Ozonolysis of dipterocarpol and its derivatives

Article abstract of DOI:10.1134/S1070428012100193

Oxidation of dipterocarpol and its derivatives with ozone gave compounds containing lactone, lactol, alkoxytetrahydrofuran, aldehyde, and methyl ketone fragments in the side chain, as well as 1,2,4-trioxolane fragment in the A ring. The molecular and crystalline structures of dipterocarpol were determined by X-ray analysis. Pleiades Publishing, Ltd., 2012.

Full text of DOI:10.1134/S1070428012100193

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2012, Vol. 48, No. 10, pp. 1370–1376. © Pleiades Publishing, Ltd., 2012.
Original Russian Text © I.E. Smirnova, Kh. Do Tkhi Tkhu, O.B. Kazakova, G.A. Tolstikov, O.S. Kukovinets, A.N. Lobov, K.Yu. Suponitskii, 2012, published
in Zhurnal Organicheskoi Khimii, 2012, Vol. 48, No. 10, pp. 1374–1379.
Ozonolysis of Dipterocarpol and Its Derivatives
I. E. Smirnovaa, H. Do Thi Thub, O. B. Kazakovaa, G. A. Tolstikova, O. S. Kukovinetsa,
A. N. Lobova, and K. Yu. Suponitskiic
a Institute of Organic Chemistry, Ufa Research Center, Russian Academy of Sciences,
pr. Oktyabrya 71, Ufa, 450054 Bashkortostan, Russia
e-mail: obf@anrb.ru
b Institute of Chemistry, Vietnam Academy of Sciences and Technologies, Hanoi, Vietnam
c Nesmeyanov Institute of Organometallic Compounds, Russian Academy of Sciences,
ul. Vavilova 28, Moscow, 119991 Russia
Received February 8, 2012
Abstract—Oxidation of dipterocarpol and its derivatives with ozone gave compounds containing lactone,
lactol, alkoxytetrahydrofuran, aldehyde, and methyl ketone fragments in the side chain, as well as 1,2,4-trioxo-
lane fragment in the A ring. The molecular and crystalline structures of dipterocarpol were determined by X-ray
analysis.
DOI: 10.1134/S1070428012100193
formation and are fused trans with respect to each
other. The cyclopentane fragment has envelope con-
formation with the C14 atom deviating by 0.657(4) Å.
Molecules I in crystal are linked to form chains
through O2–H···O1′ hydrogen bonds [H···O 2.27,
O···O 3.070(4) Å, ∠OHO 156°].
Ozonolysis of dipterocarpol (I) was carried out in
methylene chloride, acetone, and alcohols at –40°C
without subsequent reduction of peroxide interme-
diates (Scheme 1). By reaction of I with 1 equiv of
ozone in CH2Cl2 we obtained lactol II. Compound II is
likely to be formed via ozonolysis of the C24=C25 bond
in I, followed by facile cyclization of intermediate
aldehyde A with participation of the 20-OH group
(Scheme 2).
Dammarane triterpenoid dipterocarpol [I, (20S)-20-
hydroxydammar-24-en-3-one] and its derivatives ex-
hibit various kinds of biological activity, in particular
anticancer [1], antiviral [2–6], immunosuppressive [7],
and anti-inflammatory [8]. Some transformations of
dipterocarpol were reported. For example, polymeric
derivatives of N-vinylpyrrolidone with dipterocarpol,
as well as with γ-lactone obtained by oxidation of
dipterocarpol with CrO3 in AcOH, were synthesized
[9–11]. Taking into account prospects in using dam-
marane triterpenoids in pharmacology as analogs of
ginseng root and birch leaves metabolites [12–14] and
accessibility of dipterocarpol as starting material, we
have initiated studies on its chemical transformations.
The present article reports on the oxidation of diptero-
carpol and its derivatives with ozone in protic and
aprotic solvents without reduction of peroxide inter-
mediates. As source of dipterocarpol (I) we used resin
isolated from the Vietnam tree Dipterocarpus alatus
(yield 37%).
