Acid-catalyzed reactions of 2,3-epoxy derivatives of citral with alcohols

Article abstract of DOI:10.1023/B:RUJO.0000003190.03400.91

Acid-catalyzed reactions of 2,3-epoxy derivatives of citral (which is a widely spread naturally occurring unsaturated aldehyde) with alcohols were studied under conditions of heterogeneous catalysis and in fluorosulfonic acid. A number of new products were obtained, and possible mechanisms of their formation were proposed.

Full text of DOI:10.1023/B:RUJO.0000003190.03400.91

Russian Journal of Organic Chemistry, Vol. 39, No. 7, 2003, pp. 985 991. Translated from Zhurnal Organicheskoi Khimii, Vol. 39, No. 7, 2003,
pp. 1047 1053.
Original Russian Text Copyright
2003 by Yarovaya, Korchagina, Salomatina, Polovinka, Barkhash.
Acid-Catalyzed Reactions of 2,3-Epoxy Derivatives
of Citral with Alcohols
O. I. Yarovaya1, D. V. Korchagina1, O. V. Salomatina2,
M. P. Polovinka1, and V. A. Barkhash1
1
Vorozhtsov Novosibirsk Institute of Organic Chemistry, Siberian Division, Russian Academy of Sciences,
pr. Akademika Lavrent’eva 9, Novosibirsk, 630090 Russia
e-mail: ooo@nioch.nsc.ru
2
Novosibirsk State University, Novosibirsk, Russia
Received October 23, 2002
Abstract Acid-catalyzed reactions of 2,3-epoxy derivatives of citral (which is a widely spread naturally
occurring unsaturated aldehyde) with alcohols were studied under conditions of heterogeneous catalysis and
in fluorosulfonic acid. A number of new products were obtained, and possible mechanisms of their formation
were proposed.
Interest in chemical transformations of terpene
compounds arises from their accessibility and reac-
tivity which make it possible to obtain products
having various structures [1]. Of particular interest are
acid-catalyzed transformations of terpenes and their
oxygen-containing analogs, for these processes are
accompanied by skeletal rearrangements which open
the way to selective preparation of valuable but dif-
ficultly accessible compounds or new compounds
with an unusual carbon backbone. Epoxy derivatives
of naturally occurring compounds could give rise to
cyclic and acyclic oxygen-containing products, and
studies of their transformations provide information
on the reaction mechanisms and relative reactivity
of such compounds.
We were the first to examine acid-catalyzed reac-
tions of 2,3-epoxy derivatives of citral. The latter is
widely spread in the nature as a mixture of E and
Z isomers, geranial (Ia) and neral (Ib), and wide syn-
thetic potential of its labile polyfunctional molecule
makes the use of citral and its derivatives in the syn-
thesis of various substances very promising.
2,3-Epoxy derivatives II were obtained as a mix-
ture of diastereoisomers IIa and IIb by the known
method, treatment of citral I with hydrogen peroxide
in alkaline medium in the presence of phase-transfer
Scheme 1.
1070-4280/03/3907-0985$25.00 2003 MAIK Nauka/Interperiodica

986
YAROVAYA et al.
Scheme 2.
Scheme 3.
catalyst [2]. Also, 6-methyl-5-hepten-2-one (III) was
formed as a result of decomposition of epoxy deriva-
tives II (Scheme 1). Optically active 2,3-epoxides
derived from geranial and neral have already been
reported: They were synthesized by asymmetric
epoxidation of geraniol and nerol, followed by oxida-
tion of the alcohol moiety to aldehyde [3, 4].
In the present work we used a racemic mixture of
compounds IIa and IIb at a ratio of 1:1 and studied
their reactions with methyl and allyl alcohols over
acidic -zeolite. The reaction of IIa/IIb with methyl
alcohol gave a mixture of compounds IV VIII at
a ratio of 3.8:2.7:1:2.4 (hereinafter, according to the
GLC data; Scheme 2). The structure of (1R,2R,3S,6R)-
6-isopropenyl-3-methoxy-3-methylcyclohexane-1,2-
diol (IV), (1R,2R,3R,6R)-6-isopropenyl-3-methoxy-
3-methylcyclohexane-1,2-diole (V), (1R,2R,3R,6S)-3-
methoxy-6-(1-methoxy-1-methylethyl)-3-methylcyclo-
hexane-1,2-diol (VI), and 1,1-dimethoxy-3,7-di-
methyl-6-octene-2,3-diols (VII and VIII, a mixture of
isomers) was determined by NMR spectroscopy. The
products were separated by column chromatography
on silica gel impregnated with 20% of AgNO3.
to opening of the oxirane ring with formation of
tertiary carbenium ion A which immediately reacts
with methanol molecule. The subsequent rearrange-
ments either involve ring closure to give cyclic diols
IV VI or afford acyclic compounds VII and VIII.
