IZMEST’EV et al.
1414
H1'R), 8.76 s (1H, H1'S), 11.50 s (1H, OHR), 11.54 s (1H,
OHS). 13C NMR spectrum, δ, ppm: 13.94 (C10R,S), 19.86
(C9S,8S), 20.09 (C9R,8R), 27.06 (C5S), 27.33 (C5R), 29.45
(C9'S,R,10'S,R,11'S,R), 29.80 (C3R), 31.41 (C13'S,R,14'S,R,15'S,R),
31.95 (C3S), 34.22 (C8'R,S), 35.16 (C12'R,S), 38.95 (C6R),
39.08 (C6S), 44.78 (C4S), 45.05 (C4R), 47.77 (C7S), 47.83
(C7R), 49.78 (C1S), 49.84 (C1R), 75.35 (C2R), 77.32 (C2S),
117.64 (C2'R), 117.92 (C2'S), 127.93 (C7'R,S), 129.45 (C5'S),
129.51 (C5'R), 137.05 (C4'R,S), 141.47 (C6'R,S), 157.19
(C3'S), 157.27 (C3'R), 164.24 (C1'R), 164.98 (C1'S). Found,
%: C 71.91; H 9.45; N 3.31; S 7.63. C25H39NO2S. Cal-
culated, %: C 71.89; H 9.41; N 3.35; S 7.68.
J 13.9, 9.7 Hz), 1.62–1.89 m (5H, H6R,S-exo;3S-exo;5R,S-exo),
1.81–1.94 m (2H, H4R,S), 2.16–2.26 m (1H, H3S-endo),
2.23–2.37 m (1H, H3R-endo), 2.46 d.d (1H, H2S, J 9.3,
6.4 Hz), 2.83 d.d (1H, H2R, J 9.5, 6.1 Hz), 6.94 d (1H,
H4'S, J 8.8 Hz), 6.95 d (1H, H4'R, J 8.8 Hz), 7.54 d.d
(2H, H5'R,S, J 8.8, 2.2 Hz), 7.58 d (2H, H7'R,S, J 2.0 Hz),
8.67 s (2H, H1'R,S), 11.16 s (1H, OHS), 11.18 s (1H,
OHR). 13C NMR spectrum, δ, ppm: 13.84 (C10R,S), 19.80
(C9S,8S), 20.04 (C9R,8R), 27.00 (C5S), 27.26 (C5R), 29.82
(C3R), 31.86 (C3S), 38.89 (C6R), 39.01 (C6S), 44.75 (C4S),
45.02 (C4R), 47.79 (C7S), 47.88 (C7R), 49.87 (C1S,R), 75.18
(C2R), 77.11 (C2S), 111.38 (C2'S,R), 119.26 (C4'R,S), 119.61
(C6'R,S), 135.06 (C7'S,R), 137.15 (C5'S,R), 159.16 (C3'R,S),
162.22 (C1'R), 163.04 (C1'S). Found, %: C 53.15; H 5.73;
N 3.65; S 8.36. C17H22BrNO2S. Calculated, %: C 53.13;
H 5.77; N 3.64; S 8.34.
(R,S)-N-(E)-(2-Hydroxy-5-chlorobenzylidene)-
{(1S,2S,4S)-1,7,7-trimethylbicyclo[2.2.1]heptane}-
2-sulfinamide (XVII), diastereomers mixture.
Yield 99% (de 55%), white powder, Rf 0.42 (petro-
leum ether–Et2O, 10:1). IR spectrum, ν, cm–1: 1599
(C=N), 1273 (Carom–OH), 1182 (C–Cl), 1084 (S=O).
1H NMR spectrum, δ, ppm: 0.95 s (3H, C9RH3), 0.97 s
(3H, C9SH3), 1.09 s (3H, C8RH3), 1.12 s (3H, C8SH3),
1.25 s (3H, C10RH3), 1.28 s (3H, C10SH3), 1.16–1.36 m
(4H, H5R,S-endo;6R,S-endo), 1.52 d.d (1H, H3R-exo, J 13.9,
9.6 Hz), 1.64–1.88 m (5H, H6R,S-эq;3S-exo;5R,S-exo),
1.87–1.94 m (2H, H4R,S), 2.16–2.27 m (1H, H3S-endo),
2.22–2.36 m (1H, H3R-endo), 2.46 d.d (1H, H2S, J 9.2,
6.5 Hz), 2.83 d.d (1H, H2R, J 9.5, 6.1 Hz), 6.99 d (1H, H4'S,
(R,1S,2S,4S,E)-N-(4-Nitrobenzylidene)-1,7,7-
trimethylbicyclo[2.2.1]heptane-2-sulfinamide,
22
(
RS)-XIX. Yellow crystals, mp 132–133°C, [α]D
+77.8° (C 0.26, acetone), Rf 0.45 (CHCl3–EtOAc, 5:1).