The reaction of I with 2 equiv of ozone in CH2Cl2
gave a mixture of lactol II and lactone III which were
isolated by column chromatography in 20 and 68%
yield, respectively. Compounds II and III characteris-
tically displayed in the 13C NMR spectra signals from
C20 and C24 at δC 87.6 (89.9) and 99.7 (176.6) ppm,
Complete assignment of proton and carbon signals
in the NMR spectra of dipterocarpol (I) was per-
formed, and its molecular and crystalline structures
were determined by X-ray analysis (see figure). Rogers
[15] previously succeeded in determining only the
symmetry point group and unit cell parameters. The
six-membered rings in molecule I adopt chair con-
1
respectively. The H NMR spectrum of II contained
a broadened signal at δ 4.51 ppm from the 24-OH
proton. The reaction of I with 2 equiv of O3 in acetone
afforded 87% of III. The latter was also formed in
quantitative yield by oxidation of pure lactol II with
1 equiv of ozone in methylene chloride or acetone.
1370

OZONOLYSIS OF DIPTEROCARPOL AND ITS DERIVATIVES
1371
Scheme 1.
Me
20
24
O
OH
i
i or iii
Me
Me
III, 97%
Me
O
O
O
Me Me
II, 75%
Me
HO
21Me
22
24
20
26
Me
12
17
13
14
O
O
23
11
18
19Me 19 Me
Me
Me
25
ii, iii
27Me
16
+
II, 20% (ii)
15
1
4
9
2
3
10
8
7
Me30
Me
5
6
O
29
28
Me Me
Me Me
I
III, 68% (ii), 95% (iii)
Me
O
OR
iv
Me
Me
+
III
Me
Me Me
IV–VI
i: O3 (1 equiv), CH2Cl2, –40°C; ii: O3 (2 equiv), CH2Cl2, –40°C; iii: O3 (2 equiv), Me2CO, –40°C; iv: O3 (2 equiv), MeOH (or EtOH,
or i-PrOH), –40°C; IV, R = Me; V, R = Et; VI, R = i-Pr.
Ozonolysis of dipterocarpol (I) in methyl, ethyl, or
isopropyl alcohol led to the corresponding alkoxytetra-
hydrofuran derivatives IV–VI. In all cases, the prod-
ucts were 1 :1 mixtures of diastereoisomers at C24;
attempts to separate them completely by column chro-
matography or fractional crystallization were unsuc-
cessful. The structure of IV–VI was confirmed by their
13C NMR spectra which contained a signal at
δC 103.1–108.1 ppm from the C24 atom. In the 1H NMR
spectrum of IV, the OCH3 protons resonated as two
singlets at δ 3.33 and 3.34 ppm; compound V dis-
played multiplets at δ 3.33–3.80 ppm from the OCH2
protons, and the OCH(CH3)2 proton in VI gave rise to
multiplet signals at δ 3.78 and 4.01 ppm. In all cases,
the reactions were accompanied by formation of
a small amount of lactone III.
by the action of alcohol according to nucleophilic sub-
stitution mechanism and subsequent cyclization. Anal-
ogous transformations were reported in [16] for other
substrates.
C26
C27
C25
C23
C21
C24
C22
C12
C17
C20
C11
C13
O2
C16
C15
C30
C1
C9
C2
C14
C10
C19
C6
O1
C8
C3
C18
C5
C7
C4
C28
Presumably, ozonolysis of I in alcohols involves
reaction of intermediate aldehyde A (Scheme 2) with
solvent molecule to produce the corresponding hemi-
acetal which undergoes cyclization to alkoxy deriva-
tives IV–VI. Another possible way of formation of
compounds IV–VI includes opening of the lactol ring
C29
Structure of the molecule of dipterocarpol (I) according to
the X-ray diffraction data. Non-hydrogen atoms are shown as
thermal vibration ellipsoids with a probability of 50%.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 48 No. 10 2012

SMIRNOVA et al.
1372
Scheme 2.
HO
Me
CHO
Me
Me
O3
O3
Me
Me
I
OH
O
Me
O
Me Me
A
II
III
Scheme 3.
