Synthesis of heterocyclic 1,3-oxazolines from aldehydes with trimethylphenylammonium tribromide

Article abstract of DOI:10.3987/COM-17-13695

Various heterocyclic 1,3-oxazolines were prepared from aldehydes and aminoalcohols with trimethylphenylammonium tribromide at room temperature.

Full text of DOI:10.3987/COM-17-13695

Synthesis of Heterocyclic 1,3-Oxazolines from Aldehydes with
Trimethylphenylammonium Tribromide
Shinsei Sayama*
Supporting Information
1

Table of Contents
General Information
Physical data of heterocyclic oxazolines
・・・・・・ 3
・・・・・・ 4 - 13
・・・・・・14 - 61
1
13
H NMR and C NMR Spectra
2

General Information
Melting points were measured on a Buchi Melting Point B-540 apparatus. IR spectra were recorded on a Perkin
Elmer Spectrum One FT-IR spectrometer.
1
13
H and C NMR spectra were recorded with a JEOL JNM-EX270 spectrometer at room temperature and the
chemical shifts () were given relative to internal standard SiMe in CDCl . Elemental analyses were performed on a
4
3
Yanagimoto MT-6.
Typical procedure:
To a solution of 3-quinolinecarbaldehyde 17 (79 mg, 0.5 mmol), 2-aminoethanol(200 L, 3.2 mmol), and pyridine
80 L, 1.0 mmol) in MeOH (6mL), was added PTAB(trimethylphenylammonium tribromide or phenyltrimethyl-
(
ammonium tribromide, 376 mg, 1.0 mmol) at room temperature. After stirring for 22 h at rt, the reaction mixture was
treated with 0.5 M aq Na S O (10 mL), 1.0 M NaHCO (15mL) and extracted with EtOAc (60 mL). The organic
2
2
3
3
layer was washed with 0.5 M Na S O and successively washed with saturated aq NaCl, and dried over MgSO .
2
2
3
4
After removal of solvent in vacuo, the residue was purified by column chromatography on silica gel (Wako C-200)
with CCl , CCl -CHCl (2:1 v/v). 3-(Oxazolin-2-yl)quinoline 18 (85 mg) was obtained in 86% yield.
4
4
3
3

N
N
3
O
o
-1
Pale yellow solid; mp 44.5-45.5 C. IR (neat, cm ) 3063, 2979, 2909, 2881, 1654, 1585, 1570, 1472, 1441, 1367, 1293, 1269,
1
1
248, 1195, 1151, 1122, 1098, 1044, 1000, 977, 944, 905, 802, 747, 674. H NMR (CDCl )  4.14 (2H, t, J = 8.1 Hz), 4.53
3
(
2H, t, J = 8.1 Hz), 7.40 (1H, dd, J = 8.1, 5.4 Hz), 7.79 (1H, t, J = 8.1 Hz), 8.05 (1H, d, J = 8.1 Hz), 8.71 (1H, d, J = 5.4 Hz).
13
C NMR (CDCl )  55.04, 68.13, 123.73, 125.47, 136.57, 146.66, 149.62, 163.80. Anal. Calcd for C H ON : C, 64.84; H,
3
8
8
2
5
.44; N, 18.91. Found: C, 65.01; H, 5.47; N, 18.86.
N
O
6
N
o
-1
Pale yellow solid; mp 69.0-69.5 C. IR (KBr, cm ) 3090, 3045, 2985, 2952, 2935, 2909, 2881, 1652, 1591, 1573, 1484, 1422,
1
1
359, 1263, 1240, 1189, 1116, 1080, 1034, 1022, 979, 933, 896, 819, 745, 703, 686, 622. H NMR (CDCl )  4.09 (2H, t, J =
3
8
.1 Hz), 4.47 (2H, t, J = 8.1 Hz), 7.36 (1H, dd, J = 5.4, 2.7), 8.22 (1H, d, J = 5.4 Hz), 7.71 (1H, dd, J =5 .4, 2.7 Hz), 9.16(1H,
brs). 13C NMR (CDCl )  54.92, 67.73, 123.16, 123.81, 135.46, 149.38, 151.95, 162.65. Anal. Calcd for C H ON : C,
3
8
8
2
6
4.84; H, 5.44; N, 18.91. Found: C, 64.86; H, 5.37; N, 18.84.
N
N
8
O
o
-1
Pale yellow solid; mp 113.5-114.2 C. IR (neat, cm ) 3032, 2974, 1650, 1599, 1552, 1497, 1474, 1409, 1365, 1335, 1260,
1
1
7
215, 1092, 1074, 992, 972, 943, 898, 841, 743, 672. H NMR (CDCl )  4.11 (2H, t, J = 8.1 Hz), 4.48 (2H, t, J = 8.1 Hz),
3
.78 (2H, d, J = 5.4 Hz), 8.71 (2H, d, J = 5.4 Hz). 13C NMR (CDCl )  55.06, 67.91, 121.84, 134.99, 150.22, 162.92. Anal.
3
Calcd for C H ON : C, 64.84; H, 5.44; N, 18.91. Found: C, 64.46; H, 5.29; N, 18.45.
8
8
2
4