IR spectrum, ν, cm–1: 1589 (C=N), 1522 (NO2), 1346
(NO2), 1078 (S=O). 1H NMR spectrum, δ, ppm: 0.94 s
(3H, C9H3), 1.09 s (3H, C8H3), 1.12–1.26 m (1H, H5-
endo), 1.19–1.36 m (1H, H6-endo), 1.28 s (3H, C10H3),
1.48 d.d (1H, H3-exo, J 13.8, 9.7 Hz), 1.64–1.79 m (1H,
H6-exo), 1.71–1.84 m (1H, H5-exo), 1.83–1.93 m (1H,
H4), 2.23–2.36 m (1H, H3-endo), 2.86 d.d (1H, H2, J 9.5,
J 8.7 Hz), 7.00 d (1H, H4'R, J 8.7 Hz), 7.40 d.d (2H, H5'R,S
,
6.1 Hz), 8.04 d (2H, H3',7', J 8.7 Hz), 8.35 d (2H, H4',6'
,
J 8.8, 2.4 Hz), 7.44 d (2H, H7'R,S, J 2.3 Hz), 8.67 s (2H,
H1'R,S), 11.14 s (1H, OHS), 11.15 s (1H, OHR). 13C NMR
spectrum, δ, ppm: 13.84 (C10R,S), 19.80 (C9S,8S), 20.03
(C9R,8R), 27.00 (C5S), 27.25 (C5R), 29.84 (C3R), 31.85
(C3S), 38.89 (C6R), 39.00 (C6S), 44.75 (C4S), 45.02 (C4R),
47.79 (C7S), 47.88 (C7R), 49.86 (C1S,R), 75.18 (C2R), 77.09
(C2S), 118.86 (C4'R,S), 118.98 (C2'S,R), 124.57 (C6'R,S),
132.04 (C7'S,R), 134.35 (C5'S,R), 158.69 (C3'R,S), 162.30
(C1'R), 163.13 (C1'S). Found, %: C 60.10; H 6.49; N 3.10;
S 9.45. C17H22ClNO2S. Calculated, %: C 60.07; H 6.52;
N 4.12; S 9.43.
J 8.7 Hz), 8.70 s (1H, H1'). 13C NMR spectrum, δ, ppm:
14.07 (C10), 20.02 (C9), 20.06 (C8), 27.32 (C5), 29.84
(C3), 38.93 (C6), 45.15 (C4), 47.81 (C7), 49.84 (C1), 74.34
(C2), 124.18 (C4',6'), 130.07 (C3',7'), 139.04 (C5'), 149.79
(C2'), 158.40 (C1'). Found, %: C 61.07; H 6.61; N 8.42;
S 9.54. C17H22N2O3S. Calculated, %: C 61.05; H 6.63;
N 8.38; S 9.59.
(R,S)-(1S,2S,4S,E)-N-(4-Nitrobenzylidene)-1,7,7-
trimethylbicyclo[2.2.1]heptane-2-sulfinamide (XIX),
diastereomers mixture. Yield 85% (de 53%), yellow
crystals, Rf 0.45 (CHCl3–EtOAc, 5:1). IR spectrum, ν,
cm–1: 1589 (C=N), 1522 (NO2), 1345 (NO2), 1079 (S=O).
1H NMR spectrum, δ, ppm: 0.94 s (3H, C9RH3), 0.97 s
(3H, C9SH3), 1.09 s (3H, C8RH3), 1.15 s (3H, C8SH3),
1.12–1.26 m (2H, H5R,S-endo), 1.19–1.36 m (2H, H6R,S-endo),
(R,S)-N-(E)-(2-Hydroxy-5-dibromobenzylidene)-
{(1S,2S,4S)-1,7,7-trimethylbicyclo[2.2.1]heptane}-
2-sulfinamide (XVIII), diastereomers mixture.
Yield 98% (de 52%), white powder, Rf 0.40 (petro-
leum ether–Et2O, 10:1). IR spectrum, ν, cm–1: 1597
(C=N), 1273 (Carom–OH), 1180 (C–Br), 1084 (S=O).
1H NMR spectrum, δ, ppm: 0.95 s (3H, C9RH3), 0.97 s
(3H, C9SH3), 1.10 s (3H, C8RH3), 1.13 s (3H, C8SH3),
1.25 s (3H, C10RH3), 1.28 s (3H, C10SH3), 1.16–
1.28 s (6H, C10R,SH3), 1.48 d.d (1H, H3R-exo
, J 13.8, 9.6 Hz),
1.65–1.88 m (5H, H6R,S-exo;3S-exo;5R,S-exo), 1.82–1.93 m
(2H, H4S,R), 2.23–2.51 m (3H, H2S;3R,S-endo), 2.86 d.d (1H,
H2R, J 9.5, 6.1 Hz), 8.04 d (2H, H3'S,7'S, J 8.8 Hz), 8.05 d
(2H, H4'R,6R', J 8.8 Hz), 8.71 s (1H, H1'R), 8.73 s (1H,
1.36 m (4H, H5R,S-endo;6R,S-endo), 1.52 d.d (1H, H3R-exo
,
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 48 No. 11 2012