AcO
Me
AcO
Me
CHO
Me
i
ii
Me
Me
Me
Me
Me
I
Me
Me
O
O
Me Me
Me Me
VII
VIII
Me
HO
22
Me
24
20
Me
Me
25
iii
iv
Me
Me
Me
Me
Me
Me
I
Me
Me
5
3
HO
Me Me
Me
Me
O
IX, 92%
X, 85%
Me
v
Me
Me
Me
Me
Me
O
O
O
XI, 72%
i: Ac2O, Δ; ii: O3 (1 equiv), CDCl3, –40°C; iii: NaBH4, EtOH, 68°C; iv: PCl5, CHCl3, –5 to 0°C; v: O3 (3 equiv), CH2Cl2, –40°C.
Ozonolysis of O-acetyl derivative VII, which can-
not undergo intramolecular cyclization with participa-
double bonds in molecule X was judged on the basis
of signals from the corresponding carbon atoms
(δC 123.6–140.1 ppm).
tion of the 20-OH group, gave aldehyde VIII
1
(Scheme 3); its H NMR spectrum contained a signal
Low-temperature ozonolysis of dammarane-type
3(5),20(22),24(25)-triene X afforded compound XI
possessing 1,2,4-trioxolane and methyl ketone frag-
ments. Stable ozonides derived from allobetulin were
reported by us previously [17]. Comparison of the
chemical shifts of carbon atoms in ozonide XI with
published data [17] indicated stereospecificity of
oxidation of the C3=C5 bond with formation of
(3R,5R)-ozonide.
at δ 8.0 ppm from the aldehyde proton. Compound
VIII turned out to be unstable, and it underwent fast
oxidation with formation of a mixture of products
which were difficult to separate.
Triene X was synthesized by treatment of 3β-hy-
droxydipterocarpol (IX) with PCl5 in chloroform
(Scheme 3). Compound IX was prepared by reduction
of I with sodium tetrahydridoborate. The position of
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 48 No. 10 2012

OZONOLYSIS OF DIPTEROCARPOL AND ITS DERIVATIVES
1373
Peroxides mediating the formation of compounds
II–VI and VIII are unstable, and they spontaneously
decompose within a short time.
3J1-eq,2-eq = 4.5 Hz), 2.02 m (1H, 23-HA), 2.08 m (1H,
2
3
23-HB), 2.43 d.d.d (1H, 2-Heq, J = 15.6, J2-eq,1-ax
=
3
2
7.7, J2-eq,1-eq = 4.5 Hz), 2.51 d.d.d (1H, 2-Hax, J =
3
3
15.6, J2-ax,1-ax = 9.6, J2-ax,1-eq = 7.6 Hz), 5.12 m (1H,
24-H, 3J24,23A = 7.1, 3J24,23B = 7.1, 4J24,26 = 1.5, 4J24,27
EXPERIMENTAL
=
1.5 Hz). 13C NMR spectrum (CDCl3), δC, ppm: 15.20
(C18), 16.03 (C19), 16.34 (C30), 17.72 (C26), 19.64
(C10), 21.01 (C28), 22.02 (C11), 22.55 (C23), 24.79 (C16),
25.47 (C21), 25.75 (C27), 26.69 (C29), 27.52 (C12),
31.15 (C15), 34.10 (C2), 34.53 (C6), 36.81 (C9), 39.88
(C1), 40.26 (C7), 40.45 (C22), 42.36 (C13), 47.42 (C4),
49.79 (C17), 49.99 (C8), 50.25 (C14), 55.33 (C5), 75.34
(C20), 124.68 (C24), 131.63 (C25), 218.11 (C3). Found,
%: C 81.15; H 11.10. C30H50O2. Calculated, %:
C 81.39; H 11.30.