In the reaction with allyl alcohol, opening of the
oxirane ring in IIa/IIb gives rise to either tertiary
cation A or secondary cation B. These cations take up
allyl alcohol, yielding compounds IX and X, respec-
tively. The different pathways in the reactions of
IIa/IIb with methyl and allyl alcohols may be under-
stood in terms of different nucleophilicities of these
alcohols. It should be noted that application of epoxy
derivatives IIa and IIb to solid catalysts, such as
-zeolite used in our study or other acid catalysts
(e.g., clays or solid superacids) in the absence of
a nucleophile leads to polymerization of the substrate.
In the presence of liquid superacids, the reaction
of epoxy derivatives IIa and IIb with methanol took
a radically different pathway. A mixture of com-
pounds IIa and IIb was dissolved in fluorosulfonic
acid (molar ratio HSO3F:IIa/IIb = 20:1; volume
ratio SO2FCl:HSO3F = 4:1; 115 C), and the result-
ing acid solution was quenched with a mixture of
methanol with diethyl ether at a ratio of 5:2. We
thus obtained (2R,3S,6S)-2-hydroxy-6-methyl-3-(1-
methoxy-1-methylethyl)cyclohexanone (XI). A pos-
sible mechanism of formation of compound XI is
shown in Scheme 5. It includes opening of the oxirane
ring to give tertiary cation A which then undergoes
rearrangements leading to cation C. The latter takes
up methanol molecule to afford product XI.
The reaction of IIa/IIb with allyl alcohol over
-zeolite resulted in formation of (1R,2S,3S,6R)-3-
allyloxy-6-isopropenyl-3-methylcyclohexane-1,2-diol
(IX) and (1R,2R,3S,4R)-2-allyloxy-4-isopropenyl-1-
methylcyclohexane-1,3-diol (X) at a ratio of 1:2
(Scheme 3).
A probable mechanism of formation of diols IV X
is shown in Scheme 4. In the reaction with methyl
alcohol, protonation of epoxy aldehydes IIa/IIb leads
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 39 No. 7 2003

ACID-CATALYZED REACTIONS OF 2,3-EPOXY DERIVATIVES
987
Scheme 4.
R = CH3, R = CH2CH CH2.
Scheme 5.
Thus, in fluorosulfonic acid, initial opening of the
oxirane ring is followed by isomerization, cyclization,
and addition of methanol molecule to cation C,
whereas the process over acid zeolite involves reaction
with alcohol immediately after opening of the oxirane
ring; the main pathway in the reaction with methanol
leads to formation of 1,2-dihydroxycyclohexanes, and
in the reaction with allyl alcohol, to 1,3-dihydroxy-
cyclohexanes. Compounds IV XI have not been
reported previously.
spectrum of IV, the coupling constants between 1-H
and 2-H (3J1, 2 = 3 Hz), 1-H and 6-H (3J1, 6 = 10 Hz),
3
and 6-H and two 5-H protons (3J6, 5-ax = 12, J6, 5-eq
=
4 Hz) indicate that the 1-H and 6-H protons occupy
axial positions and that 2-H is equatorial. The pres-
ence of a long-range coupling constant between 4-Hax
and protons of the methyl group on C3 suggests axial
orientation of the latter. The vicinal coupling con-
1
stants in the H NMR spectrum of V are similar to
those observed for compound IV; however, no long-
range coupling between 4-Hax and 3-CH3 was detected
even on forced narrowing of spectral lines. This
means that the C7CH3 group occupies equatorial
position. It follows from the above stated that the
hydroxy groups on C1 and C2, methoxy group on C3,
and 6-Hax are arranged cis with respect to each other
Let us consider some aspects of structure deter-
mination of the compounds prepared. By analysis of
vicinal and long-range coupling constants for protons
on C1 C6 (see Experimental) we succeeded in estab-
lishing the conformations of compounds IV and V
1
and substituent configuration therein. In the H NMR
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 39 No. 7 2003

988
YAROVAYA et al.
