DOI: 10.1039/C6OB02284G
Page 5 of 8
Journal Name
Organic & Biomolecular Chemistry
ARTICLE
8.2 Hz, 2H), 6.17 (d, J = 1.1 Hz, 1H), 4.11 (dd, J = 14.5, 2.4 Hz, 1H), – 7.07 (m, 2H), 6.34 (s, 1H), 4.19 (d, J = 15.7 Hz, 1H), 3.99 (dd, J =
3.88 (dd, J = 9.7, 2.2 Hz, 1H), 2.93 (dd, J = 14.6, 9.7 Hz, 1H), 2.45 19.3, 5.7 Hz, 2H), 3.52 (d, J = 15.7 Hz, 1H), 2.79 (dd, J = 13.6, 9.0
(s, 3H), 2.09 (d, J = 1.2 Hz, 3H); 13C NMR (100 MHz, CDCl3) δ Hz, 1H), 2.45 (s, 3H); 13C NMR (100 MHz, CDCl3) δ 144.29,
144.48, 142.26, 134.95, 132.48, 132.05, 130.12, 127.47, 126.52, 138.98, 136.96, 135.22, 134.82, 129.94, 128.91, 128.66, 128.60,
118.39, 112.60, 112.37, 72.24, 50.39, 21.66, 18.04; IR (neat): v (cm- 128.32, 127.79, 126.36, 125.83, 115.51, 73.21, 50.90, 37.55, 21.65;
1) 2960, 2919, 2852, 2230, 1660, 1597, 1345, 1159, 1088, 951, 816, IR (neat): v (cm-1) 2960, 2924, 2860, 1649, 1597, 1494, 1454, 1351,
708, 688, 581, 551; HRMS exact mass calcd for (C19H18N2O3S+H+) 1149, 1086, 965, 813, 756, 687, 651, 553; HRMS exact mass calcd
requires m/z 355.1111, found m/z 355.1120.
for (C24H23NO3S+H+) requires m/z 406.1471, found m/z 406.1496.
(Z)-5-benzylidene-2-phenyl-4-tosylmorpholine (3n’).8b Yellow oil
2-(4-(chloromethyl)phenyl)-5-methyl-4-tosyl-3,4-dihydro-2H-1,4-
oxazine (3j).
(88.9 mg, 44%, pet. ether/EtOAc = 15/1). 1H NMR (400 MHz,
1
Pale yellow oil (56.5 mg, 30%, pet. ether/EtOAc = 20/1). H NMR CDCl3) δ 7.55 (d, J = 8.2 Hz, 2H), 7.45 – 7.07 (m, 12H), 6.52 (s,
(400 MHz, CDCl3) δ 7.72 (d, J = 8.3 Hz, 2H), 7.38 (dd, J = 15.2, 8.1 1H), 4.54 (dd, J = 11.1, 2.3 Hz, 1H), 4.40 – 4.21 (m, 2H), 4.15 (dd, J
Hz, 4H), 7.09 (d, J = 8.1 Hz, 2H), 6.17 (d, J = 0.6 Hz, 1H), 4.56 (s, = 14.4, 2.5 Hz, 1H), 3.40 (dd, J = 14.3, 11.2 Hz, 1H), 2.38 (s, 3H).
2H), 4.11 (dd, J = 14.6, 2.3 Hz, 1H), 3.80 (dd, J = 9.9, 2.0 Hz, 1H), HRMS exact mass calcd for (C24H23NO3S+H+) requires m/z
2.95 (dd, J = 14.6, 9.9 Hz, 1H), 2.46 (s, 3H), 2.10 (d, J = 0.9 Hz, 406.1471, found m/z 406.1467.
3H); 13C NMR (100 MHz, CDCl3) δ 144.23, 137.82, 137.41, 135.04,
132.51, 130.02, 128.87, 127.55, 126.20, 112.18, 72.56, 50.67, 45.69, 5-methyl-2,6-diphenyl-4-tosyl-3,4-dihydro-2H-1,4-oxazine (3o).
1
21.63, 18.12; IR (neat): v (cm-1) 2957, 2925, 2855, 1657, 1454, 1354, Colorless oil (115.7 mg, 57%, pet. ether/EtOAc = 20/1). H NMR
1278, 1162, 1086, 1001, 951, 815, 757, 689, 578; HRMS exact mass (400 MHz, CDCl3) δ 7.83 (d, J = 8.2 Hz, 2H), 7.51 – 7.24 (m, 10H),
calcd for (C19H20ClNO3S+H+) requires m/z 378.0925, found m/z 7.20 (d, J = 7.9 Hz, 2H), 4.36 – 4.11 (m, 2H), 3.13 (dd, J = 14.4,
378.0881.