1
The H and 13C NMR spectra were recorded on
a Bruker AM-300 spectrometer at 75.5 and 300 MHz,
respectively, and on a Bruker Avance III spectrometer
at 500.13 and 125.47 MHz, respectively, using a 5-mm
z-gradient PABBO probe; sample temperature 298 K,
internal reference TMS. The optical rotations were
measured in chloroform on a Perkin Elmer MC-241
polarimeter. The melting points were determined on
a Boetius melting point apparatus. Ozone was generat-
ed using an Ozon-2K ozonizer. Thin-layer chromatog-
raphy was performed on Sorbfil plates (Sorbpolimer
closed corporation, Russia) using chloroform–ethyl
acetate (20:1) as eluent; spots were detected by treat-
ment with a 10% solution of sulfuric acid, followed by
heating at 100–120°C over a period of 2–3 min. The
presence of peroxide ozonolysis products was checked
by the potassium iodide test.
X-Ray analysis of dipterocarpol (I). The X-ray
diffraction data were acquired on a Bruker SMART
1000 diffractometer with a CCD area detector;
C30H50O2 (M 442.70); colorless rhombic crystals with
the following unit cell parameters (100 K): a =
8.374(2), b = 12.515(4), c = 25.018(7) Å; V =
2622.0(13) Å3; space group P212121; Z = 4; dcalc
=
1.121 g/cm3. Intensities of 38510 reflections were
measured on a Bruker Smart Apex2 CCD diffractom-
eter (λMoKα irradiation, θmax = 29°) from a 0.23×
0.17×0.16-mm single crystal. The initial array of
reflection intensities was processed using SAINT and
SADABS programs incorporated into APEX2 software
package [18]. The structure was solved by the direct
method and was refined against F2hkl by the full-matrix
least-squares procedure in anisotropic approximation
for non-hydrogen atoms. Hydrogen atoms were placed
into positions calculated on the basis of geometry
considerations; an exception was hydrogen atom in the
hydroxy group, which was localized by difference
synthesis of electron density. The O–H distance was
normalized by a value of 0.85 Å. The positions of
hydrogen atoms were refined according to the riding
model [Uiso(H) = nUeq(C,O), where n = 1.5 for methyl
carbon atoms, n = 1.2 for other carbon atoms, and n =
1.5 for the oxygen atom]. The structure was refined
using 3929 independent reflections (Rint = 0.1004). The
final divergence factors were wR2 = 0.1624, R1 =
0.0669 for 3236 reflections with I > 2σ(I). All
calculations were performed on an IBM PC using
SHELXTL software package [19]. The coordinates of
atoms and their temperature factors were deposited to
the Cambridge Crystallographic Data Centre (entry
no. CCDC 845788).
(20S)-20-Hydroxydammar-24-en-3-one (I, di-
pterocarpol) was extracted from 200 g of Diptero-
carpus alatus pitch with 500 ml of hexane. The solvent
was evaporated, the residue was kept for 3 days at 0–
5°C, the crystals were filtered off and washed with
hexane, and the residue was recrystallized twice from
hexane. Yield 74 g (37% calculated on the initial
pitch), mp 187–188°C, Rf 0.65, [α]D20 = +88° (c = 0.52,
1
CHCl3) [10]. H NMR spectrum (CDCl3), δ, ppm:
0.89 s (3H, C30H3), 0.94 s (3H, C19H3), 1.00 s (3H,
C18H3), 1.04 s (3H, C28H3), 1.08 s (3H, C29H3),
2
3
