1148
AL’FONSOV et al.
recording conditions, and refinment results are given
in Table 2. The atomic coordinates and geometric
parameters of the structures are deposited in the
Cambridge Structural Database and are also available
from the authors.
Crude alcohols IV and V obtained by reduction
with sodium borohydride of compounds I and III
were acetylated by the same procedures. The reaction
mixtures were analyzed by TLC on Silufol UV-254
plates, eluents petroleum ether ethyl acetate (1:1) and
petroleum ether diethyl ether (1:1).
The IR spectra were measured on a UR-20 spec-
1
trophotometer in the range 400 3600 cm in Vaseline
1
ACKNOWLEDGMENTS
oil. The H NMR spectra were obtained on Varian
T-60 and Bruker MSL-400 instruments.
The authors are grateful to the Khimiya i tekhno-
logiya pererabotki vozobnovlyaemogo rastitel’nogo
syr’ya Scientific Council (KhTRS grant no. 96-06) for
financial support and to the Russian Foundation for
Basic Research for help in payment for the licence for
use of Cambridge Structural Database (grant no. 96-
(
4 ,8 ,13 )-18-Methoxycarbonyl-13-methyl-16-
oxo-17-norkaurane (III) was obtained by treatment of
isosteviol (I) with diazomethane (cf. [3]).
(
4 ,8 ,13 )-16-Hydroxy-18-methoxycarbonyl-
1
3-methyl-17-norkaurane (IV). To a solution of
0
7-89187). The work was also financially supported
0
.77 g of compound III in 70 ml of methanol, heated
by the Fundamental’nye issledovaniya i vysshee
obrazovanie Russian American Program (BRHEREC
grant no. 007).
to 50 C, we added 2.0 g of NaBH . The reaction
4
mixture was left to stand at room temperature for
2
days, after which it was poured into water acidified
with HCl, and the reaction product was extracted with
diethyl ether (3 50 ml). The combined ether extracts
REFERENCES
were washed with water, dried with MgSO , and the
ether was removed to obtain 0.62 g (80%) of com-
4
1
2
. Shagidullin, R.R., Avvaakumova, L.V., Al’fonsov, V.A.,
Bakaleinik, G.A., Gubaidullin, A.T., Kataev, V.E.,
Kovylyaeva, G.I., Konovalov, A.I., Litvinov, I.A.,
Strobykina, I.Yu., Strobykin, S.I., Andreeva, O.V., and
Korochkina, M.G., Zh. Obshch. Khim., 2000, vol. 70,
no. 6, pp. 1026 1034.
pound IV, mp 173 174 C (from methanol) (163
2
0
1
66 C [3]), [ ]
,
74.9 (c 1.59, EtOH). IR spectrum,
D
1
1
cm : 1714 (C=O), 3540(OH). H NMR spectrum
(
1
DMSO-d ), , ppm: 0.63, 0.80, 1.11 s (9H, 10-CH ,
6
3
3-CH , 4-CH ); 3.59 s (3H, COOCH ).
3
3
3
. Al’fonsov, V.A., Bakaleinik, G.A., Gubaidullin, A.T.,
Kataev, V.E., Kovylyaeva, G.I., Konovalov, A.I., Lit-
vinov, I.A., Strobykina, I.Yu., Strobykin, S.I., Andre-
eva, O.V., and Korochkina, M.G., Zh. Obshch. Khim.,
2000, vol. 70, no. 6, pp. 1018 1025.
(
4 ,8 ,13 )-16-Acetoxy-13-methyl-17-norkau-
rane-18-carboxylic acid (V). To a solution of 0.3 g
of compound II in 25 ml of pyridine we added 15 ml
of acetic anhydride. The reaction mixture was left to
stand at room temperature for 2 days, poured into
water acidified with HCl, and the reaction product
was extracted with diethyl ether (3 50 ml). The com-
bined ether extracts were washed with water, dried
3
4
. Mosetting, E. and Nes, W.R., J. Org. Chem., 1955,
vol. 20, no. 7, pp. 884 890.
. Bakaleinik, G.A., Shagidullin, Rif.R., Shagidullin, R.R.,
Chernova, O.V., Musin, R.Z., and Karlin, V.V., Zh.
Obshch. Khim., 1992, vol. 62, no. 3, pp. 455 460.
with MgSO , and the ether was removed to obtain
4
0
.28 g (82%) of compound V, mp 213 215 S (from
2
0
5. Al’fonsov, V.A., Bakaleinik, G.A., Gubaidullin, A.T.,
Kataev, V.E., Kovylyaeva, G.I., Konovalov, A.I., Lit-
vinov, I.A., Strobykina, I.Yu., and Strobykin, S.I., Zh.
Obshch. Khim., 1998, vol. 68, no. 11, pp. 1813 1821.
methanol), [ ]
79 (c 2.06, MeOH). IR spectrum,
D
1
,
cm : 1705 (HO C_ =_ _O ), 1723 (CH C_ =_ _O ), 3260
3
1
(COOH). H NMR spectrum (DMSO-d ), , ppm:
6
0
0
.78, 0.91, 1.11 s (9H, 10-CH , 13-CH , 4-CH );
3 3 3
.85 2.12 m (kaurane carcass); 2.00 s (CH C=O).
6. Cambridge Structural Database System, Version 5.18,
3
Cambridge, 1999.
(
4 ,8 ,13 )-16-Acetoxy-18-methoxycarbonyl-13-
7
8
. Straver, L.H. and Schierbeek, A.J., MolEN. Structure
Determination System. Program Description, Nonius,
B.V., 1994.
methyl-17-norkaurane (VI) was obtained in a simi-
lar way from 0.1 g of compound IV in 10 ml of py-
ridine and 2.5 ml of acetic anhydride. Yield 0.08 g
1
. Altomare, A., Cascarano, G., Giacovazzo, C., and Vi-
terbo, D., Acta Crystallogr., Sect. A, 1991, vol. 47,
no. 4, pp. 744 748.
(
1
73%), mp 97 99 C. IR spectrum, , cm : 1730,
1
740 (CH O C_ =_ _O , CH C_ =_ _O ). H NMR spectrum
3 3
(
CCl ), , ppm: 0.87, 1.10, 1.32 s (9H, 10-CH , 13-
4
3
CH , 4-CH ); 0.85 2.12 m (kaurane carcass); 2.13 s
9. Spek, A.L., Acta Crystallogr., Sect. A, 1990, vol. 46,
3
3
(
CH C=O); 3.70 s (3H, COOCH ).
no. 1, pp. 34 40.
3
3
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 71 No. 7 2001