NEW DERIVATIVES OF 2O-HYDROXYECDYZONE
679
1.20 s (6H, H3C26 and H3C27), 1.26 s (3H, CH3C1' ),
1.302.15 m (18H, CH2), 2.252.40 m (2H, HC5 and
HC17), 3.15 m (1H, HC9, w1/2 25), 3.70 m (1H, HC22,
w1/2 17), 3.85 m (1H, HC2, w1/2 22), 3.96 m (1H, HC3,
w1/2 12), 5.81 d (1H, HC7, 3J 2.0). 13C NMR spectrum
CHCl3MeOH, 20:1. We obtained 0.47 g (40%) of
compound X, Rf 0.4 (CHCl3 MeOH, 7:1), and 0.80 g
(60%) of compound XV, Rf 0.6 (CHCl3-MeOH, 7:1).
Compound (X). mp 148150°C, [a]D15 32.1° (C 2.1,
1
MeOH). IR spectrum (KBr), cm : 3400, 1655. UV
(CD3OD), d
, ppm*: 9.6 q (CH3CH2C1' ), 17.7 q (C18),
1
spectrum, lmax, nm: 242. H NMR spectrum (C5D5N),
21.5 t (C11), 22.2 t (C16), 23.0 q (C21), 24.2 q (C19),
24.5 q (CH3C1' ), 24.7 t (C23), 29.1 q and 29.5 q (C26 and
C27), 31.7 t (C15), 32.3 t (C12), 32.8 t (C4), 35.1 d (C9),
36.1 t (CH2C1'), 37.4 t (C1), 39.2 s (C10), 42.2 t (C24),
50.6 d (C17), 51.7 d (C5), 68.5 d (C3), 68.6 d (C2), 71.1 s
(C25), 83.0 d (C22), 85.3 s (C14), 85.4 s (C20), 109.9 s
(C1' ), 122.1 d (C7), 167.6 s (C8), 206.4 s (C6). Found, %:
C 69.84; H 9.60. C31H50O7. Calculated, %: C 69.63;
H 9.42.
d
, ppm (J, Hz): 0.90 s (3H, H3C18), 1.05 s (3H, H3C19),
1.35 s (9H, H3C21, H3C26 and H3C27), 1.54 s (3H, CH3C1' ),
2.33 s (3H, CH3CO), 1.602.50 m (18H, CH2), 2.73 m
(1H, HC17, w1/2 17), 3.00 m (1H, HC5, w1/2 25), 3.57 m
(1H, HC9, w1/2 29), 3.93 d.d (1H, HC22, 3J 9.0 and 2.0),
4.154.25 m (2H, HC2 and HC3), 6.23 br.s (1H, HC7,
w1/2 10). 13C NMR spectrum (C5D5N), d, ppm: 17.0 q
(C18), 20.7 t (C11), 21.8 t (C16), 22.0 q (C21), 23.9 t (C23),
24.2 q (C19), 25.2 q (CH3C1' ), 29.5 q and 29.7 q (C26 and
C27), 31.3 t (C15), 31.4 t (C12), 31.6 q (CH3CO), 32.2 t
(C4), 34.1 d (C9), 37.6 t (C1), 38.4 s (C10), 41.6 t (C24),
47.5 s (C13), 49.6 d (C17), 51.1 d (C5), 56.4 t (CH2CO),
67.8 d (C3), 67.9 d (C2), 69.0 s (C25), 82.0 d (C22), 83.8 s
(C14), 85.3 s (C20), 106.0 s (C1' ), 121.5 d (C7), 165.3 s
(C8), 203.4 s (C6), 205.8 s (MeCO). Found, %: C 68.53;
H 9.00. C32H50O8. Calculated, %: C 68.30; H 8.96.
Compound (XIV). mp 128131°C, [a]D25 35.0° (C
1
3.8, CHCl3). IR spectrum (KBr), n, cm : 3400, 1655.
UV spectrum, lmax, nm: 242. 1H NMR spectrum
(CDCl3), d
, ppm (J, Hz): 0.77 s (3H, H3C18), 0.890.91
m (9H, H3C19, CH3CH2C1' and CH3CH2C1'' ), 1.12 s (3H,
H3C21), 1.20 s and 1.21 s (6H, H3C26 and H3C27), 1.25 s
(3H, CH3C1' ), 1.40 s (3H, CH3C1'' ), 1.451.85 m (20H,
CH2), 2.102.40 m (2H, HC5 and HC17), 2.77 m (1H,
HC9, w1/2 35), 3.62 m (1H, HC22, w1/2 15), 4.144.25 m
(2H, HC2 and HC3), 5.73 d (1H, HC7, 4J 2.0). 13C NMR
Compound (XV). mp 153155°C, [a]D15 18.8°
1
(C 1.7, CHCl3). IR spectrum (KBr), n, cm : 3400, 1655.