10.3 Hz, 1H), 2.46 (s, 3H), 2.26 (s, 3H); 13C NMR (100 MHz,
CDCl3) δ 144.27, 143.42, 137.55, 135.53, 135.49, 130.06, 129.19,
128.68, 128.52, 128.45, 128.09, 127.58, 125.88, 108.96, 73.57,
50.75, 21.67, 19.47; IR (neat): v (cm-1) 2960, 2928, 2875, 1662,
3-methyl-4-tosyl-4a,5,6,7,8,8a-hexahydro-4H-benzo[b][1,4]-
oxazine (3k).
1
Colorless oil (38.4 mg, 25%, pet. ether/EtOAc = 20/1). H NMR 1594, 1481, 1354, 1270, 1210, 1162 1087, 951, 828, 751, 688, 577,
(400 MHz, CDCl3) δ 7.70 (d, J = 8.2 Hz, 2H), 7.29 (d, J = 8.1 Hz, 535; HRMS exact mass calcd for (C24H23NO3S+H+) requires m/z
2H), 6.09 (s, 1H), 3.28 (td, J = 9.9, 4.2 Hz, 1H), 3.08 (ddd, J = 13.4, 406.1471, found m/z 406.1470.
10.0, 3.7 Hz, 1H), 2.42 (s, 3H), 2.01 (s, 3H), 1.99 – 1.92 (m, 1H),
1.79 – 1.55 (m, 4H), 1.26 – 1.16 (m, 3H); 13C NMR (100 MHz,
6-(4-bromophenyl)-5-methyl-2-phenyl-4-tosyl-3,4-dihydro-2H-
CDCl3) δ 143.65, 136.28, 135.88, 129.52, 127.65, 116.70, 77.43,
1,4-oxazine (3p).
63.52, 32.16, 30.86, 25.30, 23.59, 21.61, 18.44; IR (neat): v (cm-1) Colorless solid (142.5 mg, 59%, pet. ether/EtOAc = 20/1): mp 148 –
2957, 2932, 2865, 1725, 1662, 1598, 1454, 1357, 1165, 1149, 1089, 151 °C. 1H NMR (400 MHz, CDCl3) δ 7.80 (d, J = 8.2 Hz, 2H), 7.56
1008, 937, 812, 708, 659, 589, 537; HRMS exact mass calcd for – 7.46 (m, 2H), 7.45 – 7.25 (m, 7H), 7.18 (d, J = 7.4 Hz, 2H), 4.37 –
(C16H21NO3S+H+) requires m/z 308.1315, found m/z 308.1312.
4.04 (m, 2H), 3.10 (dd, J = 14.0, 9.8 Hz, 1H), 2.46 (s, 3H), 2.22 (s,
3H); 13C NMR (100 MHz, CDCl3) δ 144.35, 142.21, 137.33, 135.52,
134.44, 131.27, 130.82, 130.07, 128.72, 128.61, 127.53, 125.85,
122.47, 109.55, 73.84, 50.66, 21.67, 19.32; IR (neat): v (cm-1) 2988,
3-methyl-4-tosyl-4,4a,5,6,7,7a-hexahydrocyclopenta[b][1,4]-
oxazine (3l).
Colorless solid (32.1 mg, 22%, pet. ether/EtOAc = 20/1): mp 103 – 2923, 2867, 1586, 1487, 1350, 1264, 1164, 1073, 1007, 830, 735,
106 °C. 1H NMR (500 MHz, DMSO) δ 7.67 (d, J = 8.3 Hz, 2H), 554; HRMS exact mass calcd for (C24H22BrNO3S+H+) requires m/z
7.46 (d, J = 8.2 Hz, 2H), 6.07 (s, 1H), 3.57 (dd, J = 18.0, 8.8 Hz, 1H), 484.0577, found m/z 484.0570.
3.08 – 2.93 (m, 1H), 2.41 (s, 3H), 1.95 (s, 3H), 1.91 – 1.78 (m, 2H),
1.76 – 1.60 (m, 3H), 1.43 – 1.32 (m, 1H); 13C NMR (100 MHz,
5-methyl-2-phenyl-4-tosyl-6-(4-(trifluoromethyl)phenyl)-3,4-
CDCl3) δ 143.63, 136.00, 132.19, 129.77, 127.34, 115.23, 79.05,
dihydro-2H-1,4-oxazine (3q).
