REARRANGEMENTS OF EPOXIDES OF SOME ACYCLIC TERPENOIDS
799
residue (0.79 g) was subjected to chromatography on
a column packed with SiO2, gradient elution with a
hexane ethyl ether mixture containing 0 50% of
ether. We isolated 0.03 g of methyl ether IV. Mass
spectrum, m/z (Irel, %): 202 (M+ , 1), 140 (93), 125
epoxide I in 2 ml of CH2Cl2, and the mixture was
stirred for 1 h at 25 C. After the usual workup we
obtained 0.137 g of crude product that was percolated
with ethyl ether through a column packed with Al2O3
(of IV grade activity). As a result 0.077 g of the
reaction products mixture was separated and sub-
jected to column chromatography on SiO2 ( gradient
elution with a hexane ethyl ether mixture containing
0 50% of ether). We isolated 0.025 g of ketone VIII.
Mass spectrum: m/z (Irel, %): 170 (M+ , 10), 88 (27),
82 (97), 69 (100), 67 (28), 55 (23), 41 (51). Found:
M+ 170.13030. C10H18O2. Calculated: M 170.13067.
1H NMR spectrum ( , ppm, J, Hz): 1.08 d (C10H3,
J10,3 7), 1.39 d.d.d.d (H4, J4,4 13.5, J4,5 8, J4,5 7,
J4,3 7), 1.54 br.s (C8H3), 1.64 d.t (C9H3, J9,6 1.5,
J9,5 1), 1.70 d.d.d.d (H4 , J 13.5, J4 ,5 8.5, J4 ,5 7,
J4 ,3 7), 1.92 m (2H5), 2.50 d.d.q (H3, J 7, 7, 7),
3.16 br.s (OH), 4.20 d and 4.25 d (2H1, J 19), AB
system, 4.99 t.q.q (H6, J6,5 7, J6,8 1.5, J 1.5).
1
(35), 85 (100), 72 (38), 43 (31), 41 (29). H NMR
spectrum ( , ppm, J, Hz): 1.11 s (C9H3), 1.15 d
(C11H3, J11,5a 0.5), 1.17 s (C10H3), 1.31 1.42 m
(H4a, H5a), 1.51 m (H3e), 1.54 m (H4e), 1.63 d.d.d
(H3a, J3a,3e 14.5, J3a,4a 8, J3a,4e 1.5), 1.90 d.d.d
(H5e, J5e,5a 11, J5e,4a 5.5, J5e,4e 1), 2.60 br.s (OH),
3.17 s (OCH3), 3.38 d.d (H8, J8,8 11, J8,7 7), 3.52
d.d (H7, J 7, J7,8 6), 3.72 d.d (H8 , J 11, 6).
(b) A solution of 0.153 g of epoxide I in 0.4 ml of
SO2FCl was added at 100 C to a solution of 1.8 g of
HSO3F in 3.8 ml of SO2FCl, the mixture was
warmed to 80 C. After quenching with a mixture
CH3OH (C2H5)2O, neutralization with 17% water
solution of Na2CO3 and usual workup the residue was
passed through a column with Al2O3 (of IV grade
activity) (eluent ethyl ether). We obtained 0.085 g of
product mixture that was subjected to chromato-
graphy on column packed with SiO2 and then on that
with SiO2 + AgNO3 (20%). As a result compounds
III, V, and VI were isolated as individual substances.
Mass spectra of compounds V and VI: M+ 170
(0.92%) and M+ 170(0.08%). In the mass spectra of
isomers V and VI was observed an ion 139 (M+
Rearrangements of diastereomeric epoxides
IXa, b. To a mixture of 0.108 g of citronellol
(XXIII) and 19 ml of 0.25 M water solution of
NaHCO3 was added at 0 C 13 ml of 0.15 M water
solution of monoperphthalic acid, and the mixture
was stirred for 2 h at the same temperature. The
workup furnished 0.101 g of the reaction products
mixture that was subjected to column chromatography
on SiO2 (gradient elution with hexane ethyl ether
mixture containing 0 30% of ether). We separated
1
CH2OH). H NMR spectrum of compound V ( , ppm,
J, Hz): 1.24 s, 1.26 s (C8H3, C9H3), 1.57 m (C11H3,
J 1.5 2.5), 1.60 d.d.d (H6, J6,6 14, J6,5 6.5, J6,5 2),
1
0.061 g of the mixture of epoxides IXa, b. H NMR
spectrum of compound IXa ( , ppm, J, Hz): 0.91 d
(C10H3), J10,3 6.5), 1.24 s, 1.28 s (C8H3, C9H3),
1.32 1.62 m (2H2, 2H4, 2H5), 1.64 m (H3), 2.18
br.s (OH), 2.68 d.d (H6, J6,5 7, J6,5 6), 3.65 d.t (H1,
J1,1 10, J1,2 6.5) and 3.70 d.d.d (H1 , J 10, J1 ,2
7, J1 ,2 6), AB system. The chemical shifts of the
1.89 d.d.d.q (H6 , J 14, J6 ,5 12.5, J6 ,5 1.5, J6 ,CH
3
1), 1.94 d.d.d.d.d (H5, J5,5 16, J5,4 8, J 6.5, 1.5,
J5,2 1), 2.26 br.d.d (H12, J12,10 10, J12,10 2.5),
2.41 d.d.d.q.d.d (H5 , J 16, 12.5, J5 ,4 2.5, J5 ,11
2.5, J5 ,6 2, J5 ,2 1.5), 3.50 d.d.d (H10, J10,10 11,
J10,2 9, J10,12 2.5), 3.71 d.d.d (H10 , J 11, 10, J10 ,2
3.5), 4.33 br.d.d (H2, J 9, 3.5), 5.50 d.d.d.q H4, J 8,
1
signals from IXb isomer in the H NMR spectrum of
the IXa, b mixture are very close to that of the other
isomer. In the 13C NMR spectra of the isomers
IXa, b some signals of the carbon atoms have slightly
different chemical shifts (see table). To a dispersion
of 0.1 g of ZrO2/SO24 in 5 ml of CH2Cl2 was added
a solution of 0.051 g of epoxides IXa and IXb in 1 ml
of CH2Cl2, and the mixture was stirred for 1 h at
20 C. After the usual workup we obtained a crude
product that was percolated with ethyl ether through
a column packed with Al2O3 (of IV grade activity).
As a result 0.035 g of the reaction products mixture
was separated (containing 72% of ketone X, GLC)
and subjected to column chromatography on SiO2
(gradient elution with a hexane ethyl ether mixture
1
2.5, J4,2 2.5, J4,11 1.5). H NMR spectrum of com-
pound VI ( , ppm, J, Hz): 1.20 s, 1.21 s (C8H3,
C9H3), 1.41 1.52 m (H5, H6), 1.67 m (H6 ), 1.77 m
(H5 ), 2.14 br.s (OH), 2.15 d.d.d (H4, J4,4 13, J4,5
5, J4,5 5), 2.31 d.d.d.d.d (H4 , J 13, J4 ,5 10, J4 ,5
5, J4 ,11 1.5, J4 ,2 1), 3.44 br.d.d (H10, J10,10 11,
J10,2 5) and 3.47 br.d.d (H10 , J 11, J10 ,2 8), AB
system, 4.22 d.d.d.d (H2, J 8, 5, J2,11 1.5, J2,4 1),
4.71d.d (H11, J 1.5, J11,11 1), 4.85m (H11 , J 1 1.5).
(c) To a dispersion of 0.135 g of ZrO2/SO24 in
10 ml of CH2Cl2 was added a solution of 0.152 g of
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 37 No. 6 2001