The Journal of Organic Chemistry
Article
The mother liquor was evaporated under reduced pressure, and the
solid thus obtained was recrystallized from n-hexane−ethyl acetate to
obtain 3-benzyl-7-chlorobenzoxazolone (16c) (0.114 g, 22%) as
154.4, 142.6, 132.6, 128.4, 124.1, 110.6, 108.2, 61.0, 38.0, 32.4, 21.3,
14.0 ppm; IR (KBr) νmax 2983 (w), 2931 (w), 1776(s), 1733(s), 1620
(w), 1504(m), 1449(m), 1365(m), 1266(m), 1196(m), 1094 (w),
1028 (w), 946(m), 805(m), 751 (w), 594 (w) cm−1; HRMS (ESI-
TOF) m/z [M + Na]+ calcd for C13H15NO4Na 272.0893, found
272.0884.
1
colorless needles: mp 114 °C; H NMR (300 MHz, CDCl3) δ 7.35
(s, 5H), 7.00−7.11 (m, 2H), 6.74 (d, J = 7.5 Hz, 1H), 5.01 (s, 2H)
ppm; 13C NMR (75.5 MHz, CDCl3) δ 153.9, 139.2, 134.2, 131.9,
129.1, 128.5, 127.6, 124.5, 123.2, 115.7, 107.3, 46.5 ppm; IR (KBr)
νmax 3056 (w), 2924 (w), 1764 (s), 1617 (m), 1473 (m), 1344 (m),
1212 (w), 1137 (w), 1020 (m), 755 (m), 705 (m) cm−1; HRMS (ESI-
TOF) m/z [M + Na]+ calcd for C14H10Cl1NO2Na 282.0292, found
282.0291.
3-Allyl-6-chlorobenzoxazolone (12j):81 colorless liquid, 0.360 g,
1
86%; H NMR (300 MHz, CDCl3) δ 7.25 (d, J = 1.8 Hz, 1H), 7.15
(dd, J = 8.4, 1.8 Hz, 1H), 6.88 (d, J = 8.1 Hz, 1H), 5.82−5.95 (m, 1H),
5.27−5.34 (m, 2H), 4.45 (dt, J = 5.7, 1.5 Hz, 2H) ppm; 13C NMR
(75.5 MHz, CDCl3) δ 153.8, 142.7, 130.0, 129.5, 127.8, 123.8, 119.0,
110.8, 109.4, 44.6 ppm; IR (KBr) νmax 3073 (w), 2924 (w), 1777 (s),
1606 (m), 1489 (s), 1360 (m), 1297 (m), 1254 (m), 1179 (w), 1059
(w), 988 (m), 914 (m), 851 (w), 808 (m), 760 (w), 703 (w) cm−1.
3-(2-Ethoxycarbonylethyl)-6-chlorobenzoxazolone (12k): color-
less flakes; mp 80 °C (n-hexane−ethyl acetate) (lit.80 mp 78 °C);
0.383 g, 71%; 1H NMR (300 MHz, CDCl3) δ 7.25 (d, J = 1.5 Hz, 1H),
7.21(dd, J = 8.4, 1.8 Hz, 1H), 7.06 (d, J = 8.7 Hz, 1H), 4.10−4.17 (m,
4H), 2.83 (t, J = 6.6 Hz, 2H), 1.23 (t, J = 7.2 Hz, 3H) ppm; 13C NMR
(75.5 MHz, CDCl3) δ 170.6, 153.7, 142.5, 129.5, 127.6, 123.7, 110.6,
109.3, 60.9, 38.0, 32.1, 13.8 ppm; IR (KBr) νmax 3070 (w), 2986 (m),
1780 (s), 1726 (s), 1617 (m), 1489 (s), 1358 (s), 1321 (m), 1276
(m), 1192 (s), 1091 (m), 1030 (m), 944 (m), 910 (m), 808 (m), 753
(w), 706 (w), 594 (w) cm−1.