N
N
10
O
o
-1
Colorless solid; mp 47.0-48.0 C. IR (KBr, cm ) 3054, 2998, 2975, 2926, 2901, 2875, 1656, 1642, 1591, 1572,
1459, 1364, 1329, 1279, 1254, 1230, 1163, 1129, 1109, 1079, 1008, 996, 989, 974, 948, 911, 834, 814, 746, 690, 669.
1
H NMR (CDCl )  2.64 (3H, s), 4.12 (2H, t, J = 8.1 Hz), 4.53 (2H, t, J = 8.1 Hz), 7.27 (1H, d, J = 8.1 Hz), 7.67 (1H,
3
t, J = 8.1 Hz), 7.85 (1H, d, J = 8.1 Hz). 13C NMR (CDCl )  24.61, 54.99, 68.19, 120.90, 125.32, 136.76, 146.06,
3
1
58.79, 163.93. Anal. Calcd for C H ON : C, 66.64; H, 6.21; N, 17.27. Found: C, 66.47; H, 6.09; N, 17.07.
9 10 2
N
N
N
12
O
O
-1
Colorless solid; mp 140-160 (decomp). IR (neat, cm ) 3049, 2974, 2932, 2874, 1644, 1569, 1476, 1453, 1427, 1357,
1
1
4

6
323, 1274, 1239, 1151, 1125, 1096, 1065, 992, 975, 955, 937, 910, 894, 843, 743, 660, 648. H NMR (CDCl ) 
3
.13 (4H, t, J = 8.1 Hz), 4.54 (4H, t, J = 8.1 Hz), 7.88 (1H, t, J = 8.1 Hz), 8.16 (2H, d, J = 8.1 Hz). 13C NMR (CDCl3)
55.05, 68.32, 125.49, 137.35, 146.73, 163.44. Anal. Calcd for C H N O : C, 60.82; H, 5.10; N, 19.34. Found: C,
11 11 3 2
1.15; H, 5.28; N, 18.88.
N
N
14
S
O
o
-1
Pale yellow solid; mp 80.1-81.1 C. IR (neat, cm ) 3107, 3075, 2984, 2875, 1645, 1493, 1426, 1360, 1314, 1260,
1
1
243, 1198, 1149, 1070, 1040, 992, 972, 925, 875, 765, 695 607. H NMR (CDCl )  4.13 (2H, t, J = 8.1 Hz), 4.55
3
(
2H, t, J = 8.1 Hz), 7.51 (1H, d, J = 5.4 Hz), 7.96 (1H, d, J = 5.4 Hz). 13C NMR (CDCl )  55.04, 68.71, 122.89,
3
144.34, 155.62, 159.38.
Anal. Calcd for C H N OS: C, 46.74; H, 3.92; N, 18.17. Found: C, 46.58; H, 4.01; N, 17.75.
6
6 2
5

