490
AKHMETVALEEV et al.
alcohol IX in 4,5 ml of CH2Cl2. After 15 min (TLC
monitoring) the reaction mixture was filtered through
a thin bed of silica gel, acidified with 2 N water solu-
tion of HCl till pH 6, the organic layer was washed
with saturated water solution of NaCl (3 30 ml),
dried on MgSO4, the solvent was removed under
reduced pressure. We obtained 0.82 g of aldehyde X
(Rf 0.47, eluent ethyl acetate pentane, 1: 1). IR
stirred for 30 min, then 1.8 ml of MeOH was added,
the reaction mixture was acidified with 3% water
solution of HCl till pH 5, the reaction product was
extracted into ethyl acetate (3 30 ml), the extract
was washed with saturated water solution of NaCl
(2 15 ml), dried with MgSO4. The solvent was
evaporated under reduced pressure, and the residue
was subjected to column chromatography on SiO2
(eluent ethyl acetate pentane, 1: 1; Rf 0.23) to afford
1
spectrum ( , cm ): 1500, 1590, 1610, 1720, 2740,
1
3020, 3040. To a solution of 0.82 g of the obtained
aldehyde X, 0.54 g of phosphonate XI, and 2.3 mg
of triethylbenzylammonium chloride in 9.2 ml of
CH2Cl2 at room temperature and vigorous stirring
was added 0.2 ml of 50% water solution of NaOH,
and the mixture was stirred for 15 20 min. On
completion of reaction (TLC monitoring) the reaction
mixture was diluted with 23 ml of CH2Cl2, acidified
with 1 N HCl water solution till pH 5, washed with
saturated water solution of NaCl (3 15 ml), dried
with MgSO4. The solvent was evaporated under
reduced pressure at room temperature, and the
residue was subjected to column chromatography on
SiO2 (eluent ethyl acetate pentane, 1: 1; Rf 0.35) to
afford 0.67 g (62%) of enone XII. IR spectrum ( ,
0.61 g (91%) of alcohol XIII. IR spectrum ( , cm ):
1584, 1600, 1702, 1716, 1720, 1732, 1736, 3048,
1
3064, 3120, 3512. H NMR spectrum (CDCl3,
,
ppm): 1.16 t (3H, Me, J 7 Hz), 1.18 t (3H, Me, J
7 Hz), 1.20 2.50 m (18H, 9CH2), 2.50 2.70 m (1H,
C2H), 2.75 2.90 m (1H, C3H), 3.00 3.50 m (1H,
OH), 3.54 s and 3.56 s (3H, OMe), 3.95 4.10 m (H,
C3 H), 4.05 q (2H, CH2O, J 7 Hz), 5.15 5.54 m (4H,
2CH=CH,), 5.55 5.70 m (2H, C4H, C1H), 7.20
7.30 m (2H, 2Hm arom), 7.30 7.48 m (3H, Hp arom,
2Hm arom), 7.48 7.55 m (1H, Hp arom), 7.8
7.93m (2H, 2Ho arom), 7.93 8.12m (2H, 2Ho arom).
13C NMR spectrum (CDCl3, , ppm): 14.34 (Me),
24.73 (C5 ), 25.05 (C5 ), 25.43 (C1 ), 26.72 (C4 ),
33.22 and 33.32 (C7 ), 34.29 (C6 ), 36.84 (C4 ),
39.21 (C5), 48.67 and 48.77 (C3), 51.55 (OMe),
53.13 and 53.18 (C2), 60.27 (CH2O), 72.18 (C3 ),
75.31 and 75.45 (C4), 79.00 and 79.24 (C1), 127.92
(C2 ), 128.02 (C3 ), 128.36 and 128.53 (Cm arom),
129.62 and 129.66 (Co arom), 130.28 and 130.51
(C2 ), 130.14 and 130.61 (C arom), 133.05 and
133.18 (Cp arom), 136.22 and 136.53 (C1 ), 165.86
(CO2), 166.21 and 166.29 (CO2), 173.78 (CO2),
174.06 and 174.19 (CO2).
1
cm ): 712, 1584, 1600, 1628, 1676, 1720, 1732,
1
1736, 3048, 3064. H NMR spectrum (CDCl3,
,
ppm): 1.18 t (3H, Me, J 7 Hz), 1.40 2.70 m (19H,
9CH2, C2H), 2.90 3.04 m (1H, C3H), 3.54 s (3H,
OMe), 4.04 q (2H, OCH2, J 7.0 Hz), 5.25 5.50 m
(4H, C4H, CH=CH, C1H), 6.23 d (1H, C2H, J
15.9 Hz), 5.85 d (1H, C1H, J 15.0, 8.9 Hz), 7.20
7.30 m (2H, 2Hm arom), 7.34 7.60 m (4H, 2Hp
arom, 2Hm arom), 7.86 mm(2H, Ho arom, J 7.5),
8.05 m (2H, 2Ho arom, J 7.5). 13C NMR spectrum
(CDCl3, , ppm): 14.10 (Me), 23.25 (C5 ), 24.36
(C6 ), 24.44 (C5 ), 25.40 (C1 ), 26.52 (C4 ),
33.06 (C6 ), 33.92 (C7 ), 39.14 (C5), 39.73 (C4 ),
48.50 (C3), 51.25 (OMe), 53.16 (C2), 60.20 (OCH2),
75.23 (C4), 78.26 (C1), 127.07 (C2 ), 128.17 and
128.34 (Cm arom), 129.44 (Co arom), 129.64 and
130.11 (C arom), 130.56 (C3 ), 131.58 (C2 ), 132.96
and 133.05 (Cm arom), 145.33 (C1 ), 165.51 (CO2),
165.83 (CO2), 173.62 (CO2), 173.25 (CO2), 199.42
(C=O).
REFERENCES
1. Akhmetvaleev, R.R., Bikbulatov, R.V., Belogae-
va, T.A., Akbutina, F.A., and Miftakhov, M.S.,
Zh. Org. Khim., 2002, vol. 38, no. 3, pp. 387 391.
2. Tolstikov, G.A., Akhmetvaleev, R.R., Zhurba, V.M.,
and Miftakhov, M.S., Zh. Org. Khim., 1992, vol. 28,
no. 4, pp. 712 723.
3. Miftakhov, M.S., Akhmetvaleev, R.R., Imaeva, L.R.,
Vostrikov, N.S., Saitova, M.Yu., Zarudii, F.S., and
Tolstikov, G.A., Khim. Farm. Zh., 1996, no. 8,
pp. 22 27.
( )-1 ,4 -Dibenzoyloxy-2 -(3 , -hydroxy-7-
ethoxycarbonyl-2Z-heptenyl)-3 -(2Z-6-methoxy-
carbonyl-2-hexen-1-yl)cyclopentane (XIII). To a
stirred solution of 0.67 g of enone XII in 7 ml of
EtOH at 0 C was added freshly prepared solution of
0.18 g of NaBH4 in 3 ml of NaOH. The mixture was
4. Tolstikov, G.A., Miftakhov, M.S., Valeev, F.A.,
Vostrikov, N.S., and Akhmetvaleev, R.R., Zh. Org.
Khim., 1984, vol. 20, no. 1, pp. 221 222.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 38 No. 4 2002