg). Pale yellow Solid. M.p. 157.3 -
160.7 ℃. H NMR (400 MHz, CDCl3) δ 9.40 (d, J = 13.2 Hz, 1H), 7.64 (d, J = 14.5 Hz, 1H), 7.52 – 7.46 (m, 2H), 7.03 – 6.99 (m, 2H),
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3.85 (s, 3H), 1.41 (s, 9H) ppm. 13C{1H}NMR (100 MHz, CDCl3) δ 175.2, 161.3, 161.1, 149.3, 129.1, 121.3, 114.7, 89.4, 55.5, 54.9, 29.8
ppm. HRMS (ESI) m/z: calcd for C15H18N2O3 [M+H]+ 275.1396, found: 275.1396. IR (neat, ν, cm-1) = 3204, 2979, 2968, 1699, 1634 cm-1.
(Z)-3-(benzo[d][1,3]dioxol-5-yl)-4-((tert-butylamino)methylene)isoxazol-5(4H)-one (3f) Yield: 45% (25.9 mg). Orange Solid. M.p. 164.0
- 166.1 ℃. 1H NMR (400 MHz, CDCl3) δ 9.41 (d, J = 14.7 Hz, 1H), 7.64 (d, J = 14.6 Hz, 1H), 7.06 – 6.99 (m, 2H), 6.92 – 6.90 (m, 1H),
6.03 (s, 2H), 1.41 (s, 9H) ppm. 13C{1H}NMR (100 MHz, CDCl3) δ 175.1, 161.0, 149.5, 149.2, 148.5, 122.7, 122.0, 109.0, 108.1, 101.7,
89.3, 55.0, 29.8 ppm. HRMS (ESI) m/z: calcd for C15H16N2O4 [M+Na]+ 311.1008, found: 311.1007. IR (neat, ν, cm-1) = 3225, 2975, 1979,
1717, 1633 cm-1.
(Z)-3-(4-bromophenyl)-4-((tert-butylamino)methylene)isoxazol-5(4H)-one (3g) Yield: 44% (28.3 mg). Pale pink Solid. M.p. 188.5 -
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191.1 ℃. H NMR (400 MHz, CDCl3) δ 9.45 (d, J = 14.6 Hz, 1H), 7.66 – 7.59 (m, 3H), 7.48 – 7.40 (m, 2H), 1.42 (s, 9H) ppm.
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13C{1H}NMR (100 MHz, CDCl3) δ 175.0, 160.5, 149.1, 132.6, 129.3, 128.0, 124.9, 89.0, 55.1, 29.7 ppm. HRMS m/z: calcd for
C14H15BrN2O2 [M+H]+ 323.0395, found: 323.0398. IR (neat, ν, cm-1) = 3213, 1702, 1651, 1517 cm-1.
(Z)-4-((tert-butylamino)methylene)-3-(4-chlorophenyl)isoxazol-5(4H)-one (3h) Yield: 37% (20.6 mg). Pink Solid. M.p. 183.0 - 185.1 ℃.
1H NMR (400 MHz, CDCl3) δ 9.45 (d, J = 14.5 Hz, 1H), 7.62 (d, J = 14.6 Hz, 1H), 7.52 – 7.45 (m, 4H), 1.42 (s, 9H) ppm. 13C{1H}NMR
(100 MHz, CDCl3) δ 175.0, 160.5, 149.1, 136.6, 129.6, 129.1, 127.5, 89.0, 55.1, 29.7 ppm. HRMS (ESI) m/z: calcd for C14H15ClN2O2
[M+H]+ 279.0900, found: 279.0897. IR (neat, ν, cm-1) = 3219, 2915, 1704, 1652 cm-1.
(Z)-4-((tert-butylamino)methylene)-3-(3-fluorophenyl)isoxazol-5(4H)-one (3j) Yield: 39% (20.4 mg). Pale yellow Solid. M.p. 162.3 -
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165.9 ℃. H NMR (400 MHz, CDCl3) δ 9.47 (d, J = 12.3 Hz, 1H), 7.65 (d, J = 14.5 Hz, 1H), 7.53 – 7.43 (m, 1H), 7.39 – 7.32 (m, 1H),
7.32 – 7.27 (m, 1H), 7.24 – 7.17 (m, 1H), 1.43 (s, 10H) ppm. 13C{1H}NMR (100 MHz, CDCl3) δ 175.0, 164.3, 161.8, 160.3 (d, JC-F = 2.3
Hz), 149.2, 131.0 (d, JC-F = 8.3 Hz), 123.5 (d, JC-F = 3.2 Hz), 117.4 (d, JC-F = 21.0 Hz), 114.9 (d, JC-F = 22.8 Hz), 88.8, 55.2, 29.7 ppm.