N
N
1
6
O
o
-1
Colorless solid; mp 107.9-108.3 C. IR (KBr, cm ) 3055, 3009, 2974, 2932, 2903, 2876, 1641, 1591, 1558, 1503,
1
8
7
1
5
481, 1465, 1460, 1429, 1366, 1341, 1299, 1268, 1242, 1207, 1133, 1120, 1095, 1078, 1004, 975, 956, 936, 911, 882,
1
44, 793, 760, 625. H NMR (CDCl )  4.19 (2H, t, J = 8.1 Hz), 4.60 (2H, t, J = 8.1 Hz), 7.60 (1H, t, J = 8.1 Hz),
3
.76 (1H, t, J = 8.1 Hz), 7.78 (1H, d, J = 5.4 Hz), 8.15-8.29 (3H, m). 13C NMR (CDCl )  55.12, 68.41, 120.57,
3
27.46, 127.87, 128.85, 130.01, 130.30, 136.72, 146.66, 147.49, 164.09. Anal. Calcd for C H ON : C, 72.70; H,
12
10
2
.08; N, 14.13. Found: C, 72.85; H, 5.07; N, 13.96.
N
O
18
N
o
-1
Colorless solid; mp 128.3-128.8 C. IR (KBr, cm ) 2979, 2941, 2908, 2882, 1651, 1618, 1572, 1497, 1460, 1426,
1380, 1352, 1314, 1277, 1237, 1221, 1193, 1147, 1129, 1082, 1065, 1019, 978, 968, 933, 918, 906, 867, 785, 705,
1
6
31. H NMR (CDCl )  4.15 (2H, t, J = 8.1 Hz), 4.51 (2H, t, J = 8.1 Hz), 7.59 (1H, t, J = 8.1 Hz), 7.78 (1H, t, J =
3
8
.1 Hz), 7.88 (1H, d, J = 8.1 Hz), 8.14 (1H, d, J = 8,1 Hz), 8.67 (1H, brs), 9.45 (1H, brs). 13C NMR (CDCl )  55.09,
3
6
7.68, 120.84, 126.94, 127.25, 128.62, 129.42, 130.95, 136.01, 149.02, 149.47, 162.78. Anal. Calcd for C H ON :
12 10 2
C, 72.70; H, 5.08; N, 14.13. Found: C, 72.86; H, 5.09; N, 13.98.
6

N
O
20
N
o
-1
Pale yellow solid; 64.5-65.6 C. IR (KBr, cm ) 3079, 2978, 2931, 2908, 2875, 1641, 1577, 1509, 1463, 1353, 1326,
1
1
300, 1266, 1249, 1206, 1188, 1145, 1128, 1073, 999, 973, 943, 902, 879, 866, 813, 798, 768, 659. H NMR (CDCl )
3

4.25 (2H, t, J = 8.1 Hz), 4.49 (2H, t, J = 8.1 Hz), 7.63 (1H, t, J = 8.1 Hz), 7.76 (1H, t, J = 8.1 Hz), 7.88 (1H, d, J =
5
.4 Hz), 8.15 (1H, d, J = 8,1 Hz), 8.98 (1H, d, J = 2.7 Hz), 9.09 (1H, d, J = 8.1 Hz). 13C NMR (CDCl )  55.86,
3
6
6.89, 121.71, 125.26, 126.37, 127.73, 129.54, 129.90, 132.19, 148.83, 149.72, 162.81. Anal. Calcd for C H ON :
12 10 2
C, 72.70; H, 5.08; N, 14.13. Found: C, 72.79; H, 4.97; N, 13.94.
7

