Acid-catalyzed reactions of camphene and α-fenchene epoxides

Article abstract of DOI:10.1023/A:1020335019901

Isomerization of camphene and α-fenchene epoxides under homogeneous and heterogeneous conditions in media of various acidity was studied. The intermolecular reactions of these epoxy compounds with unsaturated aldehydes, allyl alcohol and methanol on askanite-bentonite clay yielded spiroacetals, and open-chain hydroxyethers and acetals. The results obtained are compared to those for reactions with the initial monoterpenes.

Full text of DOI:10.1023/A:1020335019901

Russian Journal of Organic Chemistry, Vol. 38, No. 6, 2002, pp. 810 822. Translated from Zhurnal Organicheskoi Khimii, Vol. 38, No. 6, 2002,
pp. 852 864.
Original Russian Text Copyright
2002 by Yarovaya, Korchagina, Gatilov, Barkhash.
Acid-catalyzed Reactions of Camphene and -Fenchene
Epoxides
O. I. Yarovaya, D. V. Korchagina, Yu. V. Gatilov, and V. A. Barkhash
Vorozhtsov Novosibirsk Institute of Organic Chemistry, Siberian Division, Russian Academy of Sciences,
Novosibirsk, 630090 Russia
Received June 18, 2001
Abstract Isomerization of camphene and -fenchene epoxides under homogeneous and heterogeneous
conditions in media of various acidity was studied. The intermolecular reactions of these epoxy compounds
with unsaturated aldehydes, allyl alcohol and methanol on askanite-bentonite clay yielded spiroacetals, and
open-chain hydroxyethers and acetals. The results obtained are compared to those for reactions with the
initial monoterpenes.
Acid-catalyzed reactions of epoxy derivatives of
natural substances are of great importance for the
chemistry of terpenes. In the present study we
investigated intra- and intermolecular reactions of
camphene epoxides II, III and -fenchene epoxides
V, VI under homogeneous and heterogeneous condi-
tions. Although the epoxides under investigation were
prepared previously [1, 2], their acid-catalyzed intra-
and intermolecular reactions are poorly understood.
Besides we compared these reactions with analogous
transformations of the initial bicyclic monoterpenes in
order to establish the effect of the way of cationic
We studied acid-catalyzed reaction of a mixture of
optically active epoxides II and III, and of a mixture
of epoxides V and VI in a system HSO3F SO2FCl at
90 C. The acid solutions were quenched with
CH3OH (C2H5)2O mixture. From epoxy compounds
II and III a racemic 2,2-dimethyl-3-endo-dimethoxy-
methylbicyclo[2.2.1]heptane (VIIa) was obtained
(Scheme 2), and epoxy compounds V and VI yielded
racemic 7,7-dimethyl-3-endo-dimethoxymethylbi-
cyclo[2.2.1]heptane (VIIb). The products VIIa, b are
racemic, thus before the ion takes up a methanol
molecule it undergoes rearrangements resulting in
center formation on the result of a cationoid rearrange- racemization.
ment.
Scheme 2.
Epoxides II, III and V, VI obtained by treating
with peracetic acid camphene (I) and -fenchene (IV)
formed in 2.3 : 1 and 1: 1 ratio respectively
(Scheme 1). Initial -fenchene (IV) was prepared by
acetolysis of -fenchol tosylate as described in [3].
The epoxides used further in reactions contained the
isomers in the above indicated ratio.
Scheme 1.
II, R = CH3, R = H; III, R = CH3, R = H; V,
R = H, R = CH3; VI, R = H, R = CH3; VIIa,
R = CH3, R = H; VIIb, R = H, R = CH3.
The variation of the acid medium provides a pos-
sibility to change the character of the arising products
and to manage their ratio. The isomerization of epoxy
compounds II and III on a solid superacid TiO2/SO42
or askanite-bentonite clay furnished a mixture of
2,2-dimethyl-3-endo- (VIIIa) and 2,2-dimethyl-3-exo-
formylnorbornanes (IXa) with aldehyde VIIIa
1070-4280/01/3806-810$27.00 2002 MAIK Nauka/Interperiodica