UV spectrum, lmax, nm: 243. 1H NMR spectrum
spectrum (CDCl3), d
, ppm: 8.9 q and 9.0 q (CH3CH2C1'
(CDCl3), d
, ppm (J, Hz): 0.76 s (3H, H3C18), 0.94 s (3H,
and CH3CH2C1'' ), 16.9 q (C18), 20.4 t (C11), 21.1 t (C16),
22.1 q (C21), 23.5 q and 23.6 q (CH3C1' and CH3C1''),
25.2 q (C19), 26.6 t (C23), 28.9 q and 29.7 q (C26 and
C27), 30.9 t (C15), 31.4 t (C12), 32.3 t (C4), 34.4 d (C9),
34.9 t and 35.6 t (C1), 37.6 t (MeCH2C1' and MeCH2
C1'' ), 37.7 s (C10), 41.3 t (C24), 47.4 s (C13), 49.1 d (C17),
50.6 d and 50.7 d (C5), 70.2 C (C25), 71.1 d, 71.6 d and
72.0 d (C2 and C3), 81.6 d (C22), 84.0 s (C20), 84.7 s
(C14), 108.8 s (C1' ), 110.1 s and 110.4 s (C1'' ), 121.2 d
(C7), 163.6 s (C8), 202.9 s (C6). Found, %: C 71.66;
H 9.71. C35H56O7. Calculated, %: C 71.39; H 9.59.
H3C19), 1.19 s and 1.20 s (9H, H3C21, H3C26 and H3C27),
1.32 s (3H, CH3C1'' ), 1.48 s (3H, CH3C1' ), 2.15 s and
2.18 s (6H, CH3CO), 1.402.40 m (20H, CH2), 2.65
2.82 m (3H, HC5, HC9 and HC17), 3.63 m (1H, HC22, w1/2
17), 4.25 m (2H, HC2 and HC3, w1/2 9), 5.77 br.s (1H,
HC7, w1/2 5). 13C NMR spectrum (CDCl3),
d, ppm: 17.0 q
(C18), 20.4 t (C11), 21.1 t (C16), 23.2 t (C23), 23.4 q (C21),
24.5 q (C19), 25.0 q (CH3C1' ), 26.2 t (C4), 26.9 q (CH3C1'' ),
29.2 q and 29.4 q (C26 and C27), 30.8 t (C15), 31.2 t (C12),
31.6 q and 31.8 q (CH3COCH2C1' and CH3COCH2C1'' ),
34.2 d and 34.3 d (C9), 37.4 t (C1), 37.6 s and 37.7 s
(C10), 41.0 t (C24), 47.3 s and 47.4 s (C13), 48.8 d (C17),
50.5 d and 50.8 d (C5), 53.2 t and 55.3 t (OCCH2C1'' ),
56.3 t (OCCH2C1' ), 70.3 s (C25), 71.3 d, 71.9 d, 72.0 d
and 72.3 d (C2 and C3), 81.6 d (C22), 84.4 s (C14), 84.9 s
(C20), 105.9 s (C1' ), 107.0 s and 107.2 s (C1'' ), 121.1 d
(C7), 163.4 s (C8), 202.6 s (C6), 205.8 s and 206.1 s
(OCC1'' ), 206.5 s (OCC1' ). Found, %: C 69.10; H 8.89.
C37H56O9. Calculated, %: C 68.92; H 8.75.
20,22-O-[(2R)-4-Oxopentan-2-ylidene]-20-
hydroxyecdyzone (X) and 2,3-O-[(2RS)-4-oxo-
pentan-2-ylidene]-20,22-O-[(2R)-4-oxopentan-2-
ylidene]-20-hydroxyecdyzone (XV). A suspension of
1.0 g (2.08 mmol) of compound I, 4.0 mg of PMA. and
10 ml of acetylacetone V was stirred at ~25°C till
homogenization of the reaction mixture (~50 min) that
was then charged on a column with 100 g of SiO2 and
washed with CHCl3 to complete removal of acetyl-
acetone. Then elution was performed with a mixture
20,22-O-[(1'R)-Furfurylidene]-20-hydroxyecdy-
zone (XI) and 2,3-O-[(1'RS)-furfurylidene]-20,22-O-
[(1'R)-furfurylidene]-20-hydroxyecdyzone (XVI). A
suspension of 1.0 g (2.08 mmol) of compound I, 4.0 mg
* The signal of C13 atom in the 13C NMR spectrum of compound IX
is overlapped with the multiplet of the solvent (d 49 ppm).
RUSSIAN JOURNALOF ORGANIC CHEMISTRY Vol. 40 No. 5 2004