Month 2014
Reactions of 4,5-Dihydro-1,4-Benzothiazepin-3(2H)-one 1,1-Dioxide and 1,5-Dihydro-4,
1-Benzothiazepin-2(3H)-one 4,4-Dioxide Derivatives with Vilsmeier Reagent and DMFDMA
(d, 1H, H3, J = 8.8 Hz), 8.22 (dd, 1H, H4, J = 2.4, 8.8 Hz), 8.59
(d, 1H, H6, J = 2.4 Hz), 8.7-9.0 (br s, 3H, N+H3); 13C nmr
(DMSO-d6): d 39.66, 125.15, 125.74, 131.21, 134.53, 140.28,
146.52. Anal. calcd. for C7H8Cl2N2O2: C, 37.69; H, 3.62; N,
12.56. Found: C, 37.70; H, 3.62; N, 12.53.
(3E)-3-[(Dimethylamino)methylene]-1-methyl-1,5-dihydro-
4,1-benzothiazepin-2(3H)-one 4,4-dioxide (10). This compound
1
was obtained as pale yellow solid (toluene, 63%); mp 196ꢀC; H
nmr (DMSO-d6): d 2.81 (s, 6H, 2CH3), 3.34 (s, 3H, NCH3), 4.39
(s, 2H, CH2), 6.64 (s, 1H, CH), 7.25-7.44 (m, 4H, C6H4); 13C nmr
(DMSO-d6): d 36.05, 36.06, 39.59, 57.90, 99.24, 124.54, 127.26,
128.47, 130.13, 130.89, 144.46, 146.04, 162.96. Anal. calcd. for
C13H16N2O3S: C, 55.70; H, 5.75; N, 9.99. Found: C, 55.70;
H, 5.77; N, 10.01.
7-Nitro-4,5-dihydro-1,4-benzothiazepin-3(2H)-one (5). To
a stirred solution of 2-chloro-5-nitrobenzylamine hydrochloride
2 (11.15 g, 0.05 mol) and triethylamine (20.9mL, 0.15 mol) in
25mL DMSO was added methyl thioglycolate (4.5 mL, 0.05 mol).
After being stirred at 60ꢀC for 5 h, the reaction mixture was
cooled to room temperature, quenched with water (250mL), and
then stirring was continued 30 min. The precipitate was filtered
off, washed by acetone and dried to give 8.51 g (76%) of
7-nitro-4,5-dihydro-1,4-benzothiazepin-3(2H)-one 5. Pale yellow
solid; mp 263–265 ꢀC; 1H nmr (DMSO-d6): d 3.93 (s, 2H, 2-CH2),
4.50 (d, 2H, 5-CH2, J = 6.4 Hz), 7.33 (d, 1H, H9, J = 8.8Hz), 7.96
(dd, 1H, H8, J = 2.0, 8.8 Hz), 8.59 (d, 1H, H6, J = 2.0 Hz), 8.18
(t, 1H, NH, J = 6.4 Hz); 13C nmr (DMSO-d6): d 32.04, 44.76,
123.24, 125.26, 128.56, 135.38, 144.55, 146.06, 169.71. Anal.
calcd. for C9H8N2O3S: C, 48.21; H, 3.60; N, 12.49. Found: C,
48.20; H, 3.62; N, 12.50.
REFERENCES AND NOTES
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7-Nitro-4,5-dihydro-1,4-benzothiazepin-3(2H)-one 1,1-dioxide
(6). A mixture of 3 (6.72g, 0.03 mol) and 30% H2O2 (18 mL)
in 200 ml acetic acid was stirred at 40ꢀC for 3 days. The resultant
reaction mixture was concentrated in vacuo. MeOH 25mL was
added to residue, precipitate was collected by filtration, washed
MeOH, dried. The pure product was obtained by crystallization
1
from AcOH. White solid; mp 296–298 ꢀC; H nmr (DMSO-d6):
d 4.80 (d, 2H, 5-CH2, J = 5.6Hz), 4.85 (s, 2H, 2-CH2), 8.16
(d, 1H, H9, J = 8.4Hz), 8.35-8.38 (m, 2H, H6, H8), 8.67 (t, 1H,
NH, J =5.6 Hz); 13C nmr (DMSO-d6): d 44.09, 59.51, 124.05,
124.76, 127.68, 138.15, 148.26, 149.23, 163.31. Anal. calcd. for
C9H8N2O5S: C, 42.19; H, 3.15; N, 10.93. Found: C, 42.21; H,
3.13; N, 10.95.
(2E)-2-[(Dimethylamino)methylene]-7-nitro-4,5-dihydro-1,
4-benzothiazepin-3(2H)-one 1,1-dioxide (7).
This compound
1
was obtained as pale yellow solid (dioxane); mp 277–278 ꢀC; H
nmr (DMSO-d6): d 2.94 (s, 3H, CH3), 3.23 (s, 3H, CH3), 4.64
(d, 2H, CH2, J = 4.8Hz), 7.39 (s, 1H, CH), 8.09 (d, 1H, H9,
J = 8 Hz), 8.22 (t, 1H, NH, J = 4.8Hz), 8.28-8.30 (m, 2H, H6, H8);
13C nmr (DMSO-d6): d 41.15, 45.20, 47.20, 96.93, 124.33,
124.71, 126.74, 138.35, 148.95, 150.36, 151.75, 167.18. Anal.
calcd. for C12H13N3O5S: C, 46.30; H, 4.21; N, 13.50. Found: C,
46.33; H, 4.20; N, 13.49.
(2E)-2-[(Dimethylamino)methylene]-7-nitro-3-oxo-2,3-dihydro-
1,4-benzothiazepine-4(5H)-carbaldehyde 1,1-dioxide (8). This
compound was obtained as pale yellow solid (dioxane);
mp 257–258 ꢀC; 1H nmr (DMSO-d6): d 2.97 (s, 3H, CH3), 3.38
(s, 3H, CH3), 5.20 (s, 2H, CH2), 7.76 (s, 1H, CH), 8.14 (d, 1H,
H9, J = 7.6 Hz), 8.34 (d, 1H, H8, J = 7.6 Hz), 8.50 (s, 1H, H6),
8.91 (s, 1H, CHO); 13C nmr (DMSO-d6): d 41.95, 44.44,
47.82, 96.84, 124.40, 125.06, 125.93, 135.18, 148.34, 149.14,
154.98, 161.90, 165.83. Anal. calcd. for C13H13N3O6S: C,
46.01; H, 3.86; N, 12.38. Found: C, 46.00; H, 3.88; N, 12.40.
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A 2008, 64,
Journal of Heterocyclic Chemistry
DOI 10.1002/jhet