The Journal of Organic Chemistry
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1.6 Hz, Ar), 7.42 (1H, dt, J = 7.9, 0.6 Hz, Ar), 7.29 (1H, d, J = 8.3 Hz,
Ar), 7.19 (2H, d, J = 8.0 Hz, Ar), 7.15 (2H, d, J = 8.0 Hz, Ar), 4.52
(1H, dd, J = 6.8, 6.0 Hz, CHCO), 3.58−3.51 (2H, m, CH2), 2.35
(3H, s, CH3), ppm; 13C NMR (125 MHz, CDCl3) δ 185.4 (CO),
153.9, 137.7, 137.6, 132.4, 129.9, 129.7, 129.6, 126.8, 120.9, 119.7 (C−
Ar), 72.2 (CH), 31.6 (CH2), 21.5 (CH3) ppm; m/z (EI, 70 eV) 302
(15, M+), 237 (100), 147 (52), 118 (67), 105 (58%) . Anal. Calcd for
C16H14O4S: C, 63.20; H, 4.63. Found: C, 63.56; H, 4.67%.
3-(4-Chlorobenzyl)benzo[e][1,2]oxathiin-4(3H)-one-2,2-dioxide
(4k): White solid (267 mg, 83%); mp 149−151 °C; IR (KBr) νmax
1
1697 (CO), 1377 (−SO2); 1169 (−SO2) cm−1; H NMR (500
MHz, CDCl3) δ 8.09 (1H, dd, J = 7.9, 1.5 Hz, Ar), 7.74 (1H, dt, J =
8.6, 1.6 Hz, Ar), 7.43 (1H, t, J = 7.3 Hz, Ar), 7.32−7.25 (5H, m, Ar),
4.52 (1H, dd, J = 6.5, 5.9 Hz, CHCO), 3.60 (1H, dd, J = 14.8, 6.8
Hz, Ph−CHH), 3.50 (1H, dd, J = 14.8, 5.7 Hz, Ph−CHH) ppm; 13C
NMR (125 MHz, CDCl3) δ 185.2 (CO), 153.9, 137.8, 134.1, 134.0,
131.1, 129.8, 129.4, 127.0, 120.8, 119.8 (C−Ar), 71.8 (CH), 31.0
(CH2) ppm; m/z (EI, 70 eV) 324 (2, M+ + 2), 322 (7, M+), 257
(100), 147 (87), 120 (87), 92 (68%). Anal. Calcd for C15H11ClO4S: C,
55.71; H, 3.31. Found: C, 55.82; H, 3.44%.
8-Methoxy-3-(4-methylbenzyl)benzo[e][1,2]oxathiin-4(3H)-one-
2,2-dioxide (4f): White solid (286 mg, 86%); mp 128−130 °C; IR
(KBr) νmax 1703 (CO), 1368 (−SO2); 1153 (−SO2) cm−1; 1H
NMR (500 MHz, CDCl3) δ 7.64 (1H, dd, J = 7.6, 1.4 Hz, Ar), 7.32
(1H, t, J = 8.0 Hz, Ar), 7.28 (1H, d, J = 6.5 Hz, Ar), 7.19 (2H, d, J =
8.0 Hz, Ar), 7.15 (2H, d, J = 7.9 Hz, Ar), 4.50 (1H, t, J = 6.5, CHC
O), 3.99 (3H, s, OCH3), 3.52 (2H, d, J = 6.5 Hz, CH2), 2.35 (3H, s,
CH3) ppm; 13C NMR (125 MHz, CDCl3) δ 185.6 (CO), 149.8,
143.2, 137.6, 132.5, 129.9, 129.5, 126.6, 121.8, 120.2, 119.7 (C−Ar),
72.1 (CH), 57.1 (OCH3), 31.6 (CH2), 21.5 (CH3) ppm; m/z (EI, 70
eV) 332 (8, M+), 268 (81), 150 (92), 122 (71), 105 (100%). Anal.
Calcd for C17H16O5S: C, 61.50; H, 4.66. Found: C, 61.43; H, 4.85%.
