ASYMMETRIC SYNTHESIS OF NEW OPTICALLY ACTIVE SULFINAMIDES
191
(S,1S,2S,5R)-N-(3,5-Di-tert-butyl-2-hydroxy-
benzyl)-2-isopropyl-5-methylcyclohexanesulfinamide
(XVII). Colorless oily fluid, [α]D22 +46.0° (с 0.20, CHCl3).
Yield 0.31 g (75%), Rf 0.53 (EtOAc–petroleum ether,
1:6). IR spectrum, ν, cm–1: 3280 (NH, OH), 2928, 1740,
1486, 1460, 1366, 1204, 1128, 1038 (S=O), 884 (S–N).
1Н NMR spectrum (CDCl3), δ, ppm: 0.93 d (3H, С7H3,
J 6.4 Hz), 0.97–1.12 m (1H, H4a), 0.98 d (3H, С10H3,
J 6.6 Hz), 1.11 d (3H, С9H3, J 6.4 Hz), 1.21–1.33 m (1H,
H6a), 1.33 s (9H, C13'H3, C14'H3, C15'H3), 1.32–1.43 m
(1H, H2), 1.46 s (9H, С9'H3, С10'H3, С11'H3), 1.61 q.d
(1H, H3a, J 12.9, J 3.4 Hz), 1.62–1.73 m (1H, H5), 1.89–
2.15 m (3H, H3e,4e,8), 2.19 d.d.t (1H, H6e, J 14.0, J 2.3,
J 1.9 Hz), 3.40–3.44 m (1H, H1), 3.99 br.d (1H, NH,
J 7.7 Hz), 4.12 d.d (1H, H1a', J 13.2, J 1.9 Hz), 4.52 d.d
(1H, H1b', J 13.2, J 7.7 Hz), 7.06 (1H, H7', J 2.3 Hz), 7.36 d
(1H, H5', J 2.3 Hz), 8.13 s (1H, OH). 13C NMR spectrum,
δ, ppm: 21.83 (C9), 22.03 (C10), 22.56 (C7), 26.23 (C3),
27.95 (C5), 29.37 (C8), 29.79 (С9',10',11'), 31.62 (С13',14',15'),
34.23 (C12'), 35.22 (C8'), 35.56 (C4), 38.62 (C6), 41.75
(C1'), 48.88 (C2), 62.79 (C1), 123.40 (C2'), 124.68 (C7'),
124.97 (C5'), 138.01 (C4'), 141.85 (C6'), 152.17 (C3').
Found, %: С 71.19; H 10.25; N 3.39; S 7.54. C25H43NO2S.
Calculated, %: С 71.21; H 10.28; N 3.32; S 7.60.
isopropyl-5-methylcyclohexanesulfinamide (XIX).
Yellowish powder, mp 101.3°С, [α]D +72.6° (с 0.22,
22
CHCl3). Yield 0.22 g (40%), Rf 0.34 (EtOAc–hexane,
1:2). IR spectrum, ν, cm–1: 3246 (NH, OH), 2949,
1440, 1357, 1286, 1224, 1034 (S=O), 997, 864 (S–N).
1Н NMR spectrum, δ, ppm: 0.71 d (3H, С7H3, J 6.4 Hz),
0.76–0.89 m (1H, H4a), 0.78 d (3H, С10H3, J 6.6 Hz),
0.90 d (3H, С9H3, J 6.5 Hz), 1.08 t.d (1H, H6a, J 12.9,
J 3.3 Hz), 1.21 d.d.t (1H, H2, J 12.5, J 10.2, J 2.5 Hz),
1.40 q.d (1H, H3a, J 12.9, J 3.3 Hz), 1.38–1.52 m (1H,
H5), 1.68–1.89 m (3H, H3e,4e,8), 1.93 d.d.t (1H, H6e,
J 14.6, J 2.6, J 2.3 Hz), 3.21–3.26 m (1H, H1), 3.87 d.d
(1H, H1a', J 14.2, J 1.8 Hz), 4.21 d.d (1H, H1b', J 14.2,
J 7.6 Hz), 5.69 br.d (1H, NH, J 7.6 Hz), 7.32 d (1H, H7',
J 2.1 Hz), 7.82 (1H, H5', J 2.1 Hz), 9.83 s (1H, OH).
13C NMR spectrum, δ, ppm: 21.74 (C9), 21.91 (C10),
22.52 (C7), 26.05 (C3), 27.61 (C5), 29.27 (C8), 35.39
(C4), 38.53 (C6), 40.02 (C1'), 48.40 (C2), 61.85 (C1),
81.68 (C4'), 89.23 (C6'), 127.43 (C2'), 139.54 (C7'), 146.24
(C5'), 158.80 (C3'). Found, %: С 36.35; H 4.41; N 2.67;
S 5.73. C17H25I2NO2S. Calculated, %: С 36.38; H 4.49;
N 2.50; S 5.71.