ACID-CATALYZED REACTIONS OF CAMPHENE
811
Scheme 3.
II, R = CH3, R = H; III, R = CH3, R = H; V, R = H, R = CH3; VI, R = H, R = CH3; VIIIa, R =
CH3, R = H; IXa, R = CH3, R = H; VIIIb, R = H, R = CH3; IXb, R = H, R = CH3.
prevailing, whereas the isomerization of the same
epoxides II and III mixture in the formic acid
provided mainly aldehyde IXa (Scheme 3).
from camphene. We showed that at quenching by a
mixture CH3OH (C2H5)2O of a solution of compound
I in acid system HSO3F SO2FCl a racemic product was
isolated, 2,2,3-trimethyl-3-exo-methoxynorbornane
(X) originating from capture of cation B with a
methanol molecule (Scheme 4).
Isomerization of epoxides V and VI on hetero-
geneous catalysts also resulted in formation of
aldehydes with considerable prevalence of 7,7-di-
methyl-3-endo-formylnorbornane (VIIIb), and in
formic acid epoxides V and VI were converted into
isomers VIIIb and IXa in 1: 1 ratio. The aldehydes
VIIIa, b, IXa) in contrast to compounds VIIa, b are
optically active; thus the ratio of rates of 1,2-hydride
shift in ion A arising at the opening of the epoxy ring
in compounds II, III, V, VI, and the rates of the
other rearrangements leading to racemization depends
on the nature of the medium:
The isomerization of the other initial olefin IV
in superacid media at various temperature led to re-
arrangement of the fenchane skeleton and its opening
into a monocyclic allyl cation [6].
We studied intermolecular reactions of epoxides
II, III, V, VI with oxygen-containing compounds in
the presence of heterogeneous catalysts, and we
compared these processes with similar reactions of
camphene (I). As was shown [7], camphene (I) with
unsaturated aldehydes and ketones on wideporous
zeolite provided either compound XI, a product of
[3+2]-carbocyclization with methacrolein, or com-
pounds XII that could be formally regarded as pro-
ducts of -substitution of a hydrogen atom in the
molecule of the initial compound (Scheme 5).
VIIIa:IXa VIIIb:IXb
Askanite-bentonite clay, 20 C
TiO2/SO24 , 20 C
HCOOH, 100 C
9: 1
9: 1
1: 6
7: 1
5: 1
1: 1
The isomerization of the initial bicyclic mono-
terpenes was investigated earlier. It is known [4] that
isomerization of an optically active camphene (I) in
acid medium results in racemization. In a superacid
[5] a stable camphene-hydrocation B was generated
In both cases the positively charged -olefin carbon
of the carbonyl compound attacks the double bond of
camphene with conservation of the carbonyl group.
Reactions of epoxides II, III with aldehydes (acrolein,
methacrolein, crotonic aldehyde), and epoxides V, VI
Scheme 4.*
*
Here and hereinafter we use the following notation of protons: H7an is 7anti-H, H7c is syn-H; x is exo, n is endo.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 38 No. 6 2002

812
YAROVAYA et al.
with acrolein on askanite-bentonite clay follow
another route. The reaction products are spiroacetals
XIII containing a 1,3-dioxolane ring (Scheme 6). The
structure of 3,3-dimethylbicyclo[2.2.1]heptane-2(S)-
spiro-5 -(2 -allyl-1 ,3 -dioxolane) (XIIIa), 3,3-di-
methylbicyclo[2.2.1]heptane-2(S)-spiro-5 -(2 -propen-
yl-1 ,3 -dioxolane) (XIIIb), 3,3-dimethylbicyclo-
[2.2.1]heptane-2(S)-spiro-5 -(2 -isopropenyl-1 ,3 -di-
oxolane) (XIIIc), 7,7-dimethylbicyclo[2.2.1]heptane-
2(S)-spiro-5 -(2 -allyl-1 ,3 -dioxolane) (XIIId) was
established from NMR spectra.
reveal the most stable and thermodynamically feasible
reaction products we performed on models calcula-
tions, semiempirical (AM1) for cations and by
molecular mechanics (MMX) for neutral compounds.
According to the calculations the protonation of
epoxides II and III with no barrier provides the same
cation A (Scheme 7, values H0f , G , kcal mol ).
1
Further reaction may take different routes: either the
carbocation reacts with the oxygen of the aldehyde
yielding an intermediate compound D, or the 1,2-
hydride shift results in cation C. Cation C may either
eliminate a proton to form aldehyde VIIIa or react
with aldehyde to afford 1,3-dioxetane XV; however
the latter compound was not observed. As show the
calculations, compound XV is less stable than spiro-
acetal XIV. Therefore, since the acetal formation is
reversible, the more stable 1,3-dioxolanes XIV
should form as we actually observe.
The side reaction, isomerization of the initial
epoxides, affords the corresponding aldehydes. The
ratio of the sum of isomerization products VIIIa +
IXa to the products of the intermolecular reaction
XIIIa, b, c in reactions of epoxides II, III with
aldehydes amounted to 1: 1 and did not depend on
the temperature; in reaction of epoxides V, VI with
acrolein this ratio was (VIIIb + IXb): (XIIId) =
1: 0.6.
The choice between the alternative structures
XIVa and XIVb in reactions of epoxides II, III with
aldehydes and of epoxides V, VI with acrolein was
made as follows. The calculations by MMX proce-
dure show, that compounds XIVa and XIVb are
Let us consider the probable mechanism of spiro-
acetals XIIIa d formation in more detail. In order to
Scheme 5.
R = H, CH3.
Scheme 6.
II, R1 = CH3, R2 = H; III, R1 = CH3, R2 = H; V, R1 = H, R2 = CH3; VI, R1 = H, R2 = CH3; XIIIa, R3 = H,
R4 = H; XIIIb, R3 = CH3, R4 = H; XIIIc, R3 = H, R4 = CH3.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 38 No. 6 2002