1.10 d.d.d (1H, 15-Heq, J = 13.8, J15-eq, 16-ax = 6.9,
3J15-eq,16-eq = 4.9 Hz), 1.15 s (3H, 21-H), 1.28 m (1H,
2
12-Hax), 1.31 d.d.d.d (1H, 11-Hax, J = 12.9,
3J11-ax,12-ax = 14.1, J11-ax,8 = 12.3, J11-ax,12-eq = 3.7 Hz),
3
3
1.32 m (1H, 6-Heq), 1.38 d.d (1H, 10-H, 3J10,5-ax = 11.6,
3J10,5-eq = 2.8 Hz), 1.43 d.d (1H, 8-H, J8,11-ax = 12.3,
3
3J8,11e 2.9 Hz), 1.46 d.d.d (1H, 1-Hax, J = 13.1,
2
3J1-ax,2-ax = 9.6, J1-ax, 2-eq = 7.7 Hz), 1.46 m (1H,
3
15-Hax), 1.47 m (1H, 5-Heq), 1.47 m (1H, 22-HA),
1.48 m (1H, 16-Heq), 1.49 m (1H, 22-HB), 1.51 m (1H,
11-Heq), 1.56 m (1H, 5-Hax), 1.57 m (1H, 6-Hax), 1.63 d
4
(3H, 26-H, J26, 24 = 1.5 Hz), 1.66 d.d.d (1H, 13-H,
3
3
3J13, 17 = 12.6, J13, 12-ax = 10.2, J13,12-eq = 3.5 Hz),
4
1.69 d (3H, 27-H, J27, 24 = 1.5 Hz), 1.57 m (1H,
16-Hax), 1.76 d.t (1H, 17-H, J17,16-ax = 12.6, J17,13
12.6, J17, 16-eq = 3.1 Hz), 1.85 m (1H, 12-Heq),
1.92 d.d.d (1H, 1-Heq, J = 13.1, J1-eq, 2-ax = 7.6,
3
3
=
3
(20S,24RS)-23,24-Epoxy-24-hydroxy-25,26,27-
trinordammaran-3-one (II). Compound I, 1 mmol
2
3
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 48 No. 10 2012

SMIRNOVA et al.
1374
(0.44 g), was dissolved in 50 ml of methylene chloride,
and 1 equiv of ozone was passed through the solution
at –40°C until the initial compound disappeared
(TLC). The solvent was removed, and the residue was
subjected to column chromatography on aluminum
oxide using in succession benzene and chloroform as
eluents. Yield 0.33 g (75%), a mixture of epimers at
compound disappeared (TLC). The mixture was evap-
orated, and the residue was subjected to column chro-
matography on aluminum oxide using in succession
benzene and chloroform as eluents.
(20S,24RS)-23,24-Epoxy-24-methoxy-25,26,27-
tri-nordammaran-3-one (IV). Yield 0.30 g (70%),
a mixture of epimers at a ratio of 1:1 (1H NMR).
mp 142–145°C, [α]D20 = +36° (c = 0.25, CHCl3).
1H NMR spectrum (CDCl3), δC, ppm: 0.90 s (3H,
CH3), 0.94 s (3H, CH3), 0.98 s (3H, CH3), 1.02 s (3H,
CH3), 1.07 s (3H, CH3), 1.36 s (3H, CH3), 1.11–1.64 m
(13H, CH, CH2), 1.70–2.19 m (8H, CH, CH2), 2.46–
2.75 m (3H, CH, CH2), 3.33 s and 3.34 s (3H, OCH3),
4.93 t (1H, 24-H, J = 4.7 Hz). 13C NMR spectrum
(CDCl3), δC, ppm: 15.2, 16.0, 16.1, 19.6, 21.0, 21.9,
25.0, 25.5, 26.7, 26.8, 29.1, 31.1, 31.2, 34.0, 34.5,
36.8, 39.8, 40.3, 41.0, 43.3, 47.4, 49.3, 50.0, 50.1,
55.3, 88.1 and 87.9 (C20), 104.7 and 105.2 (C24), 217.9
(C3). Found, %: C 77.83; H 10.55. C28H46O3. Calculat-
ed, %: C 78.09; H 10.77. In addition, 0.05 g (15%) of
III was isolated.
1
a ratio of 1:1 (according to the H NMR data),
mp 208–210°C, [α]D20 = +106° (c = 0.25, CHCl3).
1H NMR spectrum (CDCl3), δ, ppm: 0.83 s and 0.84 s
(3H, CH3), 0.91 s (3H, CH3), 0.96 s and 0.98 s (3H,
CH3), 0.97 s (3H, CH3), 1.04 s (3H, CH3), 1.08 s (3H,
CH3), 1.15–1.65 m (13H, CH, CH2), 1.67–2.11 m (7H,
CH, CH2), 2.35–2.59 m (3H, CH, CH2), 3.32 m and
3.68 m (1H, OH), 4.96 br.s (1H, 23-H). 13C NMR
spectrum (CDCl3), δC, ppm: 15.2, 16.2, 19.6, 22.1,
24.3, 25.4, 26.7, 27.1, 28.8, 31.1, 31.7, 32.4, 32.8,
33.8, 34.1, 34.6, 36.8, 40.3, 43.5, 47.4, 49.7, 50.0,
55.3, 62.2 and 61.9, 87.9 and 87.6 (C20), 103.6 and
103.1 (C24), 217.9 (C3). Found, %: C 61.72; H 7.28.
