0
.87 (6H, d, J = 6.5, 26-Me, 27-Me), 0.89 (3H, s, 19-Me), 0.96 (3H, d, J = 6, 21-Me), 2.05 (3H, s, AcO), 2.47 (1H, dd, J = 12,
1
J = 3.5, H-5α), 2.60 (1H, dd, J = 13, J = 4.5, H-1β), 4.22 (1H, ddd, J = 14, J = 12, J = 4, H-2β), 4.92 (1H, td, J = 11.5,
2
1
2
1
2
3
1
J2 = 5, H-3α), 5.68 (1H, br.t, J = 2, H-7).
Elution by petroleum ether:ethylacetate (3:1) isolated the target 2β,3β-diacetoxy-5α-cholest-7-en-6-one (12, 0.440 g,
-1
5
1
5% calculated for pure 7), mp 180-184°C, lit. [12] mp 213-216°C. UV spectrum (λmax, nm): 245. IRspectrum ( , cm ): 1750,
250 (AcO), 1680 (C O), 1630 (C C). PMR spectrum (CD Cl , δ, ppm, J/Hz): 0.60 (3H, s, 18-Me), 0.88 (6H, d, J = 6.5, 26-
2
2
Me, 27-Me), 0.94 (3H, d, J = 6, 21-Me), 0.99 (3H, s, 19-Me), 2.00 (3H, s, AcO), 2.05 (3H, s, AcO), 2.40 (1H, dd, J = 12,
1
J = 3.5, H-5α), 4.81 (1H, ddd, J = 12, J = 5, J = 3.5, H-3α), 5.27 (1H, br.d, J = 2.5, H-2 ), 5.70 (1H, br.t, J = 2, H-7).
2
1
2
3
2
β,3β-Diacetoxy-14α-hydroxy-5α-cholest-7-en-6-one (13). A solution of 11 (0.39 g) in dioxane (5 mL) was treated
with a boiling solution of SeO (0.30 g) in dioxane (8 mL). The mixture was held at 81-85°C for 35 min, cooled to room
2
temperature, and filtered through a layer of silica gel. The filtrate was evaporated in vacuo. The solid was chromatographed
over a silica-gel column with elution by petroleum ether:ethylacetate of increasing polarity (from 5:1 to 3:1) to give 13
(
0.36 g, 89%), mp 221-223°C, lit. [8] mp 230-232°C. UV spectrum (λmax, nm): 242. PMR spectrum (CD Cl , δ, ppm, J/Hz):
2 2
0
2
.70 (3H, s, 18-Me), 0.88 (6H, d, J = 6.5, 26-Me, 27-Me), 0.92 (3H, d, J = 6, 21-Me), 1.00 (3H, s, 19-Me), 1.98 (3H, s, AcO),
.04 (3H, s, AcO), 2.42 (1H, dd, J = 12, J = 3.5, H-5α), 2.72 (1H, m, W/2 = 22, H-9α), 4.81 (1H, ddd, J = 12, J = 5,
1
2
1
2
J3 = 3.5, H-3α), 5.26 (1H, br.d, J = 2.5, H-2α), 5.89 (1H, d, J = 2.5, H-7).
Hydrolysis of 2β,3β-Diacetoxy-14α-hydroxy-5α-cholest-7-en-6-one (13). A solution of 13 (0.30 g) in MeOH
25 mL) at 50°C was treated with K CO (0.30 g) in aqueous MeOH (4 mL, 1:1). The reaction mixture was held at 45-50°C
(
2
3
for 25 min, cooled to room temperature, and diluted with water. The precipitate was filtered off. The mother liquor was
extracted with ethylacetate. The organic layer was washed with water and evaporated in vacuo. The solid was combined with
the previously obtained product and chromatographed over a silica-gel column with elution by CHCl :CH OH of increasing
3
3
polarity (from 20:1 to 15:1) to give 5 -22,25-dideoxyecdysone (1a, 0.092 g, 36%), mp 231-233°C (CHCl ), lit. [8] mp 245-
3
2
49°C (CH OH). UV spectrum (λ , nm): 242. PMR spectrum (C D N, δ, ppm, J/Hz): 0.72 (3H, s, 18-Me), 0.88 (6H, d,
3 5 5
max
J = 6.5, 26-Me, 27-Me), 1.04 (3H, d, J = 6.5, 21-Me), 1.42 (3H, s, 19-Me), 3.03 (1H, m, W/2 = 24, H-9α), 3.90 (1H, m,
W/2 = 17, H-3α), 4.40 (1H, m, W/2 = 11, H-2α), 6.24 (1H, d, J = 2.5, H-7).
Continued elution by CHCl :CH OH (12:1, 10:1) isolated 22,25-dideoxyecdysone (1, 0.101 g, 40%), mp 206-208°C
3
3
(
ethylacetate), lit. [8] mp 208-210°C. UV spectrum (λmax, nm): 243. PMR spectrum (C D N, δ, ppm, J/Hz): 0.75 (3H, s, 18-
5 5
Me), 0.88 (6H, d, J = 6.5, 26-Me, 27-Me), 1.02 (3H, d, J = 6.5, 21-Me), 1.06 (3H, s, 19-Me), 3.04 (1H, br.d, J = 13, H-5β), 3.59
1H, m, W/2 = 24, H-9α), 4.20 (1H, br.d, J = 12, H-3α), 4.28 (1H, m, W/2 = 11, H-2α), 6.25 (1H, d, J = 2.5, H-7).
(
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.
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343