3-Allyl-6-bromobenzoxazolone (12l): colorless liquid, 0.412 g,
81%; 1H NMR (300 MHz, CDCl3) δ 7.39 (s, 1H), 7.31 (d, J = 8.4 Hz,
1H), 6.85 (d, J = 8.4 Hz, 1H), 5.82−5.95 (m, 1H), 5.34 (d, J = 4.5 Hz,
1H), 5.29 (d, J = 11.4 Hz, 1H), 4.44 (d, J = 5.4 Hz, 2H) ppm; 13C
NMR (75.5 MHz, CDCl3) δ 153.8, 143.0, 130.1, 130.0, 126.8, 119.1,
114.8, 113.6, 109.9, 44.7 ppm; IR (KBr) νmax 3081 (w), 2926 (w),
1785 (s), 1684 (w), 1615 (w), 1485 (m), 1436 (w), 1360 (m), 1260
(w), 1076 (w), 1004 (w), 930 (w), 806 (w), 756 (w), 702 (w) cm−1;
HRMS (ESI-TOF) m/z [M + H]+ calcd for C10H9BrNO2 253.9811,
found 253.9812.
3-Propylbenzoxazolone (12b):79 colorless liquid, 0.319 g, 90%; 1H
NMR (300 MHz, CDCl3) δ 7.07−7.21 (m, 3H), 6.98 (d, J = 7.5 Hz,
1H), 3.79 (t, J = 6.6 Hz, 2H), 1.82 (sext, J = 7.2 Hz, 2H), 1.00 (t, J =
7.2 Hz, 3H) ppm; 13C NMR (75.5 MHz, CDCl3) δ 154.6, 142.6,
131.2, 123.7, 122.2, 109.9, 108.2, 43.8, 21.1, 11.1 ppm; IR (KBr) νmax
2968 (m), 2938 (m), 2877 (w), 1782 (s), 1614 (m), 1486 (m), 1363
(m), 1245 (m), 1128 (w), 1073 (m), 1015 (m), 964 (m), 752 (m),
682 (w) cm−1.
3-(2-Ethoxycarbonylethyl)benzoxazolone (12c): colorless flakes;
mp 42 °C (n-hexane−ethyl acetate) (lit.80 mp 42−44 °C); 0.343 g,
73%; 1H NMR (300 MHz, CDCl3) δ 7.21 (t, J = 7.2 Hz, 2H), 7.12 (t,
J = 7.5 Hz, 2H), 4.08−4.17 (m, 4H), 2.84 (t, J = 6.9 Hz, 2H), 1.22 (t, J
= 7.2 Hz, 3H) ppm; 13C NMR (75.5 MHz, CDCl3) δ 170.8, 154.3,
142.6, 130.8, 123.8, 122.4, 110.0, 108.6, 61.0, 38.0, 32.4, 14.0 ppm; IR
(KBr) νmax 2984 (w), 1779 (s), 1732 (s), 1625 (w), 1486 (m), 1365
(m), 1253 (m), 1194 (m), 1149 (w), 1094 (w), 1050 (w), 1021 (w),
944 (w), 752 (m) cm−1.
3-(2-Cyanoethyl)benzoxazolone (12d): colorless cubes; mp 118
°C (n-hexane−ethyl acetate) (lit.80 mp 120 °C); 0.320 g, 85%; H
1
NMR (300 MHz, CDCl3) δ 7.10−7.27 (m, 4H), 4.14 (t, J = 6.6 Hz,
2H), 2.88 (t, J = 6.6 Hz, 2H) ppm; 13C NMR (75.5 MHz, CDCl3) δ
153.9, 142.4, 130.0, 124.2, 123.1, 116.8, 110.4, 108.2, 38.1, 16.8 ppm;
IR (KBr) νmax 3045 (w), 2979 (w), 2936 (w), 2251 (w), 1777 (s),
1613 (w), 1482 (m), 1447 (m), 1363 (s), 1249 (m), 1222 (m), 1152
(w), 1095 (w), 1048 (w), 940 (w), 904 (w), 756 (s), 673 (w) cm−1.