in molecule IV and that the methoxy group on C3 in
molecule V is axial and is arranged trans with respect
to the above listed groups. The location of methoxy
group in diols IV and V on C3 rather than on C1 or
C2 was proved by the LRJMD technique. Irradiation
at a frequency corresponding to resonance of the
OCH3 protons ( 3.21 and 3.13 ppm, respectively)
Like other compounds, the configuration of XI was
determined from vicinal coupling constants for the
corresponding protons. 2,3-Epoxy neral derivative IIb
1
was previously characterized by the H and 13C NMR
spectra [4, 5], but no complete signal assignment was
given. The chemical shifts measured in the present
work are in agreement with those reported in [4, 5].
gave rise to singlets at
76.74 (compound IV) and
C
76.93 ppm (V), which belong to C3.
EXPERIMENTAL
The positions of hydroxy groups in VI (at C1 and
C2) were determined on the basis of the 13C NMR
data. After addition of D2O (H D exchange in the
hydroxy groups), we observed upfield shift of two
The H and 13C NMR spectra were recorded on
1
a Bruker AM-400 spectrometer operating at 400.13
and 100.61 MHz, respectively. A mixture of CCl4
with CDCl3 ( 1:1, by volume) was used as solvent,
and chloroform signals were taken as reference
doublets at
(
70.72 (
= 0.10) and 73.68 ppm
C
C
= 0.15 ppm), which belong, respectively, to C1
(
7.24 ppm,
76.90 ppm). The structure of the
and C2. The configuration of substituents in VI is
the same as in V.
C
products was determined by analysis of coupling con-
1
stants in the 1H H double resonance spectra and
by analysis of the 13C NMR spectra recorded with
selective decoupling from protons, off-resonance
The fact that both methoxy groups in diols VII and
VIII are attached to the same carbon atom follows
from the LRJMD spectrum. Suppression of signals
from all methoxy group protons ( 3.41 ppm) in the
LRJMD spectrum of a mixture of VII with VIII at
a ratio of 1:2 gave a response only at the C1 signal
1
spectra, two-dimensional 13C H correlation spectra
1
(COSY, direct couplings, JC, H = 135 Hz), and one-
1
dimensional 13C H correlation spectra (LRJMD,
long-range couplings, JC, H = 10 Hz). For some com-
pounds, direct coupling constants JC, H are given,
which were obtained from the monoresonance spectra;
their values do not contradict the assigned structures.
at
104.46 and 104.27 ppm, respectively. If one or
C
1
both methoxy groups were attached to C2 and/or C3,
additional carbon signals would appear in the LRJMD
spectrum at
only the latter).
73.92, 74.29 and/or 73.03 ppm (or
C
The purity of the initial compounds was checked,
and the product mixtures were analyzed, by GLC on
a Biokhrom-1 chromatograph using the following
columns: (a) XE-60 glass capillary column, 53 m
0.26 mm, and (b) BS-30 (an analog of SE-30) quartz
capillary column, 20 m 0.27 mm; flame ionization
detector; carrier gas helium. The product mixtures
were separated by column chromatography on silica
gel (Czechia, 40 100 and 100 160 m), SiO2/AgNO3,
and Al2O3. The ratio crude product sorbent was 1:20
to 1:40. The elemental compositions were determined
from the high-resolution mass spectra which were
recorded on a Finnigan MAT 8200 instrument.