6-Bromo-3-(4-methylbenzyl)benzo[e][1,2]oxathiin-4(3H)-one-
2,2-dioxide (4g): White solid (370 mg, 87%); mp 129−131 °C; IR
(KBr) νmax 1684 (CO), 1387 (−SO2); 1173 (−SO2) cm−1; 1H
NMR (500 MHz, CDCl3) δ 8.19 (1H, d, J = 2.4 Hz, Ar), 7.82 (1H, dd,
J = 8.7, 2.4 Hz, Ar), 7.19−7.14 (5H, m, Ar), 4.51 (1H, t, J = 6.4,
CHCO), 3.52 (2H, d, J = 6.4 Hz, CH2), 2.35 (3H, s, CH3) ppm;
13C NMR (125 MHz, CDCl3) δ 184.3 (CO), 152.8, 140.2, 137.8,
3-(4-Chlorobenzyl)-8-methoxybenzo[e][1,2]oxathiin-4(3H)-one-
2,2-dioxide (4l): White solid (306 mg, 87%); mp 154−156 °C; IR
(KBr) νmax 1686 (CO), 1377 (−SO2); 1152 (−SO2) cm−1; 1H
NMR (500 MHz, CDCl3) δ 7.63 (1H, dd, J = 7.7, 1.5 Hz, Ar), 7.34
(2H, d, J = 8.0 Hz, Ar), 7.32−7.28 (2H, m, Ar), 7.26 (2H, d, J = 8.4
Hz, Ar), 4.49 (1H, dd, J = 6.7, 5.8 Hz, CHCO), 3.58 (1H, dd, J =
14.8, 7.0 Hz, Ph−CHH), 3.51 (1H, dd, J = 14.8, 5.7 Hz, Ph−CHH)
ppm; 13C NMR (125 MHz, CDCl3) δ 185.5 (CO), 149.8, 143.7,
134.1, 133.9, 131.1, 129.4, 126.7, 121.8, 120.2, 119.9 (C−Ar), 71.7
(CH), 57.1 (OCH3), 31.1 (CH2) ppm; m/z (EI, 70 eV) 354 (2, M+ +
2), 352 (7, M+), 288 (42), 150 (89), 91 (44), 69 (100%). Anal. Calcd
for C16H13ClO5S: C, 54.55; H, 3.54. Found: C, 54.47; H, 3.71%.
6-Bromo-3-(4-chlorobenzyl)benzo[e][1,2]oxathiin-4(3H)-one-2,2-
dioxide (4m): Yellow solid (356 mg, 89%); mp 166−168 °C; IR
(KBr) νmax 1694 (CO), 1375 (−SO2); 1158 (−SO2) cm−1; 1H
NMR (500 MHz, CDCl3) δ 8.19 (1H, d, J = 2.4 Hz, Ar), 7.83 (1H, dd,
J = 8.7, 2.4 Hz, Ar), 7.32 (2H, d, J = 8.4 Hz, Ar), 7.25 (2H, d, J = 8.4
Hz, Ar), 7.18 (1H, d, J = 8.7 Hz, Ar), 4.50 (1H, t, J = 6.3 Hz, CHC
O), 3.58 (1H, dd, J = 14.9, 8.8 Hz, Ph−CHH), 3.50 (1H, dd, J = 14.9,
5.0 Hz, Ph−CHH), ppm; 13C NMR (125 MHz, CDCl3) δ 184.1 (C
O), 152.8, 140.5, 133.7, 132.2, 131.1, 129.4, 122.2, 121.6, 120.2 (C−
Ar), 71.7 (CH), 31.0 (CH2) ppm; m/z (EI, 70 eV) 402 (11, M+ + 2),
400 (8, M+), 338 (100), 200 (63), 138 (32), 125 (58%). Anal. Calcd
for C15H10BrClO4S: C, 44.80; H, 2.18. Found: C, 44.85; H, 2.51%.
3-Benzyl-6-chlorobenzo[e][1,2]oxathiin-4(3H)-one-2,2-dioxide
(4n): White solid (283 mg, 88%); mp 128−130 °C; IR (KBr) νmax
133.0, 132.0, 130.0, 129.5, 122.2, 121.6, 120.0 (C−Ar), 72.0 (CH),
31.7 (CH2), 21.5 (CH3) ppm; m/z (EI, 70 eV) 382 (8, M+ + 2), 380
(8, M+), 317 (37), 118 (100), 105 (73), 77 (23%). Anal. Calcd for
C16H13BrO4S: C, 50.40; H, 3.21. Found: C, 50.41; H, 3.44%.