HRMS (ESI) m/z: calcd for C14H15FN2O2 [M+Na]+ 285.1015, found: 285.1011. IR (neat, ν, cm-1) = 3255, 3222, 2982, 1698, 1643 cm-1.
(Z)-4-((tert-butylamino)methylene)-3-(3-chlorophenyl)isoxazol-5(4H)-one (3k) Yield: 37% (20.6 mg). Pale pink Solid. M.p. 164.3 -
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166.2 ℃. H NMR (400 MHz, CDCl3) δ 9.46 (d, J = 13.3 Hz, 1H), 7.63 (d, J = 14.6 Hz, 1H), 7.59 – 7.54 (m, 1H), 7.50 – 7.45 (m, 1H),
7.45 – 7.38 (m, 2H), 1.42 (s, 9H) ppm. 13C{1H}NMR (100 MHz, CDCl3) δ 175.0, 160.2, 149.1, 135.3, 130.8, 130.6, 130.5, 127.9, 125.9,
88.9, 55.2, 29.7 ppm. HRMS (ESI) m/z: calcd for C14H15ClN2O2 [M+H]+ 279.0900, found: 279.0892. IR (neat, ν, cm-1) = 3233, 2059, 2013,
1695,1639 cm-1.
(Z)-4-((tert-butylamino)methylene)-3-(3,4-difluorophenyl)isoxazol-5(4H)-one (3l) Yield: 34% (19.0 mg). Orange Solid. M.p. 168.0-
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170.1 ℃. H NMR (400 MHz, CDCl3) δ 9.49 (d, J = 14.9 Hz, 1H), 7.65 (d, J = 14.6 Hz, 1H), 7.49 – 7.37 (m, 1H), 7.35 – 7.23 (m, 2H),
1.45 (s, 9H) ppm. 13C{1H}NMR (100 MHz, CDCl3) δ 174.9, 159.6, 151.2, 149.1, 129.7, 126.0, 124.2, 117.7, 116.5, 88.8, 55.3, 29.7 ppm.
HRMS (ESI) m/z: calcd for C14H14F2N2O2 [M+H]+ 281.1102, found: 281.1102. IR (neat, ν, cm-1) = 3217, 2972, 1695, 1634 cm-1.
(Z)-4-((tert-butylamino)methylene)-3-(naphthalen-2-yl)isoxazol-5(4H)-one (3m) Yield: 36% (21.2 mg). Pink Solid. M.p. 154.9 -
156.2 ℃. 1H NMR (400 MHz, CDCl3) δ 9.46 (d, J = 14.6 Hz, 1H), 8.05 – 8.04 (m, 1H), 7.97 (d, J = 8.5 Hz, 1H), 7.94 – 7.87 (m, 2H), 7.75
– 7.72 (m, 1H), 7.67 – 7.65 (m, 1H), 7.61 – 7.53 (m, 2H), 1.42 (s, 9H) ppm. 13C{1H}NMR (100 MHz, CDCl3) δ 175.2, 161.5, 149.4, 134.1,
133.3, 129.2, 128.6, 128.0, 127.7, 127.5, 127.0, 126.4, 124.8, 89.5, 55.0, 29.8 ppm. HRMS (ESI) m/z: calcd for C18H18N2O2 [M+Na]+
317.1266, found: 317.1266. IR (neat, ν, cm-1) = 3256, 3212, 2964, 2920, 1691, 1639 cm-1.
(Z)-4-((tert-butylamino)methylene)-3-(3-(trifluoromethyl)phenyl)isoxazol-5(4H)-one (3n) Yield: 40% (25.0 mg). Pale yellow Solid. M.p.
167.2 - 169.1 ℃. 1H NMR (400 MHz, CDCl3) δ 9.47 (d, J = 14.4 Hz, 1H), 7.82 (s, 1H), 7.76 – 7.74 (m, 2H), 7.68 – 7.59 (m, 2H), 1.42 (s,
9H) ppm. 13C{1H}NMR (100 MHz, CDCl3) δ 174.9, 160.2, 149.0, 131.9, 131.6, 131.0, 129.9, 127.1 (q, JC-F = 3.6 Hz), 124.7 (q, JC-F = 3.8
Hz), 123.8 (d, JC-F = 270.1 Hz), 88.8, 55.3, 29.7 ppm. HRMS (ESI) m/z: calcd for C15H15F3N2O2 [M+Na]+ 335.0983, found: 335.0988. IR
(neat, ν, cm-1) = 3277, 2962, 2358, 2190, 1699, 1634 cm-1.