Doubly distilled fluorosulfonic acid (bp 158
161 C) was used for preparation of acid solutions.
Fluorosulfonyl chloride (diluent) was purified by
passing through sulfuric acid. The acid mixtures were
quenched with a mixture of methanol with diethyl
ether (5:2, by volume). The procedures for prepara-
tion and qienching of acid solutions were described
in [6]. Wide-pore -zeolite (SiO2/Al2O3 22.4; pore
diameter 0.75 0.80 nm; oxide concentration, %:
Na2O 0.01, Al2O3 4.50, SiO2 59.20, Fe2O3 0.08%)
was manufactured by Tseosit (Novosibirsk, Russia);
it was calcined for 3 h at 500 C prior to use. The fol-
lowing reagents were used: citral (from Fluka) with
1
In the H NMR spectrum of X, the vicinal coupling
constant between the 3-H and 4-H protons (3J3, 4
=
10.5 Hz) indicates their axial orientation, and a small
3
value of J2, 3 (3 Hz) suggests equatorial orientation
of 2-H. Protons of the methyl group on C1 are charac-
4
terized by a coupling constant J7, 6-ax of 0.6 Hz,
which is typical of axial orientation of C7H3. There-
fore, the methyl group on C1 and isopropenyl group
on C4 are arranged cis with respect to each other and
trans with respect to 2-OR and 3-OH.
On the basis of the vicinal coupling constants for
1-H 2-H and 1-H 6-H (J = 9 Hz) and the appearance
4
of J = 0.7 Hz between the C7H3 protons and 4-Hax
we concluded that the 1-H, 2-H, and 6-H protons and
the 3-CH3 group in molecule IX are axial. This means
that the 3-CH3 group is located cis with respect to 1-H
and trans with respect to 2-H and 6-H.
The position of the allyloxy group at the C2 atom
in molecule X and at C3 in IX follows from the
LRJMD spectra. Suppression of the 8-H resonance
( 3.94 and 3.91 ppm, respectively) gives rise in the
first case to a doublet signal at
74.33 ppm (C2) in
addition to those belonging to C9Cand C10, and in the
second, to a singlet at
77.77 ppm (C3).
C
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ACID-CATALYZED REACTIONS OF 2,3-EPOXY DERIVATIVES
989
a purity of no less than 97%, cis/trans isomer ratio
1:2 (according to the H NMR data), and technical-
Compound IV. Found [M]+: 200.14099. C11H20O3.
1
1
Calculated M: 200.14123. H NMR spectrum, , ppm
(J, Hz): 1.15 d (C7H3, J7, 4-ax = 0.7), 1.22 d.d.d.d
(5-Hax, J5-ax, 5-eq = 14, J5-ax, 4-ax = 12.5, J5-ax, 6-ax = 12,
grade citral containing 13% of dehydrolinalool,
cis/trans isomer ratio 1:1 (1H NMR).
The reaction of citral with hydrogen peroxide
under conditions of phase-transfer catalysis was
carried out following the procedure described in [2].
From 3 g of citral we obtained 2.35 g of a crude prod-
uct containing compounds IIa, IIb, and III at a ratio
of 3.8:3.3:1. The products were separated by column
chromatography on silica gel using hexane as eluent:
0.10 g of III and 1.95 g of a IIa/IIb mixture were
isolated. Isomer mixture IIa/IIb was then separated
on basic Al2O3 using hexane as eluent; as a result,
0.25 g of pure 2,3-epoxy derivative IIb was isolated.
J5-ax, 4-eq = 3.5), 1.47 d.d.d.d (4-Heq, J4-eq, 4-ax = 12.5,
J = 3.5, J4-eq, 5-eq = 3.5, J4-eq, 2-eq = 1.2), 1.55 d.d.d.d
(5-Heq, J = 14, J5-eq, 4-ax = 4, J5-eq, 6-ax = 4, J = 3.5),
1.67 d.d.d (4-Hax, J = 12.5, 12.5, 4), 1.69 d.d (C11H3,
J11, 10 = 1.5, J11, 10 = 1), 2.24 br.d (1-OH, J = 6),
2.37 d.d.d (6-Hax, J = 12, J6-ax, 1-ax = 10, J = 4),
2.72 br.s (2-OH), 3.21 s (OCH3), 3.45 br.m (1-Hax,
J = 10, 6, J1-ax, 2-eq = 3), 3.70 m (2-Heq, J = 3, 1.2),
4.77 d.d.q (10-H, J10, 10 = 2, J10, 6-ax = 1, J10, 11 = 1),
4.80 d.q (10 -H, J = 2, 1.5). 13C NMR spectrum,
,
C
1
The H and 13C NMR spectra of geranial epoxide IIa
ppm (1JC, H, Hz): 70.95 d (142) (C1), 74.13 d (146)
(C2), 76.74 s (C3), 29.86 t (128) (C4), 25.58 t (128)
were reported in [3].
Compound IIb. Found [M]+: 168.11495. C10H16O2.