C27H43O3. Calculated, %: C 61.95; H 7.51.
(20S)-23,24-Epoxy-25,26,27-trinordammarane-
3,24-dione (III). a. Compound I, 1 mmol (0.44 g), was
dissolved in 50 ml of methylene chloride, and 2 equiv
of ozone was passed through the solution at –40°C
until the initial compound disappeared (TLC). The
mixture was evaporated, and the residue was subjected
to column chromatography on aluminum oxide using
in succession benzene and chloroform as eluents. Yield
of III 0.28 g (68%). In addition, 0.17 g (20%) of II
was isolated.
(20S,24RS)-23,24-Epoxy-24-ethoxy-25,26,27-tri-
nordammaran-3-one (V). Yield 0.37 g (85%), a mix-
ture of epimers at a ratio of 1:1 (1H NMR). mp 80–
82°C, [α]D20 = +46° (c = 0.3, CHCl3). H NMR spec-
1
trum (CDCl3), δ, ppm: 0.78 s (3H, CH3), 0.86 s (3H,
CH3), 0.90 s (3H, CH3), 0.95 s (3H, CH3), 1.00 s (3H,
CH3), 1.22 s (3H, CH3), 1.33 s (3H, CH3), 1.08–1.59 m
(4H, CH, CH2), 1.65–1.98 m (14H, CH, CH2), 2.38–
2.55 m (6H, CH, CH2), 3.33–3.46 m and 3.68–3.80 m
(1H, OCH2), 5.05 t (1H, 24-H, J = 4.1 Hz). 13C NMR
spectrum (CDCl3), δC, ppm: 15.1, 15.9, 19.6, 20.9,
22.0, 21.9, 23.7, 25.3, 25.9, 26.6, 27.0, 28.6, 30.9,
32.6, 34.0, 35.0, 34.8, 36.7, 39.8, 40.2, 43.4 and 47.3,
49.9, 50.1, 50.8, 55.2, 61.9 and 62.1, 87.8 and 87.6
(C20), 103.5 and 102.9 (C24), 217.9 (C3). Found, %:
C 78.02; H 10.15. C29H48O3. Calculated, %: C 78.33;
H 10.88.
b. When 1 equiv of ozone was passed through
a solution of 1 mmol (0.41 g) of II in 50 ml of meth-
ylene chloride or acetone at –40°C, the yield of III was
0.36 g (97%) or 0.39 g (95%), respectively. mp 182–
184°C, [α]D20 = +68° (c = 1.66, CHCl3); published data
[10]: mp 180–182°C, [α]D20 = +69°. H NMR spectrum
1
(CDCl3), δ, ppm: 0.90 s (3H, CH3), 0.94 s (3H, CH3),
0.98 s (3H, CH3), 1.02 s (3H, CH3), 1.07 s (3H, CH3),
1.36 s (3H, CH3), 1.11–1.64 m (12H, CH, CH2), 1.70–
2.19 m (8H, CH, CH2), 2.46–2.75 m (4H, CH, CH2).
13C NMR spectrum (CDCl3), δC, ppm: 15.2, 16.0, 16.1,
19.6, 21.0, 21.9, 25.0, 25.5, 26.7, 26.8, 29.1, 31.1,
31.2, 34.0, 34.5, 36.8, 39.8, 40.3, 43.3, 47.4, 49.3,
50.0, 50.1, 55.3, 89.9 (C20), 176.6 (C24), 217.7 (C3).
Found, %: C 78.02; H 9.98. C27H42O3. Calculated, %:
C 78.21; H 10.21.
