The Journal of Organic Chemistry
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1.20 (d, J = 7.1 Hz, 3H); 13C{1H} NMR (CDCl3, 100 MHz) δ 169.4,
167.0, 165.7 (d, JC‑F = 257.1 Hz), 164.9, 139.1 (d, JC‑F = 10.4 Hz),
134.3, 134.0 (d, JC−F = 9.0 Hz), 128.2 (d, JC−F = 2.0 Hz), 126.0, 115.3
(d, JC−F = 24.9 Hz), 113.1 (d, JC−F = 25.1 Hz), 61.3, 61.2, 54.5 (d, JC‑F
= 2.0 Hz), 38.7, 23.6, 14.1, 13.9; 19F NMR (CDCl3, 376 MHz) δ
−101.3; IR (cm−1) ν 3407, 3071, 2988, 1731, 1710, 1382, 1270, 1158,
1038, 959, 860, 632; HRMS (ESI) calcd for C18H24FN2O7S [M +
NH4]+ 431.1283, found 431.1285.
J = 16.1, 7.4 Hz, 1H), 2.63 (s, 3H), 1.35 (t, J = 7.1 Hz, 3H), 1.19 (t, J =
7.1 Hz, 3H); 13C{1H} NMR (CDCl3, 100 MHz) δ 169.0, 167.1, 165.0,
164.4, 136.4, 135.7, 135.2, 134.4, 131.5, 128.7, 126.4, 125.7, 61.2, 61.1,
54.8, 53.0, 38.6, 23.6, 14.1, 13.9; IR (cm−1) ν 3398, 3079, 2992, 1723,
1706, 1436, 1362, 1270, 1158, 968, 764, 607; HRMS (ESI) calcd for
C20H24NO9S [M + H]+ 454.1166, found 454.1174.
Ethyl (N-Acetyl-1,1-dioxo-5-nitro-(E)-7-(ethoxy-3-oxoprop-1-enyl)
benzo[d]isothiazol-3-yl)acetate (3j). This compound was obtained as
a light yellow solid (72.2 mg, 55%) by following general procedure A:
mp 105−107 °C; 1H NMR (CDCl3, 400 MHz) δ 8.57 (s, 1H), 8.41 (s,
1H), 8.02 (d, J = 15.8 Hz, 1H), 6.78 (d, J = 15.8 Hz, 1H), 5.77 (d, J =
7.4 Hz, 1H), 4.30 (q, J = 6.9 Hz, 2H), 4.13 (q, J = 7.0 Hz, 2H), 3.20
(d, J = 16.5 Hz, 1H), 3.02 (dd, J = 16.4, 7.8 Hz, 1H), 2.60 (s, 3H), 1.34
(t, J = 7.0 Hz, 3H), 1.20 (t, J = 7.1 Hz, 3H); 13C{1H} NMR (CDCl3,
100 MHz) δ 169.0, 166.8, 164.6, 151.2, 138.1, 136.5, 133.2, 133.0,
127.2, 122.6, 120.6, 61.43, 61.36, 54.7, 38.2, 23.6, 14.1, 13.9; IR (cm−1)
ν 3419, 3091, 2971, 1723, 1552, 1328, 1275, 1167, 1026, 963, 744,
611; HRMS (ESI) calcd for C18H21N2O9S [M + H]+ 441.0962, found
441.0966.
Ethyl (N-Acetyl-1,1-dioxo-5-chloro-(E)-7-(ethoxy-3-oxoprop-1-
enyl)benzo[d]isothiazol-3-yl)acetate (3e). This compound was
obtained as a light yellow solid (124.3 mg, 96%) by following general
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procedure A: mp 124−126 °C; H NMR (CDCl3, 400 MHz) δ 7.94
(d, J = 15.8 Hz, 1H), 7.70 (s, 1H), 7.56 (s, 1H), 6.62 (d, J = 15.9 Hz,
1H), 5.65 (d, J = 7.5 Hz, 1H), 4.27 (q, J = 7.1 Hz, 2H), 4.12 (q, J = 7.1
Hz 2H), 3.13 (d, J = 16.4 Hz, 1H), 2.92 (dd, J = 16.3, 8.0 Hz, 1H),
2.58 (s, 3H), 1.32 (t, J = 7.0 Hz, 3H), 1.19 (t, J = 6.7 Hz, 3H);
13C{1H} NMR (CDCl3, 100 MHz) δ 169.3, 167.0, 164.9, 140.8, 137.7,
134.1, 132.6, 130.5, 127.9, 125.9, 125.7, 61.3, 61.2, 54.4, 38.6, 23.6,
14.1, 13.9; IR (cm−1) ν 3075, 2992, 1731, 1702, 1569, 1432, 1266,
1171, 1021, 955, 856, 615; HRMS (ESI) calcd for C18H21ClNO7S [M
+ H]+ 430.0722, found 430.0719.