(C5), 46.44 d (129) (C6), 18.87 q (126) (C7), 48.41 q
(141) (C8), 145.85 s (C9), 112.55 t (155) (C10),
19.73 q (126) (C11).
1
Calculated M: 168.11502. H NMR spectrum, , ppm
(J, Hz): 1.38 s (C9H3), 1.55 br.s (C10H3), 1.63 m
(C8H3), 1.63 m (4-H), 1.81 d.d.d (4 -H, J4 , 4 = 14,
J4 , 5 = 8.5, J4 , 5 = 5.5), 1.96 2.26 m (2H, 5-H), 3.11 d
Compound V. Mass spectrum: Found [M H2O]+
(fragment ion): m/z 182.13049. C11H18O2. Calculated:
(2-H, J2, 1 = 5), 5.00 t.q.q (6-H, J6, 5 = 7, J6, 8 = 1.5,
182.13067. 1H NMR spectrum, , ppm (J, Hz):
J6, 10 = 1.5), 9.38 d (1-H, J = 5). 13C NMR spectrum,
C, ppm: 198.74 d (C1), 64.47 d (C2), 64.42 s (C3),
33.27 t (C4), 24.04 t (C5), 122.27 d (C6), 133.15 s
(C7), 25.44 q (C8), 21.97 q (C9), 17.45 q (C10).
1.18 s (C7H3), 1.33 m (5-Heq), 1.43 d.d.d.d (5-Hax,
J5-ax, 5-eq = 12.5, J5-ax, 4-ax = 12.5, J5-ax, 6-ax = 12.5,
J5-ax, 4-eq = 4), 1.51 d.d.d (4-Hax, J4-ax, 4-eq = 12.5, J =
12.5, J4-ax, 5-eq = 4), 1.58 m (4-Heq), 1.69 d.d (C11H3,
J11, 10 = 1.5, J11, 10 = 1), 2.08 br.s and 2.66 br.s (2H,
1
Compound III. H NMR spectrum, , ppm (J, Hz):
1.57 br.s (C8H3), 1.63 br.s (C7H3), 2.08 s (C1H3),
OH), 2.24 d.d.d (6-Heq, J6-ax, 5-ax = 12.5, J6-ax, 1-ax
=
2.19 br.t.d (2H, 4-H, J4, 3 = 7, J4, 5 = 7), 2.39 t (2H,
3-H, J3, 4 = 7), 5.00 t.q.q (5-H, J = 7, J5, 7 = 1.5, J5, 8
=
11, J6-ax, 5-eq = 4), 3.13 s (OCH3), 3.62 d.d (2-Heq,
J2-eq, 1-ax = 3, J2-eq, 4-eq = 1), 3.75 d.d (1-Hax, J = 11,
3), 4.81 br.s (10-H), 4.83 d.q (10 -H, J10 , 10 = 2, J =
1.5). 13C NMR spectrum, C, ppm (1JC, H, Hz):
69.17 d (146) (C1), 73.48 d (146) (C2), 76.93 s (C3),
28.17 t (128) (C4), 24.20 t (130) (C5), 45.87 d (127)
(C6), 20.96 q (126) (C7), 48.12 q (141) (C8), 146.30 s
(C9), 113.05 t (155) (C10), 19.02 q (126) (C11).
1.5). 13C NMR spectrum, C, ppm: 29.70 q (C1),
207.62 s (C2), 43.58 t (C3), 22.43 t (C4), 122.76 d
(C5), 132.41 s (C6), 25.63 q (C7), 17.58 q (C8).
Reaction of epoxy derivatives IIa/IIb with
methanol over -zeolite. Methanol (preliminarily
dried by passing through calcined aluminum oxide),
0.5 ml, and a solution of 0.27 g of a mixture of com-
pounds IIa and IIb (at a ratio of 1:1) in 1 ml of
methylene chloride were added in succession to
a mixture of 0.4 g of -zeolite in 3 ml of methylene
chloride. After 30 min, the mixture was filtered, the
catalyst was washed with diethyl ether, and the filtrate
was combined with the washings and evaporated to
obtain 0.25 g of a crude product. The product was
subjected to column chromatography, first on SiO2
and then on SiO2/AgNO3, using hexane diethyl ether
mixtures as eluent (0.5 to 10% of diethyl ether,
gradient elution) to isolate 0.044 g of compound IV,
0.022 g of V, 0.008 g of VI, 0.011 g of VII/VIII
(isomer mixture, 4:1), 0.015 g of VII/VIII (1:2), and
0.015 g of VII/VIII (1:1).
