Rearrangement of carane derivatives
Russ.Chem.Bull., Int.Ed., Vol. 54, No. 8, August, 2005
1897
(C6D6), δ: 173.26 (C(4)); 54.25 (C(3)); 33.12 (C(2)); 28.26
(C(10)); 22.65 (C(7)); 22.60 (C(9)); 20.33 (C(6)); 18.98 (C(5));
17.48 (C(1)); 14.60 (C(8)); signals for the heptanoic acid resiꢀ
due: 161.26 (C=O); 37.23 (C(1)); 31.66 (C(4)); 28.98 (C(3));
26.10 (C(2)); 18.05 (C(5)); 14.18 (C(6)).
lic acid residue: 2.00 (s, 3 H, H(3)); 1.90 (m, 6 H, H(2)); 1.69
(m, 6 H, H(4)). 13C NMR (CDCl3), δ: 177.14 (C=O); 161.61
(C(4)); 54.03 (C(3)); 34.16 (C(2)); 27.97 (C(10)); 22.20 (C(9));
20.59 (C(6)); 19.30 (C(7)); 17.68 (C(5)); 16.75 (C(11)); 14.18
(C(8)); signals for the adamantyl fragment: 40.89 (C(2´)); 39.21
(C(4´)); 36.38 (C(1´)); 28.04 (C(3´)).
(1S,3S,6R)ꢀ3ꢀ(Nonadecanoylamido)caranꢀ4ꢀone (E)ꢀoxime
(3d). Colorless glassy substance. The yield was 85%; [α]20578 +100
(c 0.70, CHCl3). Highꢀresolution MS, found: m/z 462.41853
(1S,3S,6R)ꢀ3ꢀ(Benzamido)caranꢀ4ꢀone (E)ꢀoxime (3g). Colꢀ
orless crystals with m.p. 124—127 °C (ButOMe), The yield
[M]+. C29H54N2O2. Calculated:
M
=
462.41853. MS,
was 78%; [α]20 +146 (c 0.65, CHCl3). Highꢀresolution MS,
578
m/z (Irel (%)): 462 (5), 447 (12), 165 (4), 150 (20), 148 (100),
132 (10), 130 (12), 123 (15), 106 (3), 100 (15), 57 (12), 43 (55),
42 (11), 41 (26), 29 (9). IR (KBr), ν/cm–1: 3303, 1647. 1H NMR
(CDCl3), δ: 8.85 (s, 1 H, N=O—H); 5.88 (s, 1 H, N—H); 2.86
(dd, 1 H, H(5β), J = 18.6 Hz, J = 1.5 Hz); 2.65 (dd, 1 H, H(2α),
J = 15.1 Hz, J = 9.6 Hz); 2.30 (dd, 1 H, H(5α), J = 18.4 Hz, J =
8.8 Hz); 1.41 (s, 3 H, H(9)); 1.28 (m, 1 H, H(2β)); 1.01 (s, 3 H,
H(10)); 0.84 (ddd, 1 H, H(6); J = 9.2 Hz, J = 8.8 Hz, J =
1.5 Hz); 0.83 (s, 3 H, H(8)); 0.70 (ddd, 1 H, H(1), J = 9.2 Hz,
J = 9.2 Hz, J = 5.7 Hz); signals for the nonadecanoic acid
residue: 1.58 (tt, 2 H, CO—CH2, J = 7.3 Hz, J = 7.3 Hz); 1.24
(m, 32 H, (CH2)16); 0.87 (t, 3 H, CH3, J = 7.1 Hz). 13C NMR
(CDCl3), δ: 172.62 (C(4)); 54.66 (C(3)); 33.52 (C(2)); 28.29
(C(10)); 22.66 (C(7)); 22.60 (C(9)); 20.49 (C(6)); 17.87 (C(5));
17.38 (C(1)); 14.60 (C(8)); signals for the nonadecanoic acid
residue: 161.16 (C=O); 31.96 (C(1)); 29.74 (9 S, CH2); 29.69
(CH2); 29.66 (CH2); 29.48 (CH2); 29.39 (CH2); 29.34 (CH2);
25.96 (CH2); 19.15 (CH2); 14.17 (C(18)).