N
N
O
21
-1
Pale yellow oil. IR (neat, cm ) 3063, 2968, 2938, 2878, 1651, 1644, 1585, 1569, 1530, 1471, 1441, 1382, 1359, 1291, 1269,
1
1
247, 1201, 1102, 1045, 992, 964, 929, 909, 802, 747, 678. H NMR (CDCl )  1.03 (3H, t, J = 8.1 Hz), 1.73 (2H, m), 3.74
3
(1H, dd, J = 13.5, 8.1 Hz), 4.17 (1H, dd, J = 13.5, 8.1 Hz), 4.78 (1H, m), 7.38 (1H, m), 7.77 (1H, t, J = 8.1 Hz), 8.03 (1H, d, J
=
8.1 Hz), 8.71 (1H, d, J = 5.4 Hz). 13C NMR (CDCl )  8.87, 27.97, 59.44, 81,84, 123.65, 125.32, 136.49, 146.84, 149.58,
3
1
63.24. Anal. Calcd for C H N O: C, 68.16; H, 6.86; N, 15.90. Found: C, 68.01; H, 6.80; N, 15.73.
10 12 2
N
O
22
N
-
1
Pale yellow oil. IR (neat, cm ) 3046, 2968, 2938, 2878, 1651, 1594, 1571, 1484, 1475, 1463, 1430, 1416, 1351, 1297, 1263,
1
1
193, 1085, 1036, 1024, 963, 929, 902, 819, 708. H NMR (CDCl )  1.03 (3H, t, J = 8.1 Hz), 1.73 (2H, m), 3.69 (1H, dd, J
3
=
13.5, 8.1 Hz), 4.13 (1H, dd, J = 13.5, 8.1 Hz), 4.71 (1H, m), 7.34 (1H, m), 8.22 (1H, d, J = 8.1 Hz), 8.70 (1H, d, J = 5.4 Hz),
9
.15 (1H, brs). 13C NMR (CDCl )  9.12, 28.24, 59.54, 81.50, 123.17, 124.15, 135.47, 149.35, 151.85, 162.11. Anal. Calcd
3
for C H N O: C, 68.16; H, 6.86; N, 15.90. Found: C, 68.20; H, 7.05; N, 15.75.
10 12 2
N
23
N
O
-1
Colorless oil. IR (neat, cm ) 2969, 2939, 2878, 1651, 1600, 1556, 1497, 1463, 1412, 1383, 1357, 1321, 1296, 1263, 1228,
1
1
094, 1063, 994, 963, 928, 905, 838, 745, 680. 1H NMR (CDCl )  1.04 (3H, t, J = 8.1 Hz), 1.77 (2H, m), 3.70 (1H, dd, J =
3.5, 8.1 Hz), 4.15 (1H, dd, J = 13.5, 8.1 Hz), 4.71 (1H, m), 7.79 (2H, d, J = 5.4 Hz), 8.70 (2H, d, J = 5.4 Hz). 13C NMR
3
(
CDCl )  8.89, 28.02, 59.45, 81.51, 121.70, 135.19, 149.92, 162.11. Anal. Calcd for C H N O: C, 68.16; H, 6.86; N, 15.90.
3 10 12 2
Found: C, 68.32; H, 6.99; N, 15.48.
8

N
N
24
O
-1
Pale yellow oil. IR (neat, cm ) 3065, 2966, 2938, 2877, 1639, 1590, 1575, 1463, 1380, 1351, 1275, 1256, 1236, 1166, 1119,
1
1
084, 1016, 966, 929, 837, 810, 747, 695, 670. H NMR (CDCl )  1.02 (3H, t, J = 8.1 Hz), 1.77 (2H, m), 2.64 (3H, s), 3.72
3
(1H, dd, J = 13.5, 8.1 Hz), 4.16 (1H, dd, J = 13.5, 8.1 Hz), 4.76 (1H, m), 7.24 (1H, d, J = 8.1 Hz), 7.68 (1H, t, J = 8.1 Hz),
7
1
.80 (1H, d, J = 8.1 Hz). 13C NMR (CDCl )  8.96, 24.56, 28.08, 59.51, 81.81, 120.77, 125.19, 136.65, 146.22, 158.84,
3
63.34. Anal. Calcd for C H N O: C, 69.45; H, 7.42; N, 14.73. Found: C, 69.69; H, 7.41; N, 14.81.
11
14
2
N
N
N
25
O
O
-
1
Pale yellow oil. IR (neat, cm ) 2968, 2938, 2878, 1660, 1575, 1536, 1461, 1434, 1382, 1344, 1273, 1244, 1172, 1138, 1111,
1
1
8
2
1
079, 996, 966, 930, 831, 748, 667, 649. H NMR (CDCl )  1.03 (6H, t, J = 8.1 Hz), 1.76 (4H, m), 3.73 (2H, dd, J = 16.2,
3
.1 Hz), 4.17 (2H, dd, J = 16.2, 8.1 Hz), 4.77 (2H, m), 7.86 (1H, t, J = 8.1 Hz), 8.08 (2H, m). 13C NMR (CDCl )  9.14, 9.17,
3
8.12, 28.16, 59.55, 59.58, 82.26, 82.30, 125.32, 137.34, 146.92, 162.90. Anal. Calcd for C H N O : C, 65.91; H, 7.01; N,
15 19 3 2
5.37. Found: C, 65.79: H, 6.69; N, 15.32.
N
N
26
S
O
-1
Pale yellow oil. IR (neat, cm ) 3082, 2967, 2937, 2877, 1645, 1533, 1494, 1462, 1428, 1349, 1314, 1244, 1148, 1043, 957,
1
9
24, 875, 761, 610. H NMR (CDCl )  1.04 (3H, t, J = 8.1 Hz), 1.80 (2H, m), 3.72 (1H, dd, J = 13.5, 8.1 Hz), 4.16 (1H, dd,
3
J = 13.5, 8.1 Hz), 4.81 (1H, m), 7.51 (1H, d, J = 2.7 Hz), 7.95 (1H, d, J = 2.7 Hz). 13C NMR (CDCl )  8.94, 27.95, 59.48,
3
8
2.73, 122.77, 144.25, 156.00, 158.86. Anal. Calcd for C H OSN : C, 52.72; H, 5.53; N, 15.37. Found: C, 52.25; H, 5.47;
8 10 2
N, 14.92.
9