3-(4-Bromobenzyl)benzo[e][1,2]oxathiin-4(3H)-one-2,2-dioxide
(4h): White solid (307 mg, 84%); mp 147−149 °C; IR (KBr) νmax
1
1697 (CO), 1376 (−SO2); 1170 (−SO2) cm−1; H NMR (500
MHz, CDCl3) δ 8.10 (1H, dd, J = 7.9, 1.7 Hz, Ar), 7.75 (1H, ddd, J =
8.2, 7.5, 1.7 Hz, Ar), 7.47 (2H, d, J = 8.4 Hz, Ar), 7.43 (1H, dt, J = 8.3,
1.0 Hz, Ar), 7.30 (1H, dt, J = 4.7, 0.6 Hz, Ar), 7.21 (2H, d, J = 10.7 Hz,
Ar), 4.50 (1H, dd, J = 6.8, 5.7 Hz, CHCO), 3.59 (1H, dd, J = 14.8,
6.8 Hz, Ph−CHH), 3.49 (1H, dd, J = 14.8, 5.7 Hz, Ph−CHH) ppm;
13C NMR (125 MHz, CDCl3) δ 185.1 (CO), 153.9, 137.8, 134.6,
1
1694 (CO), 1386 (−SO2); 1165 (−SO2) cm−1; H NMR (500
MHz, CDCl3) δ 8.04 (1H, s, Ar), 7.66 (1H, d, J = 8.2 Hz, Ar), 7.34−
7.23 (6H, m, Ar), 4.54 (1H, br, CHCO), 3.57 (2H, br, CH2) ppm;
13C NMR (125 MHz, CDCl3) δ 184.4 (CO), 152.2, 137.4, 135.2,
132.3, 131.5, 129.8, 127.0, 122.1, 120.9, 119.8 (C−Ar), 71.7 (CH),
31.1 (CH2) ppm; m/z (EI, 70 eV) 368 (6, M+ + 2), 366 (6, M+), 303
(83), 147 (100), 120 (96), 92 (82%). Anal. Calcd for C15H11BrO4S: C,
48.95; H, 2.72. Found: C, 49.06; H, 3.02%.
132.8, 129.7, 129.3, 129.1, 128.1, 121.9, 121.4 (C−Ar), 71.8 (CH),
31.9 (CH2) ppm; m/z (EI, 70 eV) 324 (1, M+ + 2), 322 (3, M+), 258
(100), 181 (62), 154 (79), 91 (92%). Anal. Calcd for C15H11ClO4S: C,
55.51; H, 3.22. Found: C, 55.82; H, 3.44%.
3-(4-Bromobenzyl)-8-methoxybenzo[e][1,2]oxathiin-4(3H)-one-
2,2-dioxide (4i): Yellow solid (340 mg, 85%); mp 163−165 °C; IR
(KBr) νmax 1700 (CO), 1386 (−SO2); 1151 (−SO2) cm−1; 1H
NMR (500 MHz, CDCl3) δ 7.63 (1H, dd, J = 7.7, 1.7 Hz, Ar), 7.46
(2H, d, J = 8.4 Hz, Ar), 7.33 (1H, t, J = 7.9 Hz, Ar), 7.30 (1H, dd, J =
8.1, 1.6 Hz, Ar), 7.20 (2H, d, J = 8.4 Hz, Ar), 4.48 (1H, dd, J = 6.9, 5.8
Hz, CHCO), 3.97 (3H, s, OCH3), 3.56 (1H, dd, J = 14.8, 7.0 Hz,
Ph−CHH), 3.49 (1H, dd, J = 14.8, 5.7 Hz, Ph−CHH) ppm; 13C
NMR (125 MHz, CDCl3) δ 185.4 (CO), 149.8, 143.7, 134.7, 132.3,
131.5, 126.7, 122.0, 121.8, 120.2, 119.9 (C−Ar), 71.7 (CH), 57.1
(OCH3), 31.2 (CH2), ppm; m/z (EI, 70 eV) 398 (7, M+ + 2), 396 (7,
M+), 334 (33), 169 (34), 150 (100), 122 (67%). Anal. Calcd for
C16H13BrO5S: C, 48.40; H, 3.26. Found: C, 48.38; H, 3.30%.