ACID-CATALYZED REACTIONS OF CAMPHENE
813
Scheme 7.
equally stable; also the configuration of CH3 group in
the heteroring does not notably affect the stability
of compounds XIVb and XIVc.
Yet it is known that nucleophiles attack the
3,3-substituted 2-norbornyl cations predominantly
from the exo-side both in the liquid acids [8] and on
aluminosilicate catalysts [9], whereas the 7,7-sub-
stituted 2-norbornyl cations are subjected to attack
from the endo-side. Therefore we ascribed to the
oxygen atom of the heteroring in the forming spiro-
acetals exo-orientation in compounds XIIIa c and
endo-orientation in compound XIIId.
In reaction of epoxides II, III with crotonic
aldehyde the arising spiroacetal XIIIc at standing
Scheme 8.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 38 No. 6 2002

814
YAROVAYA et al.
Scheme 9.
XVII
XVIII
4.8
1.5
6
(a) R1
(b) R1
(c) R1
=
=
=
CH3, R2
CH3, R2
=
=
H, R3
H, R3
=
=
=
CH=CH2
H
CH=CH2
1
1
1
H, R2
=
CH3, R3
XVIIIb VIIa
isomerizes into acetal XVIc with the endo-position of
the oxygen in the heteroring (Scheme 8). At room
temperature the isomer ratio of XIIIc and XVIc
attains the value of 1: 1.
of trans-1,2-bifunctional molecules [11], but these
processes also are poorly understood. In our case
main products are acetals XVIII. We calculated
stability of the final products XVIIb and XVIIIb in
reactions between epoxides II, III and methanol. The
stability of hydroxyether XVIIb should be compared
not directly with acetal XVIIIb, but with its isomer,
semiacetal XIX that is a precursor of acetal XVIIIb.
Here also, as in reaction with aldehydes, the direction
of the process is determined by the stability of the
Compound XIIIc, as also compounds XIIIa, b, d,
is optically active, but acetal XVIc is racemic. This
is an evidence of primary formation of acetal XIIIc
that further isomerizes into compound XVIc. The
racemization does not occur at the stage of ion A
formation,for ion A is rapidly trapped by aldehydes.
The racemization of acetal XVIc may be rationalized
by Scheme 8.
1
product, and compound XIX is by 10 kcal mol
more stable than compound XVIIb.
It should be noted that reactions of epoxides with
aldehydes were known [10], and Lewis acids were
used as catalyst; however the processes occurring
here were poorly investigated, and no spiroacetals
were reported as products.
The reactions of epoxides II, III with allyl alcohol
and methanol and epoxides V, VI with allyl alcohol
carried out on askanite-bentonite clay provide hydro-
xyethers XVII and acetals XVIII (Scheme 9); along-
side this process occurs isomerization of epoxides into
the corresponding aldehydes.
Thus whereas in reactions of epoxy compounds II,
III, V, VI with aldehydes on clay arise spirocyclic
acetals XIIIa d, and therewith the epoxides are
precursors of 1,2-diols, in reactions of the same
epoxides II, III, V, VI with alcohols they provide the
aldehyde fragment of open-chain acetals. In the latter
The main products in reactions of epoxides with
alcohols are usually hydroxyethers. The opening of
the epoxy ring is an important method for preparation
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 38 No. 6 2002

