Beilstein J. Org. Chem. 2011, 7, 1526–1532.
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0.9 (PzCH2CH2SО), 51.9 (PzCH2CH2SО), 105.1 (С4 (Pz)), (DMSO-d6) δ 63.2 (CH2), 111.2 (C7 (Bta)), 119.4 (C4 (Bta)),
39.5 (С5 (Pz)), 148.3 (С3 (Pz)); Anal. calcd for С14Н22N4OS: 124.8 (C5 (Bta)), 128.5 (C6 (Bta)), 133.6 (C8 (Bta)), 145.0 (C9
С, 57.11; Н, 7.53; N, 19.03; S, 10.89; found: С, 57.50; Н, 7.60; (Bta)); Anal. calcd for C14H12N6O2S: С, 51.21; Н, 3.68; N,
N, 19.15; S, 10.69. 25.59; found: С, 51.63; Н, 4.02; N, 25.98.
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,1'-(Sulfonylbis(ethane-2,1-diyl))bis(3,5-dimethylpyrazole) 1,1'-(Sulfinylbis(ethane-2,1-diyl))bis(3,5-dimethyl-4-nitropy-
7). To thioether 3 (0.87 g, 3.4 mmol) in acetic acid (1 mL), razole) (10). To thioether 3 (0.647 g, 2.33 mmol), НNO3
hydrogen peroxide (0.64 mL of 50% aqueous solution, (1.61 mL of 68% aqueous solution, 23.3 mmol) and Н2SO4
.42 mmol) was added. After being heated under reflux for 5 h, (8 mL of 96% aqueous solution) were added. After the mixture
(
9
the reaction mixture was poured into water (25 mL) and was allowed to stand for 24 h at room temperature, water
extracted with chloroform (8 × 10 mL). The extract was washed (50 mL) was added to the reaction mixture, and the solution was
with water (2 × 10 mL), dried over calcium chloride and the extracted by chloroform (5 × 10 mL). The extract was washed
solvent was evaporated in vacuo. Yield 0.75 g (77%), colorless with water to neutral reaction, dried over calcium chloride
crystals, mp 122–123 °С (toluene); IR (cm−1): 1552, 1466, and the solvent was evaporated in vacuo. Yield 0.71 g (84%),
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390 (Рz), 1298, 1128 (О=S=O), 772 (С–S); 1Н NMR (CDCl3) colorless crystals, mp 147–148 °С (iPrOH); IR (cm−1): 1561
δ 2.15, 2.23 (s, 12Н, СН3), 3.24 (t, J = 6 Hz, 4Н, (N–O), 1490, 1419 (Рz), 1356 (N–O), 1044 (S=O); 1Н NMR
PzCH2CH2SO2), 4.33 (t, J = 6 Hz, 4Н, PzCH2CH2SO2), 5.76 (CDCl3) δ 2.47, 2.66 (s, 12Н, CН3), 3.25 (ABXY m, 4Н,
(
(
(
s, 2Н, Н4 (Pz)); 13С NMR (CDCl3) δ 10.7 (5-СН3), 13.3 PzCH2CH2SО), 4.48 (ABXY m, 4Н, PzCH2CH2SО);
3-СН3), 41.3 (PzCH2CH2SO2), 53.1 (PzCH2CH2SO2), 105.5 13С NMR (CDCl3) δ 11.2 (5-СН3), 13.9 (3-СН3), 41.9
С4 (Pz)), 139.9 (С5 (Pz)), 148.7 (С3 (Pz)); Anal. calcd for (PzCH2CH2SО), 51.1 (PzCH2CH2SО), 130.9 (С4 (Pz)), 140.8
С14Н22N4O2S: С, 54.17; Н, 7.14; N, 18.05; S, 10.33; found: С, (С5 (Pz)), 146.7 (С3 (Pz)); Anal. calcd for С14Н20N6O5S: С,
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3.98; Н, 7.05; N, 18.35; S, 10.33.
43.73; Н, 5.24; N, 21.86; S 8.34; found: С, 44.06; Н, 5.23; N,
1.46; S, 8.26.
