Preparation of 8. Asolution of 7 (0.47 g, 2.13 mmol) in EtOH (2.5 mL) and Py (2.5 mL) was treated with NH OH⋅HCl
2
(0.164 g, 2.36 mmol), stirred, left at 24°C for 24 h, poured into water (50 mL), and extracted with Et O (3 × 50 mL). The
2
extract was washed with HCl (5%, 5 × 15 mL), NaHCO solution (2 × 15 mL), and water (2 × 15 mL), and dried. The Et O
3
2
was distilled in vacuo to afford 8 (0.47 g, 95%), which was crystallized by adding hexane. According to TLC, elemental
analysis, and spectral data, the product was a mixture of the Z- and E-isomers of oxime 8.
TLC: Silufol, benzene:ether (3:1), R 0.57 and 0.68. C H NO.
f
15 25
Recrystallization of the product from hexane produced the E-isomer of 8 (0.38 g, 80%), R 0.68, mp 95-96°C.
f
−1
IR spectrum (CCl , ν, cm ): 840, 1690 (>C=C<H), 930 (N–O), 1620 (C=N), 3220 (br.), 3590 (=N–OH).
4
PMR spectrum (δ, ppm, J/Hz): 0.87 (s, 3H, CH -15), 0.91 (s, 6H, CH -13, CH -14), 1.56 (s, 3H, CH -12), 2.64 (d, 1H, J = 8.8,
3
3
3
3
H-9), 5.58 (m, 1H, H-7), 7.31 (d, 1H, J = 9.6, H-11), 8.69 (1H, br.s, =NOH).
13
C NMR spectrum (δ, ppm): 15.79 (C-15), 19.16 (C-2), 22.64 (C-13), 22.83 (C-12), 24.33 (C-6), 33.72 (C-4), 33.89
(C-14), 36.83 (C-10), 40.92 (C-1), 42.89 (C-3), 50.08 (C-5), 56.48 (C-9), 124.43 (C-7), 131.20 (C-8), 154.22 (C-11).
Preparation of 10. A. A solution of 8 (0.46 g, 1.95 mmol) in Py (3.8 mL) and Ac O (1.9 mL, 2.06 g, 20.14 mmol)
2
was heated at 112-116°C for 2 h, cooled in an ice bath, treated with pieces of ice and dropwise with H SO (10%, 15 mL), and
2
4
extracted with Et O (4 × 20 mL). The extract was washed with NaHCO solution (3 × 10 mL) and water (3 × 10 mL), and
2
3
dried. The Et O was distilled. The crystallized solid (0.40 g) was recrystallized from pentane to afford a product (0.27 g, 64%)
2
with mp 87-88°C that was identical to 10 according to spectral data.
TLC: Silufol, benzene:hexane, 1:1, R 0.62. C H N.
f
15 23
−1
IR spectrum (min. oil, ν, cm ): 827, 1671 (>C=C<H), 2228 (CN). PMR spectrum (δ, ppm): 0.87 (s, 3H, CH -13),
3
0.90 (s, 3H, CH -14), 1.05 (s, 3H, CH -15), 1.82 (s, 3H, CH -12), 3.02 (s, 1H, H-9), 5.58 (m, 1H, H-7).
3
3
3
13
C NMR spectrum (δ, ppm): 15.83 (C-15), 19.13 (C-2), 22.11 (C-13), 22.68 (C-12), 23.98 (C-6), 33.44 (C-14),
33.63 (C-4), 36.53 (C-10), 40.63 (C-1), 42.77 (C-3), 48.95 (C-5), 50.66 (C-9), 119.93 (C-11), 125.43 (C-7), 125.65 (C-8).
+
+
+
Mass spectrum (m/z, I , %): 240 (68) [M + Na] , 218 (45) [M + H] , 213 (100) [M + Na - HCN] , 191 (42) [M + H
rel
+
- HCN] .
B. A solution of 8 (0.47 g, 1.99 mmol) and p-TsCl (0.61 g, 3.20 mmol) in Py (5 mL) was refluxed for 1 h, cooled in
an ice bath, treated dropwise with HCl (40 mL, 5%), and extracted with Et O (3 × 50 mL). The extract was washed with
2
NaHCO solution (2 × 15 mL) and water (2 × 15 mL), and dried. The Et O was distilled. The solid (0.47 g) was chromatographed
3
2
over a column of silica gel (9.4 g, 1:20) with elution by hexane:ether (49:1) to afford crystalline 10 (0.39 g, 90%), mp 85-86°C.
Preparation of 2. A solution of LiAlH (100 mg, 2.64 mmol) in anhydrous Et O (2.5 mL) was treated with a solution
4
2
of anhydrous AlCl (0.32 g, 2.40 mmol) in anhydrous Et O (5 mL), stirred for 5 min, treated with a solution of 10 (80 mg,
3
2
0.368 mmol) in anhydrous Et O (1 mL), refluxed and stirred for 2 h, cooled in an ice bath, and treated with several pieces of
2
ice and dropwise with H SO (10%, 5 mL) until acidic. The Et O layer was removed. The aqueous layer was extracted with
2
4
2
Et O (2 × 10 mL), neutralized with NH OH solution (24%, 5 mL), and extracted with ether (5 × 10 mL). The extract was
2
4
washed with water (3 × 5 mL) and dried. The Et O was distilled to afford a product (57 mg) that gave a positive reaction for
2
NH with Dragendorff’s solution and with aqueous ninhydrin (1%). This product was chromatographed over a column of
2
silica gel (1.7 g, 1:30) with elution by CHCl :CH OH (9:1) to afford 2 (41 mg, 50%).
3
3
TLC: Alufol, CHCl :i-PrOH, 9:1, R 0.49.
3
f
−1
IR spectrum (film, ν, cm ): 810 (>C=C<H), 1570, 3300, 3470 (NH ).
2
PMR spectrum (δ, ppm): 0.78 (s, 3H, CH -15), 0.85 (s, 3H, CH -13), 0.87 (s, 3H, CH -14), 1.77 (s, 3H, CH -12),
3
3
3
3
2.00-2.93 [m, 5H, H-9, C(11)2H and NH ].
2
13
C NMR spectrum (δ, ppm): 15.06 (C-15), 19.44 (C-2), 22.65 (C-13), 22.76 (C-12), 24.35 (C-6), 33.63 (C-4), 33.94
(C-14), 37.14 (C-10), 39.61 (C-1), 40.22 (C-11), 42.83 (C-3), 50.61 (C-9), 58.81 (C-5), 124.51 (C-7), 133.93 (C-8).
+
+
+
Mass spectrum (m/z, I , %): 222 (100) [M + H] , 205 (17) [M + H - NH ] , 191 (15) [M + H - CH NH ] , 149 (21),
rel
3
2
3
135 (31), 123 (36), 119 (60), 109 (82).
11-Aminodrim-7-ene Picrate. Yellow crystalline compound, mp 182-183°C (EtOH). C H N O ·1/2C H OH.
21 30
4
7
2 5
Preparation of the Mixture of 11-Aminodrim-7-ene (2) and 11-Amino-7,8-dihydrodrimane (11). A solution of
10 (100 mg, 0.46 mmol) in MeOH (10 mL) was treated with CoCl ⋅6H O (0.68 g, 2.86 mmol), stirred for 5 min, cooled in an
2
2
ice bath, treated in portions over 1 h with NaBH (0.53 g, 14 mmol), stirred for 2 h at 24°C, treated dropwise with HCl (30 mL,
4
3 N), stirred to dissolve Co boride, and extracted with Et O (3 × 10 mL). The extract was washed with water (3 × 3 mL). The
2
369