(20S,24R,S)-23,24-Epoxy-24-isopropoxy-25,26,27-
trinordammaran-3-one (VI). Yield 0.35 g (79%),
a mixture of epimers at a ratio of 1 : 1 (1H NMR).
mp 84–86°C, [α]D20 = +52° (c = 0.25, CHCl3). 1H NMR
spectrum (CDCl3), δ, ppm: 0.85 s (3H, CH3), 0.90 s
(3H, CH3), 0.95 s and 0.96 s (3H, CH3, 1:1), 0.97 s
(3H, CH3), 1.10 s (3H, CH3), 1.07 s (3H, CH3), 1.17 s
(3H, CH3), 1.19 s (3H, CH3), 1.12–1.61 m (13H, CH,
CH2), 1.65–1.98 m (8H, CH, CH2), 2.34–2.49 m (3H,
CH, CH2), 3.78 m and 4.01 m [1H, OCH(CH3)],
5.47 br.s (1H, CH, 24-H). 13C NMR spectrum (CDCl3),
δC, ppm: 15.2, 16.0, 16.1, 19.6, 21.0, 21.9, 22.0, 23.5,
25.0, 25.5, 26.7, 31.0, 33.8, 34.0, 34.6, 34.8, 35.5,
Compounds IV–VI. A solution of 1 mmol (0.44 g)
of compound I in 50 ml of methanol, ethanol, or
propan-2-ol was cooled to –40°C, and 2 equiv of
ozone was passed through the solution until the initial
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 48 No. 10 2012

OZONOLYSIS OF DIPTEROCARPOL AND ITS DERIVATIVES
1375
36.8, 39.9, 40.3, 43.2, 43.5, 45.7, 47.4, 49.8, 55.3,
67.4, 89.2 (C20), 108.1 and 107.7 (C24), 218.2 (C3).
Found, %: C 78.22; H 10.59. C30H50O3. Calculated, %:
C 78.55; H 10.99. In addition, 0.05 g (13%) of III was
isolated.
with 30 ml of a saturated aqueous solution of sodium
carbonate and stirred for 30 min at room temperature,
the organic phase was separated, washed with water
(3×30 ml), dried over Na2SO4, and evaporated under
reduced pressure, and the residue was subjected to
column chromatography on Al2O3 using hexane as
(20S)-3-Oxodammar-24-en-20-yl acetate (VII).
A solution of 1 mmol (0.44 g) of compound I in 2 ml
of acetic anhydride was heated for 15 h under reflux.
The mixture was poured into 50 ml of water, the
organic phase was separated, washed with water
(3×30 ml), dried over MgSO4, and evaporated under
reduced pressure, and the residue was purified by
column chromatography on Al2O3 using benzene as
eluent. Yield 0.40 g (92%), mp 107–109°C, Rf 0.93.
eluent. Yield 0.40 g (93%), mp 102–105°C, [α]D20
=
+46° (c = 0.25, CHCl3). 1H NMR spectrum (CDCl3), δ,
ppm: 0.82 s (3H, CH3), 0.93 s (3H, CH3), 0.95 s (3H,
CH3), 0.98 s (3H, CH3), 1.30 s (3H, CH3), 1.45 s (3H,
CH3), 1.55 s (3H, CH3), 1.64 s (3H, CH3), 1.15–1.49 m
(11H, CH, CH2), 1.52–1.80 m (7H, CH, CH2), 2.05–
2.30 m (3H, CH, CH2), 2.61–2.73 m (1H, CH), 5.10 m
(2H, 22-H, 24-H). 13C NMR spectrum (CDCl3), δC,
ppm: 14.0 15.7, 18.8, 19.9, 17.7, 21.3, 21.9, 23.2, 24.2,
24.9, 25.7, 26.4, 27.4, 29.7, 30.8, 31.7, 32.4, 34.4,
40.7, 42.2, 44.8, 46.1, 49.0, 50.6, 123.6 (C20), 123.7
(C24), 125.1 (C22), 131.63 (C25), 136.5 (C5), 140.1 (C3).
Found, %: C 87.98; H 11.68. C30H48. Calculated, %:
C 88.16; H 11.84.