Ethyl (1,1-Dioxo-2-acetyl-5-amino-(E)-7-(ethoxy-3-oxoprop-1-
enyl)-benzo[d]isothiazol-3-yl)acetate (3k). This compound was
obtained as a brown solid (19.5 mg, 16%) by following general
Ethyl (N-Acetyl-1,1-dioxo-5-bromo-(E)-7-(ethoxy-3-oxoprop-1-
enyl)benzo[d]isothiazol-3-yl)acetate (3f). This compound was
obtained as a yellow solid (118.7 mg, 84%) by following general
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procedure A: mp 157−159 °C; H NMR (CDCl3, 400 MHz) δ 7.91
(d, J = 15.9 Hz, 1H), 6.87 (s, 1H), 6.68 (s, 1H), 6.53 (d, J = 15.9 Hz,
1H), 5.55 (d, J = 7.6 Hz, 1H), 4.44 (s, 2H), 4.27 (q, J = 7.1 Hz, 2H),
4.14 (q, J = 7.1 Hz, 2H), 3.09 (d, J = 16.2 Hz, 1H), 2.88 (dd, J = 16.0,
7.9 Hz, 1H), 2.58 (s, 3H), 1.33 (t, J = 7.1 Hz, 3H), 1.21 (t, J = 7.0 Hz,
3H); 13C{1H} NMR (CDCl3, 100 MHz) δ 169.9, 167.4, 165.6, 152.0,
138.3, 136.2, 132.4, 124.1, 120.6, 113.5, 109.2, 61.1, 61.0, 54.5, 39.2,
23.5, 14.2, 14.0; IR (cm−1) ν 3469, 3378, 3253, 2975, 2913, 1743,
1706, 1631, 1374, 1304, 1196, 1042, 963, 681; HRMS (ESI) calcd for
C18H23N2O7S [M + H]+ 411.1222, found 411.1222.
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procedure A: mp 129−130 °C; H NMR (CDCl3, 400 MHz) δ 7.96
(d, J = 15.9 Hz, 1H), 7.87 (s, 1H), 7.73 (s, 1H), 6.63 (d, J = 15.9 Hz,
1H), 5.66 (dd, J = 8.0, 3.1 Hz, 1H), 4.28 (q, J = 7.1 Hz, 2H), 4.15 (q, J
= 7.1 Hz, 2H), 3.14 (dd, J = 16.4, 3.2 Hz, 1H), 2.93 (dd, J = 16.4, 8.0
Hz, 1H), 2.59 (s, 3H), 1.33 (t, J = 7.1 Hz, 3H), 1.21 (t, J = 7.1 Hz,
3H); 13C{1H} NMR (CDCl3, 100 MHz) δ 169.3, 167.0, 164.9, 137.7,
134.1, 132.6, 131.0, 130.9, 129.1, 128.7, 126.0, 61.3, 61.2, 54.4, 38.7,
23.6, 14.2, 14.0; IR (cm−1) ν 3075, 2984, 1714, 1565, 1316, 1279,
1167, 1042, 968, 619, 569; HRMS (ESI) calcd for C18H21BrNO7S [M
+ H]+ 474.0217, found 474.0220.