3-(4-Methoxybenzyl)benzoxazolone (12f): colorless plates; mp
108 °C (n-hexane−ethyl acetate); 0.398 g, 78%; 1H NMR (300 MHz,
CDCl3) δ 7.30 (d, J = 8.4 Hz, 2H), 7.17−7.21 (m, 1H), 7.06−7.10 (m,
2H), 6.84−6.88 (m, 3H), 4.94 (s, 2H), 3.78 (s, 3H) ppm; 13C NMR
(75.5 MHz, CDCl3) δ 159.5, 154.7, 142.7, 130.8, 129.1, 126.8, 123.7,
122.4, 114.3, 110.0, 108.9, 55.3, 45.6 ppm; IR (KBr) νmax 3019 (w),
2960 (w), 2835 (w), 1756 (s), 1612 (m), 1511 (m), 1482 (m), 1356
(m), 1242 (s), 1175 (m), 1147 (m), 1072 (m), 1023 (m), 826 (m),
754 (s), 676 (m) cm−1; HRMS (ESI-TOF) m/z [M + Na]+ calcd for
C15H13NO3Na 278.0788, found 278.0788.
3-(2-Ethoxycarbonylethyl)-6-(ethoxycarbonylmethyl)-
1
benzoxazolone (12m): colorless liquid, 0.456 g, 71%; H NMR (300
MHz, CDCl3) δ 7.17 (s, 1H), 7.11 (d, J = 8.1 Hz, 1H), 7.05 (d, J = 8.1
Hz, 1H), 4.09−4.19 (m, 6H), 3.63 (s, 2H), 2.81 (t, J = 6.6 Hz, 2H),
1.19−1.28 (m, 6H) ppm; 13C NMR (75.5 MHz, CDCl3) δ 171.3,
170.7, 154.3, 142.6, 129.8, 128.7, 124.8, 111.0, 108.5, 61.0, 41.0, 38.0,
32.3, 14.1, 14.0 ppm; IR (KBr) νmax 2981 (m), 1779 (s), 1733 (s),
1577 (m), 1505 (m), 1451 (m), 1367 (m), 1266 (m), 1193 (m), 1093
(m), 1031 (m), 956 (w), 795 (w), 756 (w) cm−1; HRMS (ESI-TOF)
m/z [M + Na]+ calcd for C16H19NO6Na 344.1105, found 344.1109.
3-(2-Ethoxycarbonylethyl)-6-[(N-methyl-N-phenyl)-
aminocarbonylmethyl]benzoxazolone (12n): colorless liquid, 0.521
g, 68%; 1H NMR (300 MHz, CDCl3) δ 7.39−7.46 (m, 3H), 7.16 (d, J
= 6.9 Hz, 2H), 6.88−6.98 (m, 3H), 4.07−4.15 (m, 4H), 3.46 (s, 2H),
3.28 (s, 3H), 2.80 (t, J = 6.6 Hz, 2H), 1.22 (t, J = 7.2 Hz, 3H) ppm;
13C NMR (75.5 MHz, CDCl3) δ 170.72, 170.66, 154.3, 143.6, 142.5,
130.1, 129.8, 129.4, 128.1, 127.4, 124.6, 110.9, 108.2, 61.0, 40.4, 38.0,
37.6, 32.4, 14.0 ppm; IR (KBr) νmax 2982 (w), 1776 (s), 1731 (s),
1654 (s), 1594 (m), 1500 (m), 1450 (m), 1376 (m), 1267 (m), 1196
(m), 1118 (m), 955 (w), 774 (w), 702 (w), 558 (w) cm−1; HRMS
(ESI-TOF) m/z [M + Na]+ calcd for C21H22N2O5Na 405.1421, found
405.1415.