Compound VI. Mass spectrum: Found [M H2O
CH3]+ (fragment ion): m/z 183.13054. C11H19O2.
1
Calculated: 183.13067. H NMR spectrum, , ppm
(J, Hz): 1.10 m (5-Hax), 1.15 s and 1.19 s (C10H3,
C11H3), 1.18 s (C7H3), 1.29 d.d.t (5-Heq, J5-eq, 5-ax
=
13, J5-eq, 6-ax = 4, J5-eq, 4 = 4), 1.54 m (2H, 4-H),
1.80 d.d.d (6-Hax, J6-ax, 5-ax = 13, J6-ax, 1-ax = 10.5, J =
4), 2.59 br.s and 5.10 br.s (2H, OH), 3.13 s (OC8H3),
3.23 s (OC12H3), 3.52 d (2-Heq, J2-eq, 1-ax = 3),
3.88 d.d (1-Hax, J = 10.5, 3). 13C NMR spectrum,
,
C
ppm (1JC, H, Hz): 70.72 d (144) (C1), 73.68 d (145)
(C2), 76.11 s (C3), 29.11 t (128) (C4), 21.25 t (128)
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 39 No. 7 2003

990
YAROVAYA et al.
(C5), 43.29 d (127) (C6), 20.89 q (126) (C7), 48.20 q
(140) (C8), 80.44 s (C9), 19.53 q (126) (C10 or C11),
23.62 q (125) (C11 or C10), 48.43 q (141) (C12).
(4-Hax, J4-ax, 4-eq = 13, J = 13, J4-ax, 5-eq = 4),
1.56 d.d.d.d (5-Heq, J = 13, 4, J5-eq, 6-ax = 4, J5-eq, 4-eq
=
3), 1.70 br.s (C13H3), 1.80 d.d.d (4-Heq, J = 13, 4, 3),
2.04 d.d.d (6-Hax, J = 13, J6-ax, 1-ax = 9, J = 4),
2.51 br.s and 2.81 br.s (1H each, OH), 3.38 d.d
(1-Hax, J = 9, J1-ax, 2-ax = 9) and 3.42 d (2-Hax, J = 9)
(AB system), 3.91 d.d.t (8-H, J8, 8 = 12, J8, 9 = 5,
J8, 10 = 1.5) and 3.96 d.d.t (8 -H, J = 12, J8 , 9 = 5,
J8 , 10 = 1.5) (AB system), 4.79 br.s (12-H), 4.81 d.q
We failed to isolate pure diols VII and VIII, and
the NMR spectra were recorded for their mixtures
containing mainly one or another isomer (see above).
1
Isomer VII. H NMR spectrum, , ppm (J, Hz):
1.15 s (C11H3), 1.40 d.d.d (4-H, J4, 4 = 13.5, J4, 5 = 10,
J4, 5 = 6.5), 1.54 d.d.d (4 -H, J = 13.5, J4 , 5 = 10,
J4 , 5 = 6.5), 1.59 br.s (C12H3), 1.65 br.s (C8H3),
2.05 m (2H, 5-H), 2.41 br.s (2-OH), 2.71 br.s (3-OH),
3.41 br.d (2-H, J2, 1 = 6), 3.41 s and 3.43 s (3H each,
OCH3), 4.38 d (1-H, J = 6), 5.08 t.q.q (6-H, J6, 5 = 7,
J6, 8 = 1.5, J6, 12 = 1.5). 13C NMR spectrum, C, ppm:
(12 -H, J12 , 12 = 2, J12 , 13 = 1.5), 5.06 d.d.t (10-Hcis,
J10-cis, 9 = 10, J10-cis, 10-trans = 1.5, J = 1.5), 5.20 d.d.t
(10-Htrans, J10-trans, 9 = 17, J = 1.5, 1.5), 5.84 d.d.t
(9-H, J = 17, 10, 5). 13C NMR spectrum, C, ppm:
72.05 d (C1), 79.94 d (C2), 77.77 s (C3), 33.95 t (C4),
26.28 t (C5), 50.76 d (C6), 16.47 q (C7), 62.42 t (C8),
104.46 d (C1), 73.92 d (C2), 73.03 s (C3), 38.47 t
(C4), 21.85 t (C5), 124.90 d (C6), 131.07 s (C7),
25.76 q (C8), 54.53 q (C9 or C10), 54.05 q (C10 or C9),
23.18 q (C11), 17.67 q (C12).