ACID-CATALYZED REACTIONS OF CAMPHENE
815
Scheme 10.
R = CH2CH=CH2.
reactions the skeleton of the initial bicyclic terpene
remains intact.
C10H2 group appear as doublets of AB-system with
chemical shifts characteristic for CH2OH substituent
(3.60 and 3.65 ppm) [13], and the signal at 3.65 ppm
is a broadened doublet that sharply narrows in the
double resonance spectrum at decoupling from the
proton of the hydroxy group at 2.00 ppm indicating
that the latter is a neighboring group, In the 13C NMR
spectrum the chemical shift of C10 carbon atom also
proves the presence of CH2OH and not CH2OCH3
Yet in the reaction we previously studied between
olefin I and allyl alcohol on zeolite [12] the process
took another route: Deep rearrangements occurred in
the skeleton of the initial terpene affording finally a
mixture of alkoxylation products (Scheme 10).
All the intramolecular reactions studied occur only
in the presence of the heterogeneous catalyst and are
not realized in acetic acid medium. The use in these
reactions of environmentally friendly solid catalysts
(clay, zeolites, solid superacids) extends the op-
portunities of synthetic application for the easily
available natural compound camphene and its isomer,
-fenchene.
1
group [14]. In both H and 13C NMR spectra of com-
pound XVIIa the chemical shifts of C10H2 are similar
to those in the spectra of compound XVIIb thus
suggesting that a hydroxymethyl group is attached to
C3 atom.
The presence of a hydroxymethyl group in com-
pound XVIIc was demonstrated by LRJMD spectra:
on decoupling from both protons of the C10H2 group
with a signal at 3.45 ppm a signal from carbon atom
C11 is lacking in the LRJMD spectrum; the signal
should have appeared for the C10H2OC11H2CH=CH2
group attaked to the C3 atom. On decoupling from
protons of the C11H2 group giving a signal at
3.81 ppm in the LRJMD spectrum is absent the signal
from C10 atom, but appears the signal from the C3
atom at 86.74 ppm confirming the bonding of the OR
group to the latter and not to the C10 carbon atom.
The structure of all compounds obtained was
1
established from H and 13C NMR spectra; elemental
composition was confirmed by high-resolution mass
spectra. Let us consider some problems in deriving
structure of the new compounds obtained from the
NMR spectra.
The exo-orientation of H3 in compounds VIIa,
VIIIa, and XVIIIa is confirmed by the presence in
1
the H NMR spectra of W-coupling constant with
atoms H5x (4J3x,5x 1 2 Hz) and the lack of W-coupling
constants with H7an atoms. The value of coupling
constant of H3 protons with H4 protons equal to 4 Hz
also testifies to their exo-position in the above com-
The assignment of methyl group signals in the
1H NMR spectra of compounds VIIa, VIIIa, XIa,
and XVIIIa was carried out by analogy with the
published data for the related structures [15], and the
signals in the 13C NMR spectra were attributed from
3
pounds (in case of endo-orientation the value J3,4
should be less than 1 Hz).
1
the data of two-dimensional 13C H spectra.
For compounds VIIb, VIIIb and XVIIIc the exo-
1
orientation of H3 protons is proved by coupling with
Analysis of H NMR spectra of compounds VIIb,
3
H5x protons (4J3,5x 2 Hz) and by value of J3x,4
VIIIb, IXb, XIIId, XVIIc and XVIIIc demonstrated
that the chemical shifts of one among the methyl
groups are in all cases of close values(0.92
0.97 ppm), and those of the second methyl group are
different (0.71 1.20 ppm). Since the substituents in
the molecules are different only at the C3 atom, they
should more affect the C9H3 group, and consequently
the changing chemical shifts belong to this methyl
group. It was concluded from the above reasoning
that the methyl groups C8H3 have a signal at 0.92
4 Hz. In compound IXa the coupling of H3 proton
with H7an (4J3,7an 2 Hz) and lack of coupling with
H4 and H5x protons is an evidence of the endo-posi-
tion of H3 proton.
In compound XVIIb the addition of a methoxy
group to the C3 carbon and of an oxy group to C10
carbon and not vice versa was proved by the follow-
1
ing data. In the H NMR spectrum the protons of
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 38 No. 6 2002