[α]D20 = +35° (c = 0.5, CHCl3). H NMR spectrum
1
(CDCl3), δ, ppm: 0.79 s (3H, C30H3), 0.87 s (3H,
C19H3), 0.90 s (3H, C18H3), 0.94 s (3H, C28H3), 1.00 s
(3H, C29H3), 1.10–1.49 m (12H, CH, CH2), 1.31 s (3H,
21-H), 1.89 s (3H, COCH3), 1.90–2.11 m (8H, CH,
4
CH2), 1.43 d (3H, 26-H, J26,24 = 1.5 Hz), 1.53 d (3H,
4
(3R,5R)-3,5-Epidioxy-3-isopropyl-4-oxa-
22,23,24,25,26,27-hexanordammaran-20-one (XI).
Compound X, 1 mmol (0.41 g), was dissolved in 30 ml
of methylene chloride, 3 equiv of ozone was passed
through the solution at –40°C, the solvent was re-
moved, and the residue was subjected to column chro-
matography on Al2O3 using in succession hexane and
benzene as eluents. Yield 0.34 g (82%), mp 83–85°C,
27-H, J27,24 = 1.5 Hz), 2.31–2.53 m (4H, CH, CH2),
5.05 m (1H, 24-H). 13C NMR spectrum (CDCl3), δC,
ppm: 15.3, 15.8, 16.0, 16.2, 17.7, 19.6, 20.9, 21.0,
22.0, 22.6, 24.7, 25.47, 25.7, 26.7, 28.8, 31.3, 34.0,
34.6, 36.8, 39.7, 39.9, 42.1, 45.3, 46.5, 47.7, 50.2,
55.3, 87.8 (C20), 124.4 (C24), 131.5 (C25), 170.4
(COCH3), 218.2 (C3). Found, %: C 79.03; H 10.67.
C32H52O3. Calculated, %: C 79.29; H 10.81.
[α]D20 = +45° (c = 0.1, CHCl3). H NMR spectrum
1
(20S)-3,24-Dioxo-25,26-dinordammaran-20-yl
acetate (VIII). Compound VII, 0.25 mmol (100 mg),
was dissolved in 2 ml of CDCl3, and 1 equiv of ozone
was passed through the solution at –40°C until the
initial compound disappeared (TLC, Rf 0.85). After
(CDCl3), δ, ppm: 0.90 s (3H, CH3), 0.93 s (3H, CH3),
0.96 s (3H, CH3), 0.98 s (3H, CH3), 1.00 s (3H, CH3),
1.13–1.40 m (11H, CH, CH2), 1.42–1.77 m (5H, CH,
CH2), 1.80–2.10 m (3H, CH, CH2), 2.11 s (3H, CH3),
2.50–2.61 m (1H, CH). 13C NMR spectrum (CDCl3),
δC, ppm: 15.6, 16.1, 17.0, 17.4, 20.3, 21.8, 25.2, 25.5,
25.9, 26.0, 29.5, 29.9, 31.5, 31.6, 33.6, 38.7, 39.6,
40.3, 45.0, 50.5, 54.1, 110.9, 113.1, 212.0 (C20).
Found, %: C 73.31; H 9.36. C24H38O4. Calculated, %:
C 73.81; H 9.81.
1
30 min, H NMR spectrum was recorded (CDCl3), δ,
ppm: 0.80 s (3H, C30H3), 0.85 s (3H, C19H3), 0.92 s
(3H, C18H3), 0.95 s (3H, C28H3), 1.02 s (3H, C29H3),
1.09–1.50 m (12H, CH, CH2), 1.34 s (3H, 21-H),
1.95 s (3H, COCH3), 1.90–2.11 m (7H, CH, CH2),
2.31–2.53 m (4H, CH, CH2), 8.00 br.s (1H, 24-H).
C29H46O4. After 3 h, the solvent was removed under
reduced pressure. Yield 0.1 g (99%). According to the
TLC data, the product was a mixture of four com-
pounds, Rf 0.22, 0.27, 0.35, 0.51.
This study was performed under financial support
by the Russian Foundation for Basic Research (project
no. 10-03-90303).
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