6-Bromo-3-(4-bromobenzyl)benzo[e][1,2]oxathiin-4(3H)-one-
2,2-dioxide (4j): White solid (375 mg, 84%); mp 174−175 °C; IR
(KBr) νmax 1695 (CO), 1374 (−SO2); 1157 (−SO2) cm−1; 1H
NMR (500 MHz, CDCl3) δ 8.19 (1H, d, J = 2.3 Hz, Ar), 7.83 (1H, dd,
J = 8.7, 2.4 Hz, Ar), 7.47 (2H, d, J = 8.2 Hz, Ar), 7.19 (3H, d, J = 8.4
Hz, Ar), 4.50 (1H, t, J = 6.2 Hz, CHCO), 3.57 (1H, dd, J = 14.9, 6.8
Hz, Ph−CHH), 3.49 (1H, dd, J = 14.8, 5.6 Hz, Ph−CHH) ppm; 13C
NMR (125 MHz, CDCl3) δ 184.1 (CO), 152.8, 140.3, 134.2, 132.4,
132.2, 131.4, 122.3, 122.2, 121.6, 120.2 (C−Ar), 71.6 (CH), 31.1
(CH2) ppm; m/z (EI, 70 eV) 446 (6, M+ + 2), 444 (4, M+), 200 (86),
171 (67), 77 (59), 63 (100%). Anal. Calcd for C15H10Br2O4S: C,
40.51; H, 2.08. Found: C, 40.38; H, 2.26%.
Synthesis of 3-[Methoxy(phenyl)methyl]benzo[e][1,2]-
oxathiine-2,2-dioxide Derivatives 5. General procedure: To a
stirring solution of DBU (0.076 g, 50 mol %) in MeOH (10 mL) was
added 2-formylphenyl-(E)-2-phenylethenesulfonate (3a) (0.288 g,
1 mmol) at room temperature. The progress of the reaction was
followed by TLC. After completion, the solvent was removed under
reduced pressure and H2O (30 mL) and CH2Cl2 (30 mL) were added.
The two phases were separated, and the organic phase was washed
with a solution of Na2CO3 (5%, 3 × 15 mL). The organic phase was
then dried over Na2SO4, and the solvent was removed under reduced
pressure. The residue was purified by column chromatography (SiO2,
eluent: 1:2, n-hexane/CH2Cl2) to afford 3-[methoxy(phenyl)methyl]-
benzo[e][1,2]oxathiine-2,2-dioxide (5a).
3-[Methoxy(phenyl)methyl]benzo[e][1,2]oxathiine-2,2-dioxide
(5a): White solid (160 mg, 53%); mp 114−116 °C; IR (KBr) νmax
1
1365 (−SO2), 1171 (−SO2), 1096, 905, 762 cm−1; H NMR (500
MHz, CDCl3) δ 7.51−7.43 (6H, m, Ar), 7.35 (1H, d, J = 6.7 Hz, Ar),
7.29 (1H, d, J = 4.9 Hz, Ar), 7.27 (1H, s, Ar), 6.82 (1H, s, CCH),
5.39 (1H, s, ArCH), 3.49 (3H, s, OCH3) ppm; 13C NMR (125 MHz,
CDCl3) δ 151.4, 138.5, 136.8, 132.1, 131.9, 129.9, 129.5, 129.3, 128.1,
126.3, 120.5, 119.1 (C−Ar), 80.2 (C−OMe), 58.2 (OCH3), ppm; m/z
(EI, 70 eV) 302 (3, M+), 238 (24), 207 (100), 178 (16), 77 (5%).
Anal. Calcd for C16H14O4S: C, 63.60; H, 4.44. Found: C, 63.56; H,
4.67%.
9980
dx.doi.org/10.1021/jo201506d | J. Org. Chem. 2011, 76, 9975−9982