135.94 d (C9), 115.67 t (C10), 145.31 s (C11), 112.67 t
(C12), 19.47 q (C13).
1
Compound X. H NMR spectrum, , ppm (J, Hz):
1.20 d (C7H3, J7, 6-ax = 0.6), 1.26 m (5-Hax),
1.51 d.d.d.d (6-Heq, J6-eq, 6-ax = 13, J6-eq, 5-ax = 4,
1
Isomer VIII. H NMR spectrum, , ppm (J, Hz):
1.12 s (C11H3), 1.43 m and 1.55 m (2H, 4-H),
1.59 br.s (C12H3), 1.65 br.s (C8H3), 2.00 m (2H, 5-H),
2.50 br.s (2H, OH), 3.36 br.d (2-H, J2, 1 = 6), 3.40 s
and 3.42 s (3H each, OCH3), 4.36 d (1-H, J = 6),
5.06 m (6-H). 13C NMR spectrum, C, ppm: 104.27 d
(C1), 74.29 d (C2), 73.03 s (C3), 38.88 t (C4), 22.25 t
(C5), 124.85 d (C6), 131.11 s (C7), 25.75 q (C8),
54.61 q (C9 or C10), 54.18 q (C10 or C9), 22.44 q
(C11), 17.66 q (C12).
J6-eq,5-eq = 4, J6-eq, 2-eq = 1), 1.57 d.d.d.d (5-Heq,
J5-eq, 5-ax = 13.5, J5-eq, 4-ax = 4, J5-eq, 6-ax = 4, J = 4),
1.70 br.s (C13H3), 1.74 d.d.d (6-Hax, J = 13, J6-ax, 5-ax
=
13, J = 4), 2.32 br.s (3-OH), 2.40 d.d.d (4-Hax,
J4-ax, 5-ax = 12, J4-ax, 3-ax = 10.5, J = 4), 2.77 br.s
(1-OH), 3.49 br.d (3-Hax, J = 10.5), 3.74 d.d (2-Heq,
J2-eq, 3-ax = 3, J2-eq, 6-eq = 1), 3.90 d.d.t (8-H, J8, 8 = 13,
J8, 9 = 5, J8, 10 = 1.5) and 3.94 d.d.t (8 -H, J = 13,
J8 , 9 = 5, J8 , 10 = 1.5) (AB system), 4.79 br.s (12-H),
Reaction of compounds IIa and IIb with allyl
alcohol over -zeolite. Allyl alcohol (preliminarily
dried by boiling over K2CO3 and purified by fractional
distillation; bp 96 C), 0.6 ml, and a solution of 0.3 g
of a 1:1 mixture of compounds IIa and IIb in 1 ml
of methylene chloride were added in succession under
stirring to a mixture of 0.4 g of -zeolite and 3 ml
of methylene chloride. After 1 h, the mixture was
filtered, the catalyst was washed with diethyl ether,
and the filtrate was combined with the washings and
evaporated to obtain 0.27 g of a crude product. The
product was purified from tars by passing through
a column charged with Al2O3. We thus isolated
0.156 g of a mixture containing compounds IX and
X at a ratio of 1:2 and 10% of unidentified products.
This mixture was subjected twice to chromatographic
separation on silica gel (gradient elution with hexane
diethyl ether, 0.5 to 50% of the latter) to isolate
0.035 g of compound IX and 0.042 g of X.
4.82 d.q (12 -H, J12 , 12 = 2, J12 , 13 = 1.5), 5.10 d.d.t
(10-Hcis, J10-cis, 9 = 10, J10-cis, 10-trans = 1.5, J = 1.5),
5.22 d.d.t (10-Htrans, J10-trans, 9 = 17, J = 1.5,
J10-trans, 8 = 1.5), 5.86 d.d.t (9-H, J = 17, 10, 5). 13C
NMR spectrum, C, ppm: 77.23 s (C1), 74.33 d (C2),
70.92 d (C3), 46.40 d (C4), 25.45 t (C5), 30.33 t (C6),
19.60 q (C7), 62.04 t (C8), 135.24 d (C9), 116.18 t
(C10), 145.78 s (C11), 112.60 t (C12), 19.63 q (C13).
