42 Laconde et al.
3.28 (s, 3H, NCH3), 3.90 (s, 3H, COOCH3), 4.11 (t,
2H, J = 8.47 Hz, CH2), 7.05 (m, 1H, ArH), 7.15 (d,
1H, J = 7.92 Hz, ArH), 7.55 (m, 4H, ArH), 7.94 (m,
1H, ArH). MS: m/z (%) = 388 (100).
aluminum chloride, and was refluxed for 1 h. After
cooling, the mixture was evaporated under reduced
pressure. The resulting mixture was taken up in wa-
ter and added NaOH 12 N having a pH of 10. The
precipitate formed was filtered off and recrystallized
from MeOH. The precipitate was recrystallized from
EtOH.
N-(1-Acetylindolin-5-yl)-N-methyl-2-sulfamoyl
Benzoic Acid (7a)
8a: Yellow crystals, yield 36%, mp 205–206◦C. IR
(KBr): νmax = 1650 (CO) and 1340,1170 (SO2N) cm−1.
1H NMR δ = 3.28 (s, 3H, NCH3), 3.30 (t, 2H, J = 8.47
Hz, CH2), 4.14 (t, 2H, J = 8.47 Hz, CH2), 7.13 (s, 1H,
ArH), 7.72 (m, 1H, ArH), 7.98 (m, 1H, ArH), 8.97 (s,
1H, ArH). MS: m/z (%) = 314 (100).
Methyl N-(1-acetylindolin-5-yl)-N-methyl-2-sul-
famoyl benzoate 6a (5.00 g, 0.013 mol) in ethanol/
water 1/1 was added potassium hydroxide (2.16 g,
0.038 mol). The resulting mixture was stirred at
100◦C for 2 h. After cooling, the reaction medium
was added to water and acidified with HCl 12 N for
pH 1. The precipitate formed was filtered off and re-
crystallized from MeOH.
The preparation of 8b was accomplished as 8a.
8b: Yellow crystals, yield 44%, mp 212–213◦C. IR
(KBr): νmax = 1640 (CO) and 1340,1160 (SO2N) cm−1.
1H NMR δ = 3.28 (t, 2H, J = 8.45 Hz, CH2), 3.31 (s,
3H, NCH3), 4.17 (t, 2H, J = 8.45 Hz, CH2), 7.72 (m,
2H, ArH), 7.97 (m, 2H, ArH), 8.15 (s, 1H, ArH), 8.21
(s, 1H, ArH). MS: m/z (%) = 314.
7a: White crystals, yield 89%, mp 227–228◦C.
IR (KBr): νmax = 3400 (OH) and 1360,1160 (SO2N)
cm−1. 1H NMR δ = 2.15 (s, 3H, CH3CO), 3.19 (t,
2H, J = 8.52 Hz, CH2), 3.28 (s, 3H, NCH3), 4.11 (t,
2H, J = 8.52 Hz, CH2), 6.92 (m, 1H, ArH), 7.09 (m,
1H, ArH), 7.32 (m, 1H, ArH), 7.50 (m, 1H, ArH),
7.58 (m, 1H, ArH), 7.70 (m, 1H, ArH), 7.95 (m, 1H,
ArH), 13.50 (m, 1H, COOH). MS: m/z (%) = 374
(100).
5,11-Dihydro-5-methyl-1-(3,4,5-trimethoxy
benzyl)benzo-[c]-1H-indolo[5,6,f][1,2]
thiazepin-11-one 6,6-dioxide (9)
The preparation of 7b was accomplished as 7a.
7b: White crystals, yield 92%, mp 228–229◦C. IR
(KBr): νmax = 3420 (OH) and 1350,1160 (SO2N) cm−1.
1H NMR δ = 2.12 (s, 3H, CH3CO), 3.13 (t, 2H, J =
8.49 Hz, CH2), 3.15 (s, 3H, NCH3), 4.11 (t, 2H, J =
8.49 Hz, CH2), 6.77 (m, 1H, ArH), 7.18 (m, 1H, ArH),
7.38 (m, 1H, ArH), 7.57 (m, 2H, ArH), 7.69 (m, 1H,
ArH), 7.92 (m, 1H, ArH), 13.50 (m, 1H, COOH). MS:
m/z (%) = 374 (100).
1-Acetyl-5,11-dihydro-5-methylbenzo[c]indolino-
[5,6, f ] [1, 2] thiazepin-11-one 6,6-dioxyde 8a
(0.15 g, 1 mmol) in DMF was added dropwise to
a solution of NaH (0.08 g, 2 mmol) in DMF. The
solution was stirred at room temperature. After 3
h, 3,4,5-trimethoxybenzyl chloride (0.55 g, 2 mmol)
in DMF was added dropwise over 10 min and the
mixture was stirred for 16 h at room temperature.
The solution was evaporated in vacuo to dryness
and H2O was added. The resulting precipitate
was collected by filtration, washed with H2O, and
recrystallized from ethanol.
5,11-Dihydro-5-methylbenzo[c]indolino[5,6,f]
[1,2]thiazepin-11-one 6,6-dioxide (8a)
9: Yellow crystals, yield 77%, mp 110–111◦C. IR
(KBr): νmax = 1650 (CO) and 1340,1170 (SO2N) cm−1.
1H NMR δ = 3.30 (s, 3H, NCH3), 3.77 (s, 6H, m,mꢁ-
OCH3), 3.82 (s, 3H, p-OCH3), 5.31 (s, 2H, CH2), 6.40
(s, 2H, ArH), 6.59 (d, 1H, J = 3.17 Hz, ArH), 7.37 (d,
1H, J = 3.17 Hz, ArH), 7.63 (s, 1H, ArH), 7.73 (m,
2H, ArH), 8.02 (m, 1H, ArH), 8.11 (m, 1H, ArH), 8.43
(s, 1H, ArH). MS: m/z (%) = 492 (100).
N-(1-acetylindolin-5-yl)-N-methyl-2-sulfamoyl ben-
zoic acid 7a (2.00 g, 0.005 mol) in toluene was added
thionyl chloride (1.11 mL, 0.016 mol). The reac-
tion was refluxed for 1 h. After cooling, the reaction
medium was evaporated under reduced pressure.
The resulting mixture was taken up in chloroform,
added aluminum chloride (2.12 g, 0.016 mol), and
refluxed for 1 h. After cooling, the reaction was
evaporated under reduced pressure. The resulting
mixture was taken up in water and extracted with
dichloromethane. The organic layer was washed
with NaOH 1 N, water, and dried with magnesium
sulfate. The precipitate was taken up in ethanol and
was added HCl 12 N. The reaction was refluxed for
2 h. After cooling to room temperature, the reac-
tion was evaporated under reduced pressure. The re-
sulting mixture was taken up in chloroform, added
5,11-Dihydro-5-methyl-1-(3,4,5-trimethoxy
benzyl)benzo-[f]-1H-indolo[6,5,c][1,2]-
thiazepin-11-one 6,6-dioxide (10)
1-Acetyl-5,11-dihydro-5-methylbenzo[c]indolino-
[5, 6, f ][1, 2]thiazepin-11-one 6,6-dioxyde 8b (0.30 g,
2 mmol) in DMF was added dropwise to a solution
of NaH (0.16 g, 4 mmol) in DMF. The solution