Ethyl (N-Acetyl-1,1-dioxo-(E)-9-(ethoxy-3-oxoprop-1-enyl)-
naphtho[1,2-d]isothiazol-3-yl)acetate (3l). This compound was
obtained as a white solid (54.4 mg, 41%) by following general
Ethyl (N-Acetyl-1,1-dioxo-5-methoxy-(E)-7-(ethoxy-3-oxoprop-1-
enyl)benzo[d]isothiazol-3-yl)acetate (3g). This compound was
obtained as a white solid (91.0 mg, 71%) by following general
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procedure A: mp 143−145 °C; H NMR (CDCl3, 400 MHz) δ 8.19
(s, 1H), 8.11 (d, J = 15.9 Hz, 1H), 8.08−8.04 (m, 1H), 8.03−7.98 (m,
1H), 7.74 (dd, J = 6.1, 3.1 Hz, 2H), 6.72 (d, J = 15.8 Hz, 1H), 6.16 (t,
J = 3.3 Hz, 1H), 4.29 (q, J = 7.1 Hz, 2H), 4.13 (dd, J = 6.9, 5.2 Hz,
2H), 3.21 (dd, J = 15.6, 3.2 Hz, 1H), 2.93 (dd, J = 15.6, 5.2 Hz, 1H),
2.65 (s, 3H), 1.35 (t, J = 7.1 Hz, 3H), 1.18 (t, J = 7.1 Hz, 3H);
13C{1H} NMR (CDCl3, 100 MHz) δ 169.5, 167.1, 165.5, 136.0, 135.3,
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procedure A: mp 147−149 °C; H NMR (CDCl3, 400 MHz) δ 7.97
(d, J = 15.9 Hz, 1H), 7.19 (d, J = 1.9 Hz, 1H), 7.01 (d, J = 1.7 Hz,
1H), 6.60 (d, J = 15.9 Hz, 1H), 5.63 (dd, J = 8.0, 3.2 Hz, 1H), 4.27 (q,
J = 7.1 2H), 4.13 (q, J = 7.1 2H), 3.88 (s, 3H), 3.14 (dd, J = 16.2, 3.3
Hz, 1H), 2.89 (dd, J = 16.2, 8.1 Hz, 1H), 2.59 (s, 3H), 1.33 (t, J = 7.1
Hz, 3H), 1.20 (t, J = 7.2 Hz, 3H); 13C{1H} NMR (CDCl3, 100 MHz)
δ 169.7, 167.2, 165.3, 164.1, 138.4, 135.5, 132.7, 124.8, 124.1, 114.4,
109.8, 61.2, 61.0, 56.0, 54.6, 39.1, 23.5, 14.2, 14.0; IR (cm−1) ν 3087,
2979, 2905, 1727, 1710, 1469, 1316, 1287, 1150, 1026, 968, 856, 636;
HRMS (ESI) calcd for C19H24NO8S [M + H]+ 426.1217, found
426.1223.
133.9, 129.98, 129.96, 129.7, 129.54, 129.47, 126.9, 125.9, 123.8,
123.7, 61.3, 60.9, 54.6, 40.5, 23.5, 14.2, 13.9; IR (cm−1) ν 2918, 1740,
1694, 1329, 1288, 1159, 1035, 757, 512; HRMS (ESI) calcd for
C22H24NO7S [M + H]+ 446.1268, found 446.1271.
Ethyl (N-Acetyl-1,1-dioxo-4-bromo-(E)-7-(ethoxy-3-oxoprop-1-
enyl)benzo[d]isothiazol-3-yl)acetate (3m). This compound was
obtained as a yellow solid (116.0 mg, 82%) by following general
Ethyl (N-Acetyl-1,1-dioxo-5-trifluoromethoxy-(E)-7-(ethoxy-3-ox-
oprop-1-enyl)benzo[d]isothiazol-3-yl)acetate (3h). This compound
was obtained as a yellow solid (115.5 mg, 80%) by following general
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procedure A: mp 117−119 °C; H NMR (CDCl3, 400 MHz) δ 8.02
(d, J = 15.9 Hz, 1H), 7.85 (d, J = 8.3 Hz, 1H), 7.65 (d, J = 8.3 Hz,
1H), 6.63 (d, J = 15.9 Hz, 1H), 5.64 (t, J = 3.4 Hz, 1H), 4.29 (q, J =
7.1 Hz, 2H), 4.03 (q, J = 7.1 Hz, 2H), 3.31 (dd, J = 15.3, 3.9 Hz, 1H),
3.24 (dd, J = 15.4, 4.3 Hz, 1H), 2.62 (s, 3H), 1.34 (t, J = 7.1 Hz, 3H),
1.10 (t, J = 7.1 Hz, 3H); 13C{1H} NMR (CDCl3, 100 MHz) δ 168.6,
167.0, 165.2, 137.9, 134.7, 134.5, 130.3, 129.0, 125.2, 120.2, 61.19,
61.15, 56.2, 35.8, 23.7, 14.2, 13.8 (one signal missing due to overlap);
IR (cm−1) ν 2988, 1723, 1648, 1466, 1263, 1117, 1026, 819, 603, 537;
HRMS (ESI) calcd for C18H21BrNO7S [M + H]+ 474.0217, found
474.0215.