N
N
27
O
o
-1
Pale yellow solid; mp 81.4-83.0 C. IR (neat, cm ) 3061, 2966, 2937, 2876, 1637, 1595, 1561, 1505, 1464, 1429, 1377,
364, 1354, 1302, 1268, 1243, 1209, 1125, 1085, 949, 929, 840, 766. 1H NMR (CDCl )  1.05 (3H, t, J = 8.1 Hz), 1.84
1
3
(2H, m), 3.80 (1H, dd, J = 16.2, 8.1 Hz), 4.23 (1H, dd, J = 16.2, 8.1 Hz), 4.84 (1H, m), 7.59 (1H, t, J = 8.1 Hz), 7.75 (1H, t,
J = 8.1 Hz), 7.83 (1H, d, J = 8.1 Hz), 8.16-8.30 (3H, m). 13C NMR (CDCl )  8.89, 28.03, 59.57, 82.08, 120.51, 127.37,
3
1
27.73, 128.59, 129.85, 130.35, 136.60, 146.88, 147.54, 163.56. Anal. Calcd for C H N O: C, 74.31; H, 6.24; N, 12.38.
14 14 2
Found: C, 74.32; H, 6.40; N, 12.33.
N
O
28
N
-1
Pale yellow oil. IR (neat, cm ) 2967, 2938, 2876, 1651, 1620, 1571, 1497, 1462, 1428, 1382, 1315, 1275, 1236, 1196, 1128,
1
1
070, 1007, 968, 927, 865, 844, 787, 756. H NMR (CDCl )  1.07 (3H, t, J = 8.1 Hz), 1.84 (2H, m), 3.75 (1H, dd, J = 16.2,
3
8.1 Hz), 4.19 (1H, dd, J = 16.2, 8.1 Hz), 4.76 (1H, m), 7.60 (1H, t, J = 8.1 Hz), 7.79 (1H, t, J = 8.1 Hz), 7.89 (1H, d, J = 8.1
Hz), 8.15 (1H, d, J = 8,1 Hz), 8.68 (1H, brs), 9.44 (1H, brs). 13C NMR (CDCl )  9.13, 28.23, 59.64, 81.46, 121.10, 126.98,
3
1
27.24, 128.60, 129.33, 130.92, 135.98, 148.93, 149.43, 162.24. Anal. Calcd for C H N O: C, 74.31; H, 6.24; N, 12.38.
14 14 2
Found: C, 74.44; H, 6.39; N, 12.31.
N
29
N
O
-
1
Pale yellow oil. IR (neat, cm ) 3066, 2966, 2937, 2876, 1644, 1576, 1509, 1463, 1434, 1380, 1337, 1322, 1296, 1268, 1247,
1
1
8
7
180, 1144, 1130, 1093, 1073, 1026, 1001, 959, 931, 904, 878, 858, 816, 770, 657, 627. H NMR (CDCl )  1.05 (3H, t, J =
3
.1 Hz), 1.79 (2H, m), 3.85 (1H, dd, J = 16.2, 8.1 Hz), 4.28 (1H, dd, J = 16.2, 8.1 Hz), 4.73 (1H, m), 7.63 (1H, t, J = 8.1 Hz),
.75 (1H, t, J = 8.1 Hz), 7.89 (1H, d, J = 5.4 Hz), 8.15 (1H, d, J = 8,1 Hz), 8.98 (1H, d, J = 5.4 Hz), 9.08 (1H, d, J = 8.1 Hz).
13
C NMR (CDCl )  9.14, 28.23, 60.35, 80.61, 121.66, 125.31, 126.34, 127.67, 129.51, 129.81, 132.59, 148.78, 149.67,
3
1
62.31.Anal. Calcd for C H N O: C, 74.31; H, 6.24; N, 12.38. Found: C, 74.28; H, 6.03; N, 12.14.
14 14 2
1
0