816
YAROVAYA et al.
Table 1. 13C NMR spectra of compounds synthesized ( , ppm)
Carbon
atom
II
III
V, VI
VIIa
VIIb
VIIIa
number
1
2
3
4
5
6
7
8
9
48.28 d
38.81 s
71.92 s
45.00 d
23.69 t
24.92 t
35.67 t
47.97 t
23.60 q
24.06 q
48.81 d
37.32 s
71.32 s
43.65 d
23.23 t
24.10 t
35.01 t
51.51 t
27.42 q
21.08 q
44.95 d
36.98 t
66.56 s
49.52 d
22.78 t
28.28 t
47.02 s
55.89 t
21.43 q
21.64 q
44.89 d
38.41 t
66.85 s
50.30 d
24.59 t
27.74 t
46.88 s
48.63 t
21.22 q
21.43 q
49.48 d
37.05 ©
50.89 d
40.26 d
21.64 t
24.73 t
37.15 t
32.57 q
20.99 q
103.52 d
43.84 d
33.09 t
39.93 d
45.59 d
22.42 t
29.50 t
47.26 s
21.25 q
20.89 q
106.51 d
52.65a q
51.32a q
49.14 d
39.08 ©
63.39 d
39.95 d
21.99 t
24.43 t
37.22 t
32.52 q
23.01 q
204.21 d
10
11
12
49.85a
53.26a q
q
a
Here and hereinafter: the chemical shift values marked with the same letters should probably be interchanged within the same
column.
Table 2. 13C NMR spectra of compounds synthesized ( , ppm)
Carbon
atom
XIIIa
IXa
VIIIb
IXb
X
(1JC n, Hz)
XIIIb
XIIIc
number
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
48.16 d
42.42 s
65.27 d
39.12 d
27.97 t
24.21 t
37.14 t
25.54 q
28.30 q
203.00 d
44.35 d
28.55 t
53.20 d
45.66 d
23.78 t
28.98 t
47.81 s
20.69 q
20.90 q
203.89 d
43.71 d
31.16 t
56.43 d
45.90 d
49.80 d
44.68 s
83.92 s
44.52 d
23.46 t
24.24 t
34.23 t
49.06 d (141)
42.74 s
90.64 s
49.00 d
42.40 s
90.82 s
45.56 d
22.38 t
24.14 t
35.10 t
48.94 d
42.68 s
90.29 s
46.40 d
22.35 t
23.99 t
35.16 t
46.44 d (141)
22.58 t (131)
24.15 t (131)
35.26 t (133)
26.04b q (126)
24.09b q (126)
67.67 t (146)
102.86 d (166)
135.20 d (158)
119.06 t (157)
29.70b
28.70b
t
t
46.12 s
21.27 q
22.12 q
203.07 d
25.37b
24.12b
q
q
25.47b
q
q
25.95b
q
q
24.32b
23.99b
15.28 q
49.60 q
67.05 t
104.14 d
142.49 s
114.76 t
16.30 q
67.74 t
103.11 d
128.43 d
131.49 d
17.57 q
0.97 ppm, and C9H3 groups at 0.71 1.20 ppm. The
assignment of these groups signals in the 13C NMR
spectra was performed with the use of a two-dimen-
EXPERIMENTAL
1H and13C NMR spectra were recorded on spectro-
meter Bruker AM-400 at operating frequencies
400.13 and 100.61 MHz respectively, as solvent was
used a mixture CDCl3 CCl4, 1: 1, as internal refer-
1
sional correlation 13C H procedure COSY.
The presence in compound XIIIa of a 1,3-dioxo-
lane ring was confirmed by the values of direct coupl-
ence served the chloroform signals (
7.24 ppm,
H
1
ing constants JC H between C10 and C11 carbons
76.90 ppm). The structure of compounds was
C
obtained from the monoresonance spectra (see
EXPERIMENTAL, cf. [16]).
established with the use of NMR spectra analysis:
from the coupling constants estimated by the double
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 38 No. 6 2002