Transformation of epoxy derivatives IIa and IIb
in HSO3F SO2FCl at 115 C. A solution of 0.3 g
of a 1.5:1 mixture of compounds IIa and IIb in
1.8 ml of methylene chloride was added at 115 C
to a solution of 2.8 g (1.6 ml) of HSO3F in 6.4 ml
of SO2FCl. The mixture was vigorously stirred for
5 min at that temperature and was poured into 25 ml
of CH3OH Et2O. Yield of the crude product 0.24 g.
By column chromatography on silica gel using
hexane diethyl ether as eluent (gradient elution, 0 to
20% of diethyl ether) we isolated 0.04 g of compound
1
Compound IX. H NMR spectrum, , ppm (J, Hz):
1.16 s (C7H3), 1.31 d.d.d.d (5-Hax, J5-ax, 5-eq
=
1
J5-ax, 4-ax = J5-ax, 6-ax = 13, J5-ax, 4-eq = 4), 1.49 d.d.d
XI. IR spectrum (CCl4), , cm : 3464 (O H),
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 39 No. 7 2003

ACID-CATALYZED REACTIONS OF 2,3-EPOXY DERIVATIVES
991
1
1711 (C O). H NMR spectrum, , ppm (J, Hz):
database (project no. 00-03-32721) through the STN
Center, Novosibirsk Institute of Organic Chemistry,
Siberian Division, Russian Academy of Sciences.
1.06 d (C11H3, J11, 6 = 6.5), 1.21 s and 1.28 s (3H
each, C8H3 and C9H3), 1.25 m (5-Hax), 1.52 d.d.d.d
(4-Hax, J4-ax, 4-eq = 13, J4-ax, 5-ax = 13, J4-ax, 3-ax = 12,
J4-ax, 5-eq = 3.5), 1.72 m (3-Hax, J = 12, J3-ax, 2-ax = 11,
J3-ax, 4-eq = 3.5), 1.93 d.d.d.d (4-Heq, J = 13, 3.5,
REFERENCES
1. Gerout, V., Usp. Khim., 1989, p. 1736.
J4-eq, 5-ax = 3.5, J4-eq, 5-eq = 3.5), 2.07 d.d.d.d (5-Heq,
J5-eq, 5-ax = 13, J5-eq, 6-ax = 6.5, J = 3.5, 3.5),
2.38 d.q.d.d (6-Hax, J6-ax, 5-ax = 13, J = 6.5, 6.5,
J6-ax, 2-ax = 1.5), 3.16 s (OCH3), 4.02 br.m (2-Hax,
J = 11, J2-ax, OH = 2, J = 1.5). 13C NMR spectrum,
C, ppm: 211.79 s (C1), 76.72 d (C2), 54.52 d (C3),
24.10 t (C4), 34.37 t (C5), 43.09 d (C6), 76.72 s (C7),
2. Glushko, A.P., Samsonova, V.N., Malinovskii, M.S.,
and Yanovskaya, L.A., Izv. Akad. Nauk SSSR, Ser.
Khim., 1980, no. 5, p. 1048.
3. Marty, M., Stoeckli-Evans, H., and Neice, R., Tetra-
hedron, 1996, vol. 52, p. 4645.
4. Mori, N. and Kuwahara, Y., Tetrahedron Lett., 1995,
vol. 36, p. 1477.
5. Narco, K., Baltas, M., Escudier, J., and Gorrichon, L.,
24.34 q (C8 or C9), 22.54 q (C9 or C8), 48.65 q (C10),
Tetrahedron, 1996, vol. 52, p. 9047.
14.19 q (C11).
The authors are grateful to the Russian Foundation
for Basic Research for the licence for using the STN
6. Osadchii, S.A., Polovinka, M.P., Korchagina, D.V.,
Pankrushina, N.A., Dubovenko, Zh.V., and Bar-
khash, V.A., Zh. Org. Khim., 1981, vol. 17, p. 1211.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 39 No. 7 2003