A. Nagaraju et al. / Tetrahedron 70 (2014) 3740e3746
3745
HRMS (ESIþ): calcd for C18H17NO4S2 [MþNa]þ 398.0491, found
J¼6.9 Hz, 2H, CH2), 3.26 (s, 2H, SCH2), 2.42 (s, 3H, ArCH3),1.55 (s, 3H,
allylic CH3), 1.33 (t, J¼6.9 Hz, 3H, CH3); 13C NMR (75 MHz, CDCl3):
398.0498.
d
188.0, 166.1, 154.7, 145.0, 141.1, 139.2, 134.1, 133.5, 129.5, 129.3,
4.5.10. 6-Allylsulfanyl-5-benzoyl-2-carbomethoxy methylene-3-oxo-
116.4, 115.8, 112.9, 60.8, 44.3, 21.7, 20.5, 14.1; IR (KBr, cmꢁ1): 3168,
3055, 2921, 1689, 1665, 1640, 1366, 1305, 1189, 828; HRMS (ESIþ):
calcd for C20H21NO4S2 [MþNa]þ 426.0804, found 426.0813.
1,4-thiazine (4j). Yellow solid; mp 99e102 ꢀC. 1H NMR (300 MHz,
CDCl3):
d
8.81 (br s, 1H, NH), 7.77 (d, J¼7.2 Hz, 2H, ArH), 7.60 (t,
J¼7.2 Hz, 1H, ArH), 7.47 (t, J¼7.5 Hz, 2H, ArH), 7.02 (s, 1H, ]CH),
5.61e5.49 (m, 1H, allylic ]CH), 5.05 (d, J¼15.9 Hz, 2H, ]CH2), 3.81
(s, 3H, CH3), 3.30 (d, J¼7.5 Hz, 2H, CH2); 13C NMR (75 MHz, CDCl3):
4.5.16. 2-Carbomethoxy methylene-6-(2-methyl-allylsulfanyl)-5-(4-
methyl-benzoyl)-3-oxo-1,4-thiazine
(4p). Yellow
solid;
mp
d
188.5, 166.5, 154.5, 141.2, 137.0, 133.6, 133.0, 131.7, 129.2, 128.8,
117e118 ꢀC. 1H NMR (300 MHz, CDCl3):
d
8.74 (br s, 1H, NH), 7.69 (d,
128.6, 119.5, 116.1, 52.0, 39.7; IR (KBr, cmꢁ1): 3181, 3059, 2927, 1682,
1637, 1307, 1121, 1010, 788; HRMS (ESIþ): calcd for C17H15NO4S2
[MþH]þ 362.0515, found 362.0526.
J¼8.1 Hz, 2H, ArH), 7.26 (d, J¼8.1 Hz, 2H, ArH), 7.00 (s, 1H, ]CH),
4.79 (s, 1H, allylic ]CH2), 4.73 (s, 1H, allylic ]CH2), 3.81 (s, 3H,
OCH3), 3.26 (s, 2H, SCH2), 2.43 (s, 3H, ArCH3), 1.55 (s, 3H, allylic
CH3); 13C NMR (75 MHz, CDCl3):
d 188.0, 166.6, 154.6, 145.0, 141.5,
4.5.11. 6-Allylsulfanyl-2-carboethoxy methylene-5-(4-methyl-ben-
139.2, 134.2, 133.5, 129.5, 129.4, 115.5, 115.9, 113.2, 51.8, 44.4, 21.7,
20.6; IR (KBr, cmꢁ1): 3176, 3063, 2927, 1652, 1605, 1304, 1196, 1173,
833; HRMS (ESIþ): calcd for C19H19NO4S2 [MþNa]þ 412.0648, found
412.0657.
zoyl)-3-oxo-1,4-thiazine (4k). Yellow solid; mp 103e105 ꢀC. 1H
NMR (300 MHz, CDCl3):
d
8.71 (br s, 1H, NH), 7.69 (d, J¼7.8 Hz, 2H,
ArH), 7.27 (d, J¼7.5 Hz, 2H, ArH), 7.00 (s, 1H, ]CH), 5.63e5.54 (m,
1H, allylic ]CH), 5.06 (d, J¼11.4 Hz, 2H, ]CH2), 4.27 (q, J¼7.2 Hz,
2H, OCH2), 3.31 (d, J¼6.9 Hz, 2H, SCH2), 2.43 (s, 3H, ArCH3), 1.34 (t,
4.5.17. 5-Benzoyl-6-benzylsulfanyl-2-carboethoxy methylene-3-oxo-
J¼6.9 Hz, 3H, CH3); 13C NMR (75 MHz, CDCl3):
d
188.1, 166.1, 154.6,
1,4-thiazine (4q). Yellow solid; mp 163e165 ꢀC. 1H NMR (300 MHz,
145.0, 141.0, 134.1, 133.2, 131.8, 129.5, 129.4, 119.3, 116.5, 113.1, 60.9,
39.7, 21.8, 14.1; IR (KBr, cmꢁ1): 3181, 3053, 2909, 1681, 1633, 1315,
1121, 1081, 718; HRMS (ESIþ): calcd for C19H19NO4S2 [MþH]þ
390.0828, found 390.0837.