(S,1S,2S,5R)-N-(4-Nitrobenzyl)-2-isopropyl-5-
methylcyclohexanesulfinamide (XX). Yellow powder,
mp 92.7°С, [α]D22 +34.4° (с 0.45, CHCl3). Yield 0.32 g
(94%), Rf 0.45 (EtOAc). IR spectrum, ν, cm–1: 3177 (NH),
2949, 1603, 1517 (NO2), 1344 (NO2), 1036 (S=O), 853
(S–N). 1Н NMR spectrum, δ, ppm: 0.87 d (3H, С7H3,
J 6.5 Hz), 0.91–1.02 m (1H, H4a), 0.92 d (3H, С10H3,
J 6.6 Hz), 1.04 d (3H, С9H3, J 6.4 Hz), 1.19–1.29 m
(1H, H6a), 1.35 d.d.t (1H, H2, J 12.5, J 9.8, J 2.7 Hz),
1.56 q.d (1H, H3a, J 13.0, J 3.5 Hz), 1.56–1.66 m (1H,
H5), 1.79–2.07 m (3H, H3e,4e,8), 2.23 d.d.t (1H, H6e, J 13.8,
J 2.5, J 2.2 Hz), 3.26–3.30 m (1H, H1), 4.35–4.45 m (3H,
H1a',1b', NH), 7.55 d (2H, H3',7', J 8.5 Hz), 8.21 d (2H,
H4',6', J 8.5 Hz). 13C NMR spectrum, δ, ppm: 21.88 (C9),
21.96 (C10), 22.56 (C7), 26.13 (C3), 27.96 (C5), 29.10 (C8),
35.47 (C4), 38.13 (C6), 46.24 (C1'), 49.11 (C2), 63.49 (C1),
123.84 (C4',6'), 128.82 (C3',7'), 146.16 (C2'), 147.50 (C5').
Found, %: С 60.29; H 7.77; N 8.33; S 9.51. C17H26N2O3S.
Calculated, %: С 60.33; H 7.74; N 8.28; S 9.47.
(S,1S,2S,5R)-N-(3,5-Dibromo-2-hydroxybenzyl)-2-
isopropyl-5-methylcyclohexanesulfinamide (XVIII).
22
Yellowish powder, mp 98.4°С, [α]D +67.3° (с 0.30,
CHCl3). Yield 0.33 g (72%), Rf 0.33 (ССl4–EtOAc,
2:1). IR spectrum, ν, cm–1: 3280 (NH, OH), 2929, 1742,
1490, 1455, 1334, 1206, 1132, 1038 (S=O), 854 (S–N).
1Н NMR spectrum, δ, ppm: 0.90 d (3H, С7H3, J 6.4 Hz),
0.95–1.08 m (1H, H4a), 0.96 d (3H, С10H3, J 6.6 Hz),
1.07 d (3H, С9H3, J 6.3 Hz), 1.28 t.d (1H, H6a, J 13.2,
J 3.5 Hz), 1.39 d.d.t (1H, H2, J 12.7, J 10.1, J 3.0 Hz),
1.57 q.d (1H, H3a, J 12.9, J 3.3 Hz), 1.55–1.68 m (1H, H5),
1.83–2.06m (3H, H3e,4e,8), 2.13 d.d.t (1H, H6e, J 14.7, J 2.7,
J 2.3 Hz), 3.37–3.41 m (1H, H1), 4.11 d.d (1H, H1a', J 14.0,
J 1.9 Hz), 4.25 br.d (1H, NH, J 7.4 Hz), 4.44 d.d (1H,
H1b', J 14.0, J 7.4 Hz), 7.29 d (1H, H7', J 2.4 Hz), 7.64 d
(1H, H5', J 2.4 Hz), 8.91s (1H, OH). 13C NMR spec-
trum, δ, ppm: 21.84 (C9), 21.97 (C10), 22.57 (C7), 26.18
(C3), 27.90 (C5), 29.32 (C8), 35.53 (C4), 38.54 (C6),
40.65 (C1'), 48.77 (C2), 62.65 (C1), 111.14 (C4'), 113.54
(C6'), 127.27 (C2'), 132.19 (C7'), 135.25 (C5'), 151.42
(C3'). Found, %: С 44.01; H 5.36; N 2.82; S 6.83.
C17H25Br2NO2S. Calculated, %: С 43.70; H 5.39; N 3.00;
S 6.86.
(S,1S,2S,5R)-N-[4-(Dimethylamino)benzyl]-2-
isopropyl-5-methylcyclohexanesulfinamide (XXI). Yel-
22
lowish powder, mp 84.3°С, [α]D +49.1° (с 0.27, CHCl3).
Yield 0.30 g (88%), Rf 0.48 (EtOAc). IR spectrum, ν, cm–
1: 3184 (NH), 2951, 1614, 1524, 1450, 1348, 1049 (S=O),
1
947 (S–N), 810, 754. Н NMR spectrum, δ, ppm: 0.90 d
(S,1S,2S,5R)-N-(2-Hydroxy-3,5-diiodobenzyl)-2-
(3H, С7H3, J 6.4 Hz), 0.95–1.08 m (1H, H4a), 0.96 d (3H,
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 48 No. 2 2012