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procedure A: mp 101−103 °C; H NMR (CDCl3, 400 MHz) δ 8.01
(d, J = 15.9 Hz, 1H), 7.54 (s, 1H), 7.46 (s, 1H), 6.65 (d, J = 15.9 Hz,
1H), 5.72 (dd, J = 8.4, 3.0 Hz, 1H), 4.30 (q, J = 7.1 Hz, 2H), 4.15 (q, J
= 7.1 Hz, 2H), 3.20 (dd, J = 16.4, 3.2 Hz, 1H), 2.90 (dd, J = 16.4, 8.4
Hz, 1H), 2.61 (s, 3H), 1.35 (t, J = 7.1 Hz, 3H), 1.21 (t, J = 7.1 Hz,
3H); 13C{1H} NMR (CDCl3, 100 MHz) δ 169.4, 167.0, 164.9, 153.2
(q, JC−F = 1.9 Hz), 138.7, 134.1, 133.6, 130.3, 126.3, 120.0 (d, JC−F
=
260.8 Hz), 119.9, 117.5 (d, JC−F = 1.0 Hz), 61.4, 61.3, 54.6, 38.8, 23.6,
14.2, 13.9; 19F NMR (CDCl3, 376 MHz) δ −57.7; IR (cm−1) ν 3407,
3083, 2996, 1710, 1590, 1366, 1258, 1171, 1038, 972, 851, 694;
HRMS (ESI) calcd for C19H21F3NO8S [M + H]+ 480.0935, found
480.0940.
Butyl (N-Acetyl-1,1-dioxo-4-bromo-(E)-7-(butoxy-3-oxoprop-1-
enyl)benzo[d]isothiazol-3-yl)acetate (3n). This compound was
obtained as a colorless oil (103.2 mg, 60%) by following general
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procedure A: H NMR (CDCl3, 400 MHz) δ 8.02 (d, J = 15.9 Hz,
Ethyl (N-Acetyl-1,1-dioxo-5-methoxycarbonyl-(E)-7-(ethoxy-3-ox-
oprop-1-enyl)benzo[d]isothiazol-3-yl) acetate (3i). This compound
was obtained as a white solid (101.0 mg, 74%) by following general
1H), 7.85 (d, J = 8.3 Hz, 1H), 7.65 (d, J = 8.3 Hz, 1H), 6.64 (d, J =
15.9 Hz, 1H), 5.64 (t, J = 4.1 Hz, 1H), 4.23 (t, J = 6.7 Hz, 2H), 3.98 (t,
J = 6.8 Hz, 2H), 3.32 (dd, J = 15.3, 4.0 Hz, 1H), 3.26 (dd, J = 15.4, 4.3
Hz, 1H), 2.62 (s, 3H), 1.73−1.66 (m, 2H), 1.48−1.40 (m, 4H), 1.23−
1.20 (m, 2H), 0.96 (t, J = 7.4 Hz, 3H), 0.86 (t, J = 7.4 Hz, 3H);
13C{1H} NMR (CDCl3, 100 MHz) δ 168.6, 167.0, 165.2, 137.9, 134.7,
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procedure A: mp 138−140 °C; H NMR (CDCl3, 400 MHz) δ 8.41
(s, 1H), 8.17 (s, 1H), 8.06 (d, J = 15.9 Hz, 1H), 6.74 (d, J = 15.9 Hz,
1H), 5.72 (dd, J = 7.3, 3.3 Hz, 1H), 4.31 (q, J = 7.1 Hz, 2H), 4.13 (q, J
= 7.1 Hz, 2H), 3.99 (s, 3H), 3.16 (dd, J = 16.1, 3.4 Hz, 1H), 3.03 (dd,
F
dx.doi.org/10.1021/jo5015239 | J. Org. Chem. XXXX, XXX, XXX−XXX