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,1'-(Sulfinylbis(methylene))bis(benzotriazole) (8). Thioether
(0.209 g, 0.706 mmol), selenium dioxide (0.157 g, 1.41 1,5-Bis(4-iodo-3,5-dimethylpyrazol-1-yl)-3-thiapentane (11).
mmol) and hydrogen peroxide (0.1 mL of 50% aqueous solu- Thioether 3 (0.278 g, 1 mmol), sodium acetate (0.328 g,
tion, 1.41 mmol) in methanol (4 mL) were stirred at 60 °C for 6 4 mmol), potassium iodide (1.99 g, 12 mmol) and iodine
h. Subsequently, the reaction mixture was poured into water (20 (1.02 g, 4 mmol) were dissolved in the mixture of water (5 mL)
mL), and the precipitate was filtered, washed with water and and ethanol (2.5 mL) and were allowed to stand overnight at
dried. Yield 0.173 g (79%), colorless crystals, mp 229–230 °C room temperature. The formed precipitate was filtered and thor-
(
DMF); IR (cm−1): 1614, 1593, 1494, 1057 (S=O), 768 (C–S), oughly washed with water and Na2SO3 solution to remove
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48 (Bta); 1Н NMR (DMSO-d6) δ 6.41 (AB q, JAB = 13.7 Hz, traces of unreacted iodine and was then dried. Yield 0.384 g
H, CH2, ΔνAB 0.26 ppm), 7.47 (t, J = 7.5 Hz, 2H, H5 (Bta)), (72%), colorless crystals, mp 96–97 °C (iPrOH). Extraction of
.63 (t, J = 7.5 Hz, 2H, H6 (Bta)), 7.93 (d, J = 8.1 Hz, 2H, H4 the filtrate with chloroform gives additional 0.112 g of product
(
Bta)), 8.12 (d, J = 8.1 Hz, 2H, H7 (Bta)); 13С NMR (DMSO- 11, overall yield 94%; IR (cm−1): 1530, 1438, 1379, 1059 (Pz),
d6) δ 62.8 (CH2), 111.1 (C7 (Bta)), 119.3 (C4 (Bta)), 124.6 (C5 785 (C–S); 1Н NMR (CDCl3) δ 2.19, 2.26 (s, 12Н, СН3), 2.79
Bta)), 128.1 (C6 (Bta)), 133.9 (C8 (Bta)), 145.1 (C9 (Bta)); (t, J = 6.3 Hz, 4Н, PzCH2CH2S), 4.13 (t, J = 6.3 Hz, 4Н,
Anal. calcd for C14H12N6OS: С, 53.83; Н, 3.87; S, 10.27; PzCH2CH2S); 13С NMR (CDCl3) δ 11.9 (5-СН3), 13.9
found: С, 53.75; Н, 4.00; S, 9.86. (3-СН3), 32.0 (PzCH2CH2S), 49.5 (PzCH2CH2S), 62.6 (С4
Pz)), 140.6 (С5 (Pz)), 149.6 (С3 (Pz)); Anal. calcd for
,1'-(Sulfonylbis(methylene))bis(benzotriazole) (9). Thioether C14H20I2N4S: С, 31.71; Н, 3.80; N, 10.57; S, 6.05; found: С,
(
(
1
5
5
(0.457 g, 1.54 mmol) and hydrogen peroxide (0.35 mL of 31.96; Н, 3.90; N, 10.23; S, 6.30.
0% aqueous solution, 6.16 mmol) in acetic acid (5 mL) were
refluxed for 24 h. Then the reaction mixture was poured into 1,8-Bis(4-iodo-3,5-dimethylpyrazol-1-yl)-3,6-dithiaoctane
water (30 mL), and the precipitate was filtered, washed with (12) was prepared similarly to compound 11. Yield 64%, color-
water and dried. Yield 0.303 g (60%), colorless crystals, mp less crystals, mp 133–135 °C (EtOH); IR (cm−1): 1530, 1479,
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04–205 °C (with decomposition); IR (cm−1): 1613, 1592, 1494 1382, 1060 (Pz), 796 (C–S); 1Н NMR (CDCl3) δ 2.19, 2.30 (s,
(
(
(
Bta), 1344, 1146 (O=S=O), 752 (C–S), 747 (Bta); 1Н NMR 12Н, СН3), 2.51 (s, 4H, SCH2CH2S), 2.90 (t, J = 6.9 Hz, 4Н,
DMSO-d6) δ 6.75 (s, 2H, CH2), 7.49 (t, J = 7.5 Hz, 2H, H5 PzCH2CH2S), 4.33 (t, J = 6.9 Hz, 4Н, PzCH2CH2S); 13С NMR
Bta)), 7.66 (t, J = 7.5 Hz, 2H, H6 (Bta)), 7.98 (d, J = 8.1 Hz, (CDCl3) δ 12.0 (5-СН3), 13.8 (3-СН3), 32.0, 32.1 (SCH2CH2S
2
H, H4 (Bta)), 8.15 (d, J = 8.1 Hz, 2H, H7 (Bta)); 13С NMR and PzCH2CH2S), 49.8 (PzCH2CH2S), 62.6 (С4 (Pz)), 140.6
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