Synthesis of drimenol and its oxidation with SeO2
Russ.Chem.Bull., Int.Ed., Vol. 53, No. 12, December, 2004 2865
ν/cm–1: 875, 1654 (C=CH), 1060, 3440 (br), 3635 (OH).
1H NMR, δ: 0.83 (s, 3 H, C(15)H3); 0.90 (s, 3 H, C(13)H3);
0.93 (s, 3 H, C(14)H3); 1.76 (s, 3 H, C(12)H3); 3.60, 3.77
(both d, 1 H each, АB system, C(11)H2, J = 11.0 Hz); 5.58 (m,
1 H, C(7)H). 13C NMR, δ: 15.14 (C(15)); 18.50 (C(2)); 20.20
(C(12)); 22.20 (C(13)); 23.47 (C(6)); 31.51 (C(1)); 32.96 (C(4));
33.36 (C(14)); 40.74 (C(10)); 41.64 (C(3)); 42.74 (C(5)); 62.30
(C(11)); 75.45 (C(9)); 127.41 (C(7)); 135.16 (C(8)). The 1H
and 13C NMR spectra were identical to those reported previꢀ
ously.4,14 Found: mol. weight 238.1928 [M]+. C15H26O2. Calcuꢀ
lated: mol. weight 238.1933. MS, m/z (Irel (%)): 238 [M]+ (4),
220 [M – H2O]+ (18), 207 [M – CH2OH]+ (69), 124
[M – C6H10O2]+ (26) (retroꢀDiels—Alder reaction), 123
[M – C6H11O2]+ (49), 114 [C6H10O2]+ (100) (retroꢀDiels—Alder
reaction), 109 [M – C6H10O2 – CH3]+ (93).
References
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The subsequent elution with a hexane—ether mixture
(70 : 30) afforded 10 mg (8%) of 7αꢀethoxydrimꢀ8ꢀenꢀ11ꢀol (12),
m.p. 138—139 °C (from hexane), [α]D20 +87 (c 0.7). IR, ν/cm–1
1670 (>C=C<), 1080, 3420 (br), 3630 (OH). H NMR, δ: 0.86
:
J. M. Ramos, M. S. J. Simmonds, and W. M. Blaney, Tetraꢀ
hedron, 1995, 51, 7435.
1
(s, 3 H, C(15)H3); 0.90 (s, 3 H, C(13)H3); 0.95 (s, 3 H,
C(14)H3); 1.23 (m, 3 H, OCH2CH3, J = 7.0 Hz); 1.84 (s, 3 H,
C(12)H3); 3.35—3.51, 3.60—3.75 (both m, 1 H each, C(12)H2);
3.52 (br.s, 1 H, C(7)H); 4.10 (q, 2 H, OCH2Me, J = 11.5 Hz).
13C NMR, δ: 15.75 (C(15)); 16.96 (OCH2CH3); 18.79 (C(2));
18.82 (C(12)); 21.60 (C(13)); 23.49 (C(1)); 32.82 (C(14)); 32.87
(C(4)); 35.97 (C(1)); 38.83 (C(10)); 41.28 (C(3)); 45.84 (C(5));
58.25 (C(11)); 64.68 (OCH2Me); 77.53 (C(7)); 131.68 (C(8));
145.43 (C(9)). Found: mol. weight. 226.2248 [M]+. C17H30O2.
Calculated: mol. weight. 266.425. MS, m/z (Irel (%)): 266 [M]+
(7), 251 [M – CH3]+ (15), 236 [M – 2 CH3]+ (16), 235
[M – CH2OH]+ (100), 119 [M – CH3 – CH3OH]+ (25), 109
[M – C9H17O2]+ (11).
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G. Bocelli, A. A. Panasenko, and P. F. Vlad, Synthesis,
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Nauk, Ser. Khim., 1997, 896 [Russ. Chem. Bull., 1997, 46,
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Lithgow, P. M. Gomes, P. Basabe, and N. M. Garrido,
Tetrahedron, 1994, 50, 10995.
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The subsequent elution with a hexane—ether mixture
(55 : 45) gave 37 mg (35%) of drimꢀ7ꢀenꢀ11,12ꢀdiol (11), m.p.
20
69.5—70 °C (from hexane), [α]D –7.5° (c 2.0) (cf. Ref. 15:
22
m.p. 69.5—70.5 °C (from hexane), [α]D –6.3°). IR, ν/cm–1
:
1
815, 1655, 3045 (C=CH), 1025, 3300 (br, OH). H NMR, δ:
0.76 (s, 3 H, C(10)H3); 0.87, 0.88 (both s, 2×3 H, C(4)Me2);
2.95 (s, 2 H, 2 OH); 3.67 (dd, 1 H, C(11)H, J = 8.3 Hz, J =
10.8 Hz); 3.91 (dd, 1 H, C(11)H, J = 1.8 Hz, J = 10.8 Hz); 3.97,
4.35 (both d, 2 H each, АВꢀsystem, C(12)H2, J = 12.0 Hz); 5.80
(m, 1 H, C(7)H). 13C NMR, δ: 14.53 (C(15)); 18.79 (C(2));
21.91 (C(13)); 23.56 (C(6)); 32.97 (C(4)); 33.18 (C(14)); 35.60
(C(10)); 39.32 (C(1)); 42.00 (C(3)); 49.38 (C(5)); 54.44 (C(9));
61.48 (C(11)); 67.50 (C(12)); 127.49 (C(7)); 136.92 (C(8)). The
1H and 13C NMR spectra are in good agreement with those
published previously.15—17 Found: mol. weight 238.1934 [M]+.
C15H26O2. Calculated: mol. weight 238.1933. MS, m/z (Irel (%)):
238 [M]+ (5), 220 [M – H2O]+ (6), 207 [M – CH2OH]+ (13),
124 [M – C6H10O2]+ (29) (retroꢀDiels—Alder reaction), 109
[M – C6H10O2 – Me]+ (100).
Received April 22, 2004;
in revised form September 6, 2004