61.99, 27.12, 25.52, 21.59, 18.77, 18.18; IR (neat): v (cm-1) 2955, White solid (162.8 mg, 69%, pet. ether/EtOAc = 20/1): mp 145 –
2928, 2873, 1722, 1667, 1597, 1454, 1351, 1289, 1159, 1089, 978, 148 °C. 1H NMR (400 MHz, CDCl3) δ 7.81 (d, J = 8.2 Hz, 2H), 7.64
808, 737, 654, 583; HRMS exact mass calcd for (C15H19NO3S+H+) (d, J = 8.1 Hz, 2H), 7.56 (d, J = 8.0 Hz, 2H), 7.46 – 7.32 (m, 5H),
requires m/z 294.1158, found m/z 294.1120.
7.19 (dd, J = 5.3, 2.6 Hz, 2H), 4.26 (dd, J = 18.5, 5.6 Hz, 2H), 3.13
(td, J = 11.4, 2.7 Hz, 1H), 2.47 (s, 3H), 2.25 (s, 3H); 13C NMR (100
MHz, CDCl3) δ 144.43, 141.84, 139.11, 137.21, 135.55, 130.14,
(Z)-5-ethylidene-2-phenyl-4-tosylmorpholine (3m’).
1
Colorless oil (68.6 mg, 40%, pet. ether/EtOAc = 15/1). H NMR 130.09, 129.57, 128.74, 128.67, 127.52, 125.85, 125.03 (q, JC-F = 3.8
(400 MHz, CDCl3) δ 7.84 (d, J = 8.2 Hz, 2H), 7.40 – 7.18 (m, 7H), Hz), 110.39, 100.00, 74.04, 50.66, 21.64, 19.19; IR (neat): v (cm-1)
5.82 (q, J = 6.8 Hz, 1H), 4.18 (dd, J = 11.2, 2.4 Hz, 1H), 4.09 – 3.97 2957, 2929, 2864, 1728, 1661, 1456, 1351, 1320, 1161, 1073, 1012,
(m, 2H), 3.91 (d, J = 12.3 Hz, 1H), 3.23 (dd, J = 14.5, 11.2 Hz, 1H), 949, 846, 750, 667, 550; HRMS exact mass calcd for
2.46 (s, 3H), 1.81 (dd, J = 6.9, 1.5 Hz, 3H); 13C NMR (100 MHz, (C25H22F3NO3S+H+) requires m/z 474.1345, found m/z 474.1340.
CDCl3) δ 144.13, 138.33, 138.15, 131.96, 130.06, 128.56, 128.27,
127.85, 127.70, 125.86, 75.46, 69.47, 54.54, 21.63, 13.96; IR (neat):
5,6-dimethyl-2-phenyl-4-tosyl-3,4-dihydro-2H-1,4-oxazine (3r).
v (cm-1) 2965, 2923, 2857, 1595, 1475, 1449, 1349, 1159, 1093, 973, White solid (146.1 mg, 85%, pet. ether/EtOAc = 25/1): mp 101 –
900, 816, 759, 678, 554, 537; HRMS exact mass calcd for 104 °C. 1H NMR (300 MHz, CDCl3) δ 7.65 (d, J = 8.2 Hz, 2H), 7.35
(C19H21NO3S+H+) requires m/z 344.1315, found m/z 344.1317.
– 7.14 (m, 5H), 7.02 (dd, J = 7.5, 1.6 Hz, 2H), 3.95 (ddd, J = 12.8,
12.3, 2.6 Hz, 2H), 2.81 (dd, J = 14.4, 10.2 Hz, 1H), 2.37 (s, 3H),
(3n). 2.08 (s, 3H), 1.83 (s, 3H); 13C NMR (75 MHz, CDCl3) δ 143.98,
5-benzyl-2-phenyl-4-tosyl-3,4-dihydro-2H-1,4-oxazine
1
Yellow oil (75.4 mg, 37%, pet. ether/EtOAc = 20/1). H NMR (400 140.47, 137.67, 135.51, 129.89, 128.59, 128.39, 127.63, 125.77,
MHz, CDCl3) δ 7.65 (d, J = 8.2 Hz, 2H), 7.40 – 7.18 (m, 10H), 7.14 105.80, 73.23, 50.60, 21.61, 17.75, 17.13; IR (neat): v (cm-1) 2962,
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