CDCl3):
d
8.28 (br s, 1H, NH), 7.56 (d, J¼7.2 Hz, 3H, ArH), 7.45e7.39
(m, 2H, ArH), 7.25e7.22 (m, 3H, ArH), 7.08 (s, 1H, ]CH), 6.95 (d,
J¼3.6 Hz, 2H, ArH), 4.29 (q, J¼6.9 Hz, 2H, OCH2), 3.87 (s, 2H, SCH2),
1.35 (t, J¼7.2 Hz, 3H, CH3); 13C NMR (75 MHz, CDCl3):
d 188.0, 166.2,
154.4, 143.1, 140.9, 137.3, 135.3, 133.3, 133.0, 129.0, 128.6, 128.5,
127.8, 117.0, 116.8, 61.0, 41.4, 14.2; IR (KBr, cmꢁ1): 3167, 3060, 2924,
1693, 1665, 1646, 1305, 1184, 1038, 707; HRMS (ESIþ): calcd for
4.5.12. 6-Allylsulfanyl-2-carbomethoxy methylene-5-(4-methyl-ben-
zoyl)-3-oxo-1,4-thiazine (4l). Yellow solid; mp 128e129 ꢀC. 1H NMR
(300 MHz, CDCl3):
d
8.82 (br s, 1H, NH), 7.69 (d, J¼7.5 Hz, 2H, ArH),
C
22H19NO4S2 [MþH]þ 426.0828, found 426.0835.
7.27 (d, J¼6.9 Hz, 2H, ArH), 6.99 (s, 1H, ]CH), 5.63e5.54 (m, 1H,
allylic ]CH), 5.06 (d, J¼12.6 Hz, 2H, ]CH2), 3.81 (s, 3H, OCH3), 3.30
(d, J¼7.2 Hz, 2H, SCH2), 2.43 (s, 3H, CH3); 13C NMR (75 MHz, CDCl3):
4.5.18. 6-Benzylsulfanyl-2-carboethoxy methylene-5-(4-methyl-ben-
zoyl)-3-oxo-1,4-thiazine (4r). Yellow solid; mp 133e135 ꢀC. 1H NMR
d
188.1, 166.5, 154.6, 145.1, 141.4, 134.1, 133.3, 131.8, 129.6, 129.4,
(300 MHz, CDCl3):
d
8.28 (br s, 1H, NH), 7.50 (d, J¼8.1 Hz, 2H, ArH),
119.4, 115.9, 112.8, 52.0, 39.7, 21.7; IR (KBr, cmꢁ1): 3181, 3024, 2904,
7.25e7.21 (m, 5H, ArH), 7.05 (s, 1H, ]CH), 6.98e6.95 (m, 2H, ArH),
4.26 (q, J¼7.2 Hz, OCH2), 3.87 (s, 2H, SCH2), 2.42 (s, 3H, ArCH3), 1.34
1689, 1650, 1311, 1179, 1006, 788; HRMS (ESIþ): calcd for
C
18H17NO4S2 [MþH]þ 376.0672, found 390.0674.
(t, J¼6.9 Hz, 3H, CH3); 13C NMR (75 MHz, CDCl3):
d 187.6, 166.2,
154.4, 144.6, 141.1, 135.4, 134.4, 133.3, 129.3, 129.0, 128.5, 127.8,
116.8, 114.2, 61.0, 41.3, 21.7, 14.1; IR (KBr, cmꢁ1): 3167, 3057, 2923,
1686, 1665, 1650, 1305, 1185, 1044, 699; HRMS (ESIþ): calcd for
4.5.13. 5-Benzoyl-2-carboethoxy
fanyl)-3-oxo-1,4-thiazine (4m). Yellow solid; mp 144e145 ꢀC. 1H
NMR (300 MHz, CDCl3):
methylene-6-(2-methyl-allylsul-
d
8.69 (br s, 1H, NH), 7.78 (d, J¼7.2 Hz, 2H,
C
23H21NO4S2 [MþH]þ 440.0985, found 440.0990.
ArH), 7.60 (t, J¼7.2 Hz, 1H, ArH), 7.47 (t, J¼7.5 Hz, 2H, ArH), 7.02 (s,
1H, ]CH), 4.79 (s, 1H, ]CH2), 4.72 (s, 1H, ]CH2), 4.27 (q, J¼7.2 Hz,
2H, OCH2), 3.26 (s, 2H, SCH2), 1.54 (s, 3H, allylic CH3), 1.33 (t,
4.5.19. 6-Benzylsulfanyl-2-carbomethoxy
benzoyl)-3-oxo-1,4-thiazine (4s). Yellow solid; mp 147e148 ꢀC. 1H
NMR (300 MHz, CDCl3):
methylene-5-(4-methyl-
J¼6.9 Hz, 3H, CH3); 13C NMR (75 MHz, CDCl3):
d
188.5, 166.1, 154.6,
d
8.23 (br s, 1H, NH), 7.50 (d, J¼7.8 Hz, 2H,
141.0, 139.1, 137.0, 133.6, 133.1, 129.2, 128.6, 116.7, 115.9, 114.9, 60.9,
44.4, 20.7, 14.1; IR (KBr, cmꢁ1): 3169, 3062, 2923, 1691, 1667, 1646,
1447, 1286, 1187, 1036, 708; HRMS (ESIþ): calcd for C19H19NO4S2
[MþNa]þ 412.0648, found 412.0650.
