ACCEPTED MANUSCRIPT
= 8.8 Hz, HAr), 5.46 (2H, s, СН2), 3.80 (3H, s, OCH3); 13C NMR (DMSO-
HAr), 7.47 (1H, dt,
J
= 7.3, 1.2 Hz, HAr), 7.38 (1H, dt,
J
=7.9 Hz, 1.2, HAr), 7.31 and 6.91 (4Н, AA′XX′,
J
d
6, 100.6 MHz) δ: 159.6, 150.6,
149.3, 144.3, 130.7, 126.3, 125.3, 121.9, 119.5, 117.0, 114.4, 111.6, 55.2, 49.6. MS (EI) [m/z, (I, %)]:
295 (M+, 5). Calcd for C16H13N3OS: C, 65.06; H, 4.44; N, 14.23; S, 10. 86; found, %: C, 65.45; H, 4.40;
N, 14.15; S, 10.47.
4.1.5. General procedure for the synthesis of 4-acyl- and 4-sulfonyl-4H-[1,2,3]thiadiazolo[5,4-b]indoles
18 and 20
A solution of 4H-1,2,3-thiadiazolo[5,4-b]indole 14a (0.175 g, 1.0 mmol) in CHCl3 (10 mL), TEA (0.1
g, 1.0 mmol) and acyl/sulfonyl chloride (1.5 mmol) were added. The reaction mixture was reflux for 1-
1.5 h. After the completion of the reaction (TLC), the resulting solution was diluted with hexane. The
solid was filtered off, washed with hexane, and recrystallized from ethanol.
4.1.5.1 (4H-[1,2,3]Thiadiazolo[5,4-b]indol-4-yl)(cyclohexyl)methanone (18a).
According to Section 4.1.5, 4
chloride (17a, 219 mg) and triethylamine (101 mg) were used for the reaction. After filtration, 18a was
obtained as a grey solid (270 mg, 95%), mp 124-125 °С. 1Н NMR (DMSO-
6, 400 MHz) δ: 8.23 (1H, dd,
= 0.56, 7.4 Hz, HAr), 8.10 (1H, br s, HAr), 7.61-7.51 (2H, m, HAr), 3.32 (1H, m, CH), 2.09-1.79 (5Н, m,
H-[1,2,3]thiadiazolo[5,4-b]indole (14a, 175 mg), cyclohexanecarbonyl
d
J
13
CH2), 1.68-1.35 (5H, m, СН2); C NMR (DMSO-d6, 100.6 MHz) δ: 173.6, 153.7, 147.2, 127.9, 125.3,
120.5, 116.6, 43.4, 28.9, 25.7, 25.2. MS (EI) [m/z, (I, %)]: 285 (M+, 2). Calcd for C15H15N3OS: C, 63.13;
H, 5.30; N, 14.73; S, 11. 24; found, %: C, 63.15; H, 5.25; N, 14.55; S, 11.27.
4.1.5.2 (4H-[1,2,3]thiadiazolo[5,4-b]indol-4-yl)(4-chlorophenyl)methanone (18b).
According to Section 4.1.5, 4H-[1,2,3]thiadiazolo[5,4-b]indole (14a, 175 mg), 4-chlorobenzoyl chloride (17b,
263 mg) and triethylamine (101 mg) were used for the reaction. After filtration, 18b was obtained as a white solid
(300 mg, 95%), mp 155-156 °С. 1Н NMR (DMSO-d6, 400 MHz) δ: 8.15 (1H, d, J = 7.7 Hz, HAr), 7.80 (1H, d, J =
8.3 Hz, HAr), 7.47 (1H, dt, J = 7.3, 1.2 Hz, HAr), 7.38 (1H, dt, J = 7.9 Hz, 1.2, HAr), 7.31 and 6.91 (4Н, AA′XX′, J
= 8.8 Hz, HAr), 5.46 (2H, s, СН2) 3.80 (3H, s, OCH3); 13C NMR (DMSO-d6, 100.6 MHz) δ: 166.9, 154.5, 149.2,
142.7, 138.2, 131.8, 130.7 (2C), 129.9 (2C), 127.5, 125.7, 120.4, 120.3, 116.9. MS (EI) [m/z, (I, %)]: 313 (M+, 8).
Calcd for C15H8ClN3OS: C, 57.42; H, 2.57; N, 13.39; found, %: C, 57.25; H, 2.64; N, 13.55.
4.1.5.3 (4H-[1,2,3]Thiadiazolo[5,4-b]indol-4-yl)(3-fluorophenyl)methanone (18c).
According to Section 4.1.5, 4
H-[1,2,3]thiadiazolo[5,4-b]indole (14a, 175 mg), 3-fluorobenzoyl
chloride (17c, 239 mg) and triethylamine (101 mg) were used for the reaction. After filtration, 18c was
1
obtained as a beige solid (270 mg, 90%), mp 164-165 °С. Н NMR (DMSO-
dd, = 1.0, 7.8 Hz, HAr), 7.76-7.69 (2H, m, HAr), 7.66-7.63 (2H, m, HAr), 7.59-7.45 (3H, m, HAr); C
NMR (DMSO-
6, 100.6 MHz) δ: 166.5 (d, 4J = 2.5, C=O), 162.4 (d, 1J = 245.7, C-F), 154.2 (CInd),
d6, 400 MHz) δ: 8.22 (1H,
13
J
d
149.2(CInd), 142.7 (CInd), 135.1 (d, 3J = 7.6, CAr), 132.4 (d, 3J = 8.2, CHAr), 127.6 (CHInd), 125.9 (CHInd),
124.7 (d, 4J = 3.0, CHAr), 120.5 (CHInd), 120.4 (CInd), 120.2 (d, 2J = 20.9, CHAr), 116.9 (CHInd), 115.6 (d,
2J = 23.9, CHAr). MS (EI) [m/z, (I, %)]: 297 (M+, 10). Calcd for C15H8FN3OS: C, 60.60; H, 2.71; N,
14.13; S, 10. 79; found, %: C, 60.30; H, 2.30; N, 14.12; S, 10.54.
4.1.5.4 4-(4-Methoxyphenylsulfonyl)-4H-[1,2,3]thiadiazolo[5,4-b]indole (20a).
According to Section 4.1.5, 4
H-[1,2,3]thiadiazolo[5,4-b]indole (14a, 175 mg), 4-methoxybenzene-1-
sulfonyl chloride (19a, 311 mg) and triethylamine (101 mg) were used for the reaction. After filtration,
1
20a was obtained as a brown solid (300 mg, 87%), mp 140-141 °С. Н NMR (DMSO-
MHz) δ: 8.16 (1H, d, = 7.6 Hz, HAr), 8.07 (1H, d, = 7.9 Hz, HAr), 7.56 (1Н, t, = 7.7 Hz, HAr), 7.50
(1Н, t, = 7.1 Hz, HAr), 7.95 and 7.05 (4Н, AA′XX′, = 9.0 Hz, HAr), 3.81 (3H, s, OCH3); C NMR
(DMSO-
d6+CCl4, 400
J
J
J
13
J
J
d
6, 100.6 MHz) δ: 166.4, 154.0, 148.4, 141.5, 130.1, 128.0, 126.6, 125.8, 120.9, 119.8, 116.0,
114.7, 56.4. MS (EI) [m/z, (I, %)]: 345 (M+, 2). Calcd for C15H11N3O3S2: C, 52.16; H, 3.21; N, 12.17; S,
18. 57; found, %: C, 52.30; H, 3.15; N, 12.22; S, 18.34.
16