3-Benzyl-6-acetoxybenzoxazolone (12g): colorless flakes; mp 92
°C (n-hexane−ethyl acetate); 0.351 g, 62%; 1H NMR (300 MHz,
CDCl3) δ 7.35 (s, 5H), 7.03 (d, J = 1.5 Hz, 1H), 6.8−6.83 (m, 2H),
5.00 (s, 2H), 2.29 (s, 3H) ppm; 13C NMR (75.5 MHz, CDCl3) δ
169.5, 154.8, 146.0, 142.5, 134.3, 129, 128.5, 128.4, 127.6, 117.0, 108.8,
105.1, 46.2, 20.9 ppm; IR (KBr) νmax 3084 (w), 2942 (w), 1787 (s),
1751 (s), 1625 (w), 1496 (s), 1449 (m), 1369 (m), 1341 (m), 1223
(s), 1159 (m), 1002 (m), 897 (w), 737 (w), 660 (w) cm−1; HRMS
(ESI-TOF) m/z [M + Na]+ calcd for C16H13NO4Na 306.0737, found
306.0724.
3-Allyl-6-ethoxycarbonylbenzoxazolone (12o): colorless plates;
mp 72 °C (n-hexane−ethyl acetate); 0.301 g, 61%; H NMR (300
3-Allyl-6-methylbenzoxazolone (12h): colorless liquid, 0.333 g,
88%; 1H NMR (300 MHz, CDCl3) δ 7.02 (s, 1H), 6.95 (d, J = 7.8 Hz,
1H), 6.83 (d, J = 8.1 Hz, 1H), 5.81−5.92 (m, 1H), 5.24−5.29 (m,
2H), 4.42 (d, J = 5.4 Hz, 2H), 2.40 (s, 3H) ppm; 13C NMR (75.5
MHz, CDCl3) δ 154.5, 142.6, 132.6, 130.5, 128.4, 124.1, 118.5, 110.5,
108.4, 44.5, 21.3 ppm; IR (KBr) νmax 2923 (w), 1777 (s), 1683 (w),
1642 (w), 1503(m), 1445 (m), 1366 (m), 1290 (w), 1264(m), 1183
(w), 1081 (w), 1007 (w), 936 (m), 862 (w), 805 (m), 749 (w), 702
(w), 592 (w) cm−1; HRMS (ESI-TOF) m/z [M + H]+ calcd for
C11H12NO2 190.0863, found 190.0869.
1
MHz, CDCl3) δ 7.95 (d, J = 8.1 Hz, 1H), 7.89 (s, 1H), 7.01 (d, J = 8.1
Hz, 1H), 5.85−5.98 (m, 1H), 5.29−5.35 (m, 2H), 4.49 (d, J = 5.4 Hz,
2H), 4.39 (q, J = 7.2 Hz, 2H), 1.41 (t, J = 7.2 Hz, 3H) ppm; 13C NMR
(75.5 MHz, CDCl3) δ 165.7, 154.2, 142.2, 134.7, 130.0, 126.3, 125.2,
119.2, 111.1, 108.2, 61.3, 44.8, 14.3 ppm; IR (KBr) νmax 3079 (w),
2970 (m), 1787 (s), 1704 (s), 1608 (m), 1501 (m), 1451 (s), 1362
(s), 1284 (s), 1216 (m), 1172 (m), 1114 (m), 1072 (m), 1019 (m),
995 (m), 934 (m), 894 (w), 836 (m), 763 (s), 700 (m) cm−1; HRMS
(ESI-TOF) m/z [M + Na]+ calcd for C13H13NO4Na 270.0737, found
270.0741.
3-(2-Ethoxycarbonylethyl)-6-methylbenzoxazolone (12i): color-
1
less liquid, 0.359 g, 72%; H NMR (300 MHz, CDCl3) δ 6.97−7.01
(m, 3H), 4.07−4.15 (m, 4H), 2.80 (t, J = 6.6 Hz, 2H), 2.38 (s, 3H),
4-(2,2,2-Trichloroacetamido)phenyl acetate (13): white powder;
1
1.21 (t, J = 7.2 Hz, 3H) ppm; 13C NMR (75.5 MHz, CDCl3) δ 170.7,
mp 74 °C (n-hexane−ethyl acetate); 0.065 g, 11%; H NMR (300
J
dx.doi.org/10.1021/jo401985h | J. Org. Chem. XXXX, XXX, XXX−XXX