ArH), 7.25e7.22 (m, 5H, ArH), 7.07 (s, 1H, ]CH), 6.97 (d, J¼3.6 Hz,
2H, ArH), 3.87 (s, 2H, SCH2), 3.84 (s, 3H, OCH3), 2.43 (s, 3H, ArCH3);
13C NMR (75 MHz, CDCl3):
d 184.0, 166.6, 154.3, 144.6, 135.4, 134.4,
133.3,129.3,129.0,128.6,128.2,127.8,116.3,114.4, 52.0, 41.4, 21.8; IR
(KBr, cmꢁ1): 3170, 3058, 2923, 1691, 1651, 1307, 1173, 830, 700;
HRMS (ESIþ): calcd for C22H19NO4S2 [MþH]þ 426.0828, found
426.0832.
4.5.14. 5-Benzoyl-2-carbomethoxy methylene-6-(2-methyl-allylsul-
fanyl)-3-oxo-1,4-thiazine (4n). Yellow solid; mp 137e138 ꢀC. 1H
NMR (300 MHz, CDCl3):
d
8.77 (br s, 1H, NH), 7.78 (d, J¼7.5 Hz, 2H,
ArH), 7.60 (t, J¼7.5 Hz, 1H, ArH), 7.46 (t, J¼7.2 Hz, 2H, ArH), 7.01 (s,
1H, ]CH), 4.79 (s, 1H, allylic ]CH2), 4.72 (s, 1H, allylic ]CH2), 3.81
(s, 3H, OCH3), 3.26 (s, 2H, SCH2), 1.54 (s, 3H, allylic CH3); 13C NMR
4.5.20. 6-Benzylsulfanyl-2-carboethoxy
phene-2-carbonyl)-1,4-thiazine (4t). Yellow solid; mp 165e166 ꢀC.
1H NMR (300 MHz, CDCl3):
methylene-3-oxo-5-(thio-
d
8.45 (br s, 1H, NH), 7.65 (d, J¼4.5 Hz,
(75 MHz, CDCl3):
d
188.4, 166.5, 154.5, 141.3, 139.1, 137.0, 133.6,
1H, ArH), 7.37 (d, J¼3 Hz, 1H, ArH), 7.18e7.13 (m, 3H, ArH), 7.00 (s,
3H, ArH), 6.92 (s, 1H, ArH), 4.21 (q, J¼6.9 Hz, 2H, CH2), 3.88 (s, 2H,
133.2,129.2,128.6,116.1, 115.9,114.6, 51.9, 44.4, 20.7; IR (KBr, cmꢁ1):
3174, 3057, 2924, 1691, 1666, 1651, 1563, 1307, 1280, 1174, 1037, 744;
HRMS (ESIþ): calcd for C18H17NO4S2 [MþNa]þ 398.0491, found
398.0494.
SCH2), 1.27 (t, J¼6.9 Hz, 3H, CH3); 13C NMR (75 MHz, CDCl3):
d 179.4,
166.1, 154.5, 142.0, 140.8, 135.9, 135.6, 135.2, 133.6, 129.0, 128.6,
128.3, 127.7, 116.8, 111.7, 61.0, 41.3, 14.2; IR (KBr, cmꢁ1): 3172, 3060,
2926, 1663, 1637, 1409, 1307, 1193, 700; HRMS (ESIþ): calcd for
4.5.15. 2-Carboethoxy methylene-6-(2-methyl-allylsulfanyl)-5-(4-
C
20H17NO4S3 [MþH]þ 432.0392, found 432.0392.
methyl-benzoyl)-3-oxo-1,4-thiazine
(4o). Yellow
solid;
mp
125e126 ꢀC. 1H NMR (300 MHz, CDCl3):
d
8.88 (br s,1H, NH), 7.70 (d,
4.5.21. 6-Benzylsulfanyl-2-carbomethoxy methylene-3-oxo-5-(thio-
J¼8.1 Hz, 2H, ArH), 7.26 (d, J¼7.5 Hz, 2H, ArH), 6.96 (s, 1H, ]CH),
4.78 (s, 1H, allylic ]CH2), 4.74 (s, 1H, allylic ]CH2), 4.26 (q,
phene-2-carbonyl)-1,4-thiazine (4u). Yellow solid; mp 135e137 ꢀC.
1H NMR (300 MHz, CDCl3):
d
8.76 (br s, 1H, NH), 7.73 (dd, J¼5.1 Hz,