(E)-4-((((3s,5s,7s)-adamantan-1-yl)amino)methylene)-3-phenylisoxazol-5(4H)-one (3q) Yield: 53% (34.2 mg). White Solid. M.p. 207.4 -
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209.6 ℃. H NMR (400 MHz, CDCl3) δ 9.37 (d, J = 14.7 Hz, 1H), 7.66 (d, J = 14.6 Hz, 1H), 7.58 – 7.55 (m, 2H), 7.53 – 7.48 (m, 3H),
2.24 – 2.19 (m, 3H), 1.87 (d, J = 2.9 Hz, 6H), 1.75 (d, J = 12.8 Hz, 3H), 1.66 (d, J = 11.8 Hz, 3H) ppm. 13C{1H}NMR (100 MHz, CDCl3)
δ 175.2, 161.5, 148.5, 130.4, 129.3, 129.1, 127.9, 89.1, 55.1, 42.9, 35.7, 29.3 ppm. HRMS (ESI) m/z: calcd for C20H22N2O2 [M+H]+
323.1760, found: 323.1760. IR (neat, ν, cm-1) = 3206, 2908, 2175, 1699, 1634 cm-1.
(Z)-4-((cyclohexylamino)methylene)-3-phenylisoxazol-5(4H)-one (3r) Yield: 37% (20.0 mg). Yellow Solid. M.p. 167.9 - 169.2 ℃.1H
NMR (400 MHz, CDCl3) δ 9.20 (s, 1H), 7.62 (d, J = 14.3 Hz, 1H), 7.58 – 7.56 (m, 2H), 7.50 – 7.47 (m, 3H), 3.43 – 3.26 (m, 1H), 2.00 (d,
J = 9.7 Hz, 2H), 1.84 (dd, J = 9.3, 3.6 Hz, 2H), 1.68 – 1.24 (m, 6H) ppm. 13C{1H}NMR (100 MHz, CDCl3) δ 175.2, 161.4, 151.5, 130.4,
129.2, 129.0, 127.9, 89.4, 59.1, 33.7, 24.9, 24.5 ppm. HRMS (ESI) m/z: calcd for C16H18N2O2 [M+Na]+ 293.1266, found: 293.1251. IR
(neat, ν, cm-1) = 3328, 2362, 1692, 1633 cm-1.
(Z)-3-phenyl-4-(((2,4,4-trimethylpentan-2-yl)amino)methylene)isoxazol-5(4H)-one (3s) Yield: 25% (15.0 mg). Orange Solid. M.p. 105.3
- 107.3 ℃. 1H NMR (400 MHz, CDCl3) δ 9.55 (d, J = 14.6 Hz, 1H), 7.62 (d, J = 14.6 Hz, 1H), 7.58 – 7.56 (m, 2H), 7.54 – 7.49 (m, 3H),
1.66 (s, 2H), 1.45 (s, 6H), 1.01 (s, 9H) ppm. 13C{1H}NMR (100 MHz, CDCl3) δ 161.4, 149.1, 130.4, 129.3, 129.1, 127.8, 89.1, 58.4, 55.4,
31.9, 31.5, 29.6 ppm. HRMS (ESI) m/z: calcd for C18H24N2O2 [M+H]+ 301.1916, found: 301.1915. IR (neat, ν, cm-1) = 2959, 2904, 1687,
1633 cm-1.
(Z)-4-((butylamino)methylene)-3-phenylisoxazol-5(4H)-one (3t) Yield: 26% (12.7 mg). Gray Solid. M.p. 186.2 - 188.1 ℃. 1H NMR (400
MHz, CDCl3) δ 10.50 (s, 1H), 7.71 – 7.67 (m, 2H), 7.55 – 7.47 (m, 3H), 6.03 (d, J = 2.2 Hz, 1H), 3.94 (t, 2H), 1.64 (p, J = 7.7 Hz, 2H),
1.39 (h, J = 7.4 Hz, 2H), 0.94 (t, J = 7.3 Hz, 3H) ppm. 13C{1H}NMR (100 MHz, CDCl3) δ 163.5, 153.4, 150.2, 131.66, 131.5, 129.3, 126.5,
99.0, 40.6, 29.9, 20.4, 13.9 ppm. HRMS (ESI) m/z: calcd for C14H16N2O2 [M+H]+ 245.1290, found: 245.1291. IR (neat, ν, cm-1) = 3229,
2035, 1787, 1687 cm-1.
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