N
N
30
O
-
1
Brown oil. IR (neat, cm ) 2965, 2934, 2877, 1655, 1585, 1524, 1465, 1435, 1365, 1291, 1246, 1087, 997, 947, 748.
1
H NMR (CDCl )  1.03 (3H, t, J = 8.1 Hz), 1.73 (2H, m), 4.14 (1H, t, J = 8.1 Hz), 4.29 (1H, m), 4.58 (1H, t, J = 8.1
3
Hz), 7.39 (1H, t, J = 8.1 Hz), 7.78 (1H, t, J = 8.1 Hz), 8.04 (1H, d, J = 5.4 Hz), 8.71 (1H, d, J = 5.4 Hz). 13C NMR
(
CDCl )  10.01, 28.44, 68.22, 72.65, 123.78, 125.39, 136.52, 146.76, 149.62, 162.55.
3
N
31
O
N
-
1
Yellow oil. IR (neat, cm ) 2965, 2933, 2878, 1659, 1651, 1645, 1593, 1573, 1475, 1462, 1429, 1416, 1361, 1330,
1
1
291, 1247, 1193, 1109, 1079, 1036, 1024, 947, 900, 819, 709. H NMR (CDCl )  1.01 (3H, t, J = 8.1 Hz), 1.70
3
(
2H, m), 4.08 (1H, t J = 8.1 Hz), 4.25 (1H, m), 4.51 (1H, t, J = 8.1 Hz), 7.35 (1H, t, J = 5.4 Hz), 8.22 (1H, dd, J =
5
1
.4, 2.7 Hz), 8.69 (1H, d, J = 2.7 Hz), 9.14 (1H, brs). 13C NMR (CDCl )  9.95, 28.53, 68.05, 72.30, 123.14, 124.01,
3
35.58, 149.44, 151.89, 161.52.
N
N
3
2
O
-1
Yellow oil. IR (neat, cm ) 2966, 2934, 2878, 1651, 1601, 1556, 1462, 1413, 1364, 1291, 1063, 1000, 946, 903, 838,
1
7
45, 689. H NMR (CDCl )  1.01 (3H, t, J = 8.1 Hz), 1.70 (2H, m), 4.09 (1H, t, J = 8.1 Hz), 4.27 (1H, m), 4.52 (1H,
3
t, J = 8.1 Hz), 7.78 (2H, d, J = 5.4), 8.70 (2H, d, J = 5.4 Hz). 13C NMR (CDCl )  9.87, 28.37, 68.13, 72.40, 121.91,
3
1
35.19, 150.09, 161.70.
11