found: m/z 286.16812 [M]+. C17H22N2O2. Calculated:
M = 286.16812. MS, m/z (Irel (%)): 286 (12), 269 (19), 165 (14),
150 (21), 149 (13), 148 (93), 122 (15), 106 (15), 105 (100),
77 (47), 41 (7). IR (KBr), ν/cm–1: 3323, 3242, 1637. UV,
λ
max/nm (logε): 202 (5.26), 236 (5.01). 1H NMR (CDCl3), δ:
8.93 (s, 1 H, N=O—H); 6.36 (s, 1 H, N—H); 2.95 (d, 1 H,
H(5β), J = 19.5 Hz); 2.65 (dd, 1 H, H(2α), J = 15.0 Hz, J =
10.0 Hz); 2.38 (dd, 1 H, H(5α), J = 19.0 Hz, J = 9.0 Hz); 1.57
(s, 3 H, H(9)); 1.26 (dd, 1 H, H(2β), J = 15.0 Hz, J = 6.0 Hz);
1.00 (s, 3 H, H(10)); 0.92 (dd, 1 H, H(6), J = 9.0 Hz, J =
7.0 Hz); 0.85 (s, 3 H, H(8)); 0.71 (ddd, 1 H, H(1), J = 10.0 Hz,
J = 9.0, J = 6.0 Hz); signals for the benzoic acid residue: 7.38 (t,
2 H, Hmeta); 7.45 (t, 1 H, Hpara); 7.70 (d, 2 H, Hortho). 13C NMR
(C6D6), δ: 166.60 (C(4)); 161.35 (C=O); 54.99 (C(3)); 33.98
(C(2)); 27.90 (C(10)); 22.24 (C(9)); 20.30 (C(6)); 19.35 (C(7));
17.75 (C(5)); 16.78 (C(1)); 14.23(C(8)); signals for the benzoic
acid residue: 135.09 (CO—C); 131.23 (Cpara); 128.41 (2 C,
C
meta); 126.71 (2 C, Cortho).
(1S,3S,6R)ꢀ3ꢀ(2ꢀChloroacetamido)caranꢀ4ꢀone (E)ꢀoxime
(3e). Colorless glassy substance. The yield was 94%; [α]20578 +125
(c 0.64, CHCl3). Highꢀresolution MS, found: m/z 258.11089
(1S,3S,6R)ꢀ3ꢀ(2ꢀThenoylamido)caranꢀ4ꢀone (E)ꢀoxime (3h).
Colorless crystals with m.p. 173—175 °C (ButOMe), The yield
was 65%; [α]20 +184 (c 0.58, CHCl3). Highꢀresolution MS,
578
[M]+. C12H19N2O2Cl. Calculated:
M
=
258.1135. MS,
found m/z 292.1262 [M]+. C14H20N2O2S. Calculated:
M = 292.16149. MS, m/z (Irel (%)): 193 (4), 165 (8), 150 (12),
148 (48), 111 (100), 83 (7), 39 (12). IR (KBr), ν/cm–1: 3323,
3242, 1637. UV, λmax/nm (logε): 201 (4.94). 1H NMR (CDCl3),
δ: 8.77 (s, 1 H, N=O—H); 6.27 (s, 1 H, N—H); 2.93 (dd, 1 H,
H(5β), J = 17.5 Hz, J = 1.5 Hz); 2.74 (dd, 1 H, H(2α), J =
16.0 Hz, J = 10.0 Hz); 2.38 (dd, 1 H, H(5α), J = 17.5 Hz, J =
9.0 Hz); 1.52 (s, 3 H, H(9)); 1.26 (dd, 1 H, H(2β), J = 16.0 Hz,
J = 4.0 Hz); 1.02 (s, 3 H, H(10)); 0.92 (ddd, 1 H, H(6), J =
9.0 Hz, J = 9.0 Hz, J = 1.5 Hz); 0.86 (s, 3 H, H(8)); 0.71 (ddd,
1 H, H(1), J = 10.0 Hz, J = 9.0 Hz, J = 4.0 Hz); signals for the
thiopheneꢀ1ꢀcarboxylic acid residue: 7.35 (dd, 1 H, H(1), J =
5.0 Hz, J = 4.0 Hz); 7.42 (dd, 1 H, H(2), J = 5.0 Hz, J =
1.0 Hz); 7.52 (dd, 1 H, H(3), J = 4.0 Hz, J = 1.0 Hz).
m/z (Irel (%)): 258 (3), 250 (18), 165 (27), 150 (43), 148 (100),
133 (13), 132 (12), 123 (27), 106 (23), 105 (21), 94 (10), 79 (16),
42 (31), 41 (26). 1H NMR (CDCl3), δ: 8.53 (s, 1 H, N=O—H);
6.74 (s, 1 H, N—H); 2.95 (dd, 1 H, H(5β), J = 18.2 Hz, J =
1.3 Hz); 2.55 (dd, 1 H, H(2α), J = 15.0 Hz, J = 9.5 Hz); 2.27
(dd, 1 H, H(5α), J = 18.2 Hz, J = 8.6 Hz); 1.46 (s, 3 H, H(9));
1.35 (dd, 1 H, H(2β), J = 15.1 Hz, J = 5.6 Hz); 1.03 (s, 3 H,
H(10)); 0.92 (ddd, 1 H, H(6), J = 8.6 Hz, J = 8.6 Hz, J =
1.3 Hz); 0.84 (s, 3 H, H(8)); 0.74 (ddd, 1 H, H(1), J = 9.5 Hz,
J = 8.6 Hz, J = 5.6 Hz); signals for the monochloroacetic acid
residue: 3.97 and 3.94 (both d, 1 H each, J = 14.9 Hz). 13C NMR
(CDCl3), δ: 164.84 (C(4)); 160.21 (C=O); 55.01 (C(3)); 34.05
(C(2)); 26.16 (C(10)); 22.01 (C(9)); 20.32 (C(6)); 19.40 (C(7));
17.76 (C(5)); 16.76 (C(1)); 14.52 (C(8)); signals for the
monochloroacetic acid residue: 42.77 (CO—CH2Cl).
(1S,3S,6R)ꢀ3ꢀ(3ꢀPhenylureido)caranꢀ4ꢀone (E)ꢀoxime (3i).
An equimolar amount of phenyl isocyanate (238 mg, 0.217 mL,
2 mmol) was added to a solution of imidazole (136 mg, 2 mmol)
in CH2Cl2 (3 mL) at room temperature. The resulting mixture
was kept for 15 min and added dropwise with stirring to a soluꢀ
tion of amino oxime 4 (364 mg, 2 mmol) in ButOMe (15 mL).
Then the reaction mixture was stirred for 30 min after which
H2O (15 mL) was added. The organic phase was separated and
successively washed with water (2×30 mL), 1 M HCl (5 mL), a
0.5 M aqueous Na2CO3 solution (10 mL), and a saturated aqueꢀ
ous NaCl solution (10 mL) and dried over Na2SO4. The solvent
was removed at ~10 Torr, the residue was dried at ~1 Torr, and
the product was obtained as colorless crystals (90% yield), m.p.
(1S,3S,6R)ꢀ3ꢀ(Adamantaneꢀ1ꢀcarboxamido)caranꢀ4ꢀone
(E)ꢀoxime (3f). Colorless crystals with m.p. 222—225 °C
(ButOMe), The yield was 90%; [α]20 +105 (c 0.77, CHCl3).
578
Highꢀresolution MS, found: m/z 344.24618 [M]+. C20H26N2O2.
Calculated: M = 344.26149. MS, m/z (Irel (%)): 327 (13), 180
(24), 165 (15), 149 (15), 148 (16), 147(100), 135 (77), 106 (11),
93 (17), 78 (23), 67 (11), 55 (9), 41 (11). IR (KBr), ν/cm–1
:
3461, 3341, 1644. 1H NMR (CDCl3), δ: 8.83 (s, 1 H, N=O—H);
5.60 (s, 1 H, N—H); 2.87 (dd, 1 H, H(5β), J = 18.0 Hz, J =
1.5 Hz); 2.74 (dd, 1 H, H(2α), J = 15.0 Hz, J = 10.0 Hz); 2.38
(dd, 1 H, H(5α), J = 18.0 Hz, J = 9.0 Hz); 1.39 (s, 3 H, H(9));
1.29 (dd, 1 H, H(2β), J = 15.0 Hz, J = 5.0 Hz); 1.00 (s, 3 H,
H(10)); 0.92 (ddd, 1 H, H(6), J = 9.0 Hz, J = 5.0 Hz, J =
1.5 Hz); 0.83 (s, 3 H, H(8)); 0.66 (ddd, 1 H, H(1), J = 9.0 Hz,
J = 9.0 Hz, J = 4.0 Hz); signals for the adamantaneꢀ1ꢀcarboxyꢀ
98—101°C (CH3CN), [α]20
+ 149 (c 0.46, CHCl3). Highꢀ
578
resolution MS, found: m/z 301/17883 [M]+. C17H23N3O2. Calꢀ
culated: M = 301.15903. MS, m/z (Irel (%)): 301 (8), 200 (8),
165 (13), 150 (11), 148 (41), 133 (11), 124 (13), 118 (35),