N
O
3
3
N
o
-1
Pale yellow solid; mp 50.2-51.0 C. IR (neat, cm ) 2964, 2932, 2878, 1651, 1620, 1571, 1496, 1462, 1379, 1320,
1
1
234, 1195, 1127, 1062, 981, 945, 787, 756. H NMR (CDCl )  1.04 (3H, t, J = 8.1 Hz), 1.77 (2H, m), 4.13 (1H, t, J
3
=
8.1 Hz), 4.33 (1H, m), 4.56 (1H, t, J = 8.1 Hz), 7.60 (1H, t, J = 8.1 Hz), 7.79 (1H, t, J = 8.1 Hz), 7.88 (1H, d, J =
8
1
.1 Hz), 8.15 (1H, d, J = 8,1 Hz), 8.69 (1H, brs), 9.44 (1H, brs). 13C NMR (CDCl )  10.00, 28.59, 68.25, 72.27,
3
21.02, 127.02, 127.26, 128.63, 129.43, 130.95, 136.15, 149.04, 149.54, 161.66.
N
N
3
4
O
-1
Yellow oil. IR (neat, cm ) 2964, 2932, 2874, 1645, 1576, 1509, 1462, 1347, 1274, 1248, 1182, 1145, 1072, 996, 947,
1
8
57, 770, 657. H NMR (CDCl )  1.08 (3H, t, J = 8.1 Hz), 1.80 (2H, m), 4.12 (1H, t, J = 8.1 Hz), 4.44 (1H, m), 4.55
3
(
1H, t, J = 8.1 Hz), 7.64 (1H, t, J = 8.1 Hz), 7.76 (1H, t, J = 8.1 Hz), 7.87 (1H, d, J = 5.4 Hz), 8.15 (1H, d, J = 8,1
Hz), 8.98 (1H, d, J = 5.4 Hz), 9.08 (1H, d, J = 8.1 Hz). 13C NMR (CDCl )  10.05, 28.64, 69.02, 71.51, 121.72,
3
125.36, 126.43, 127.73, 129.55, 129.87, 132.52, 148.82, 149.72, 161.60.
1
2

H
N
N
OH
4
O
-1
Brown oil. IR (neat, cm ) 3378, 3059, 2935, 2878, 1661, 1590, 1569, 1537, 1465, 1435, 1361, 1290, 1246, 1220, 1170,
1
1
147, 1065, 997, 913, 820, 750, 693, 621. H (CDCl )  3.66 (2H, t, J = 5.4 Hz), 3.86 (2H, t, J = 5.4 Hz), 7.44 (1H, m),
3
7
.86 (1H, t, J = 8.1 Hz), 8.20 (1H, d, J = 8.1 Hz), 8.55 (1H, d, J = 5.4 Hz). 13C NMR (CDCl )  42.53, 62.48, 122.29,
3
1
26.33, 137.44, 148.14, 149.71, 165.55. Anal. Calcd for C H O N : C, 57.82; H, 6.07; N, 16.86. Found: C, 57.95; H, 6.04;
8 10 2 2
N, 16.97.
1
3

1
H NMR (CDCl , 270.05 MHz)
3
H
N
N
OH
4
O
1
4

13
C NMR (CDCl , 67.80 MHz)
3
H
N
N
OH
4
O
1
5

1
H NMR (CDCl , 270.05 MHz)
3
N
N
3
O
1
6

13
C NMR (CDCl , 67.80 MHz)
3
N
N
3
O
1
7

1
H NMR (CDCl , 270.05 MHz)
3
N
O
6
N
1
8

13
C NMR (CDCl , 67.80 MHz)
3
N
O
6
N
1
9

1
H NMR (CDCl , 270.05 MHz)
3
N
N
8
O
2
0

13
C NMR (CDCl , 67.80 MHz)
3
N
N
8
O
2
1

1
H NMR(CDCl , 270.05 MHz)
3
N
N
1
0
O
2
2

13
C NMR(CDCl , 67.80 MHz)
3
N
N
10
O
2
3

1
H NMR(CDCl , 270.05 MHz)
3
N
N
N
12
O
O
2
4

13
C NMR(CDCl , 67.80 MHz)
3
N
N
N
12
O
O
2
5

1
H NMR(CDCl , 270.05 MHz)
3
N
N
14
S
O
2
6

13
C NMR(CDCl , 67.80 MHz)
3
N
N
14
S
O
2
7

1
H NMR(CDCl , 270.05 MHz)
3
N
1
6
N
O
2
8

13
C NMR(CDCl , 67.80 MHz)
3
N
1
6
N
O
2
9

1
H NMR(CDCl , 270.05 MHz)
3
N
O
18
N
3
0