ACID-CATALYZED REACTIONS OF CAMPHENE
Table 3. 13C NMR spectra of compounds synthesized ( , ppm)
817
Carbon
atom
XVIc
XIIId
XVIIa
XVIIIa
XVIIb
XVIIc
XVIIIc
number
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
49.11 d
42.98 s
90.78 s
47.97 d
23.39 t
23.93 t
35.00 t
45.26 d
47.60 t
87.94 s
51.65 d
22.77 t
27.22 t
48.32 s
21.90 q
22.77 q
75.02 t
103.92 d
136.18 d
118.54 t
50.15 d
44.75 s
86.12 s
42.56 d
21.99 t
24.07 t
34.75 t
49.40 d
36.95 s
51.66 d
40.27 d
21.42 t
24.62 t
36.99 t
32.44 q
20.99 q
101.81 d
50.00 d
44.32 s
85.57 s
41.60 d
21.77 t
24.01 t
34.49 t
44.32 d
40.68 t
86.74 s
49.01 d
22.52 t
27.42 t
47.89 s
22.77 q
22.77 q
63.48 t
62.44 t
135.08 d
115.95 t
43.95 d
33.32 t
40.59 d
45.73 d
22.42 t
29.57 t
47.36 s
21.38 q
21.01 q
104.19 d
25.32b
q
q
26.00b
22.81b
q
q
25.82b
22.72b
q
q
23.91b
66.84 t
104.62 d
129.62 d
130.78 d
59.92 t
62.24 t
135.32 d
115.12 t
59.14 t
49.23 q
63.89b
t
64.89b
t
135.05c d
135.15c d
115.94 t
115.80d
66.82b
t
t
65.77b
t
17.51 q
134.65c d
135.08c d
115.94 t
115.90d
t
1
resonance 1H H spectra, from 13C NMR mono-
resonance spectra, spectra obtained with selective and
off-resonance proton decoupling, and from two-di-
askanite-bentonite clay the catalyst used was calcined
just before the experiment in a microwave oven for
10 min at a power 450 W or for 3 h in a thermostat
cabinet at 110 C. The askanite bentonite clay was
obtained by acid activation of bentonite clays from
Askanian deposits and corresponded to the standard
113-12-86-82. The sulfate of titanium oxide
(TiO2/SO24 ) was calcined for 2 h at 400 C, and wide-
1
mensional 13C H correlation spectra on direct coupl-
1
ing constants (COSY, the applied value JC H
135 Hz) and unidimensional 13C H correlation
1
spectra on remote constants (LRJMD, experimental
conditions optimized for remote constants JC H
10 Hz). The data of 13C NMR spectra are presented
in Tables 1 3.
porous
zeolite HB-2 (SiO2/Al2O3 40) with pore
diameter 0.75 0.80 nm, and with oxides content
Na2O 0.04%, Al2O3 5.14%, SiO2 81.57% was
calcined before the reaction for 2 h at 500 C. The
zeolite was produced at Research Center Zeosit
The purity of the initial compounds was checked
and the reaction products were analyzed by GLC on
Biokhrom-1 chromatograph equipped with flame-
ionization detector and two columns: glass capillary
column 53000 0.26 mm, stationary phase XE-60, and
capillary quartz column 13000 0.22 mm, stationary
phase BS-30 (analog of SE-30), carrier gas helium.
The products were separated by column chromato-
graphy on silica gel (Czechia, 40 100 ), 20%AgNO3
on SiO2, on alumina and alkaline alumina (II Brock-
mann activity). Elemental composition of compounds
obtained was derived from high-resolution mass
spectra measured on Finnigan MAT 8200 instrument.
The optical rotation was measured on Polamat A
polarimeter. The ion salts were prepared in a double
distilled HSO3F (bp 158 161 C). For dilution was
used SO2FCl purified by passing through sulfuric
acid. As a nucleophilic quenching solution was
applied a methanol ethyl ether mixture (5: 2 by
volume). In reactions carried out in the presence of
(Novosibirsk). In the study was used -fenchol Fluka,
20
[ ]
10.1, 98% purity, and camphene containing
580
20
17% of tricyclene, [ ] 10.6 (CHCl3, c 11.7).
580
Epoxidation of camphene (I) with peracetic acid.
A mixture of 0.8 g of olefin I (5.8 mmol), 13 ml
(6.8 mmol) of a solution of CH3COOOH in CH2Cl2
(extracted from a mixture of 200 ml of CH3COOH,
200 ml of 30% H2O2, and 10 ml of concn. H2SO4 and
titrated with sodium thiosufate), and 0.9 g of
anhydrous Na2CO3 was kept for 3 h. The reaction
mixture was treated with saturated solution of
Na2CO3, with water till neutral washings, and dried
with $Na2SO4. The weight of crude product 0.89 g.
Epoxides II, III were separated from unreacted
compound I by column chromatography on Al2O3,
eluent hexane. We isolated 0.18 g of tricyclene with
camphene impurity and 0.51 g of a mixture of
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 38 No. 6 2002

818
YAROVAYA et al.
20
epoxides II and III in 2.3 : 1 ratio, [ ] of mixture
J5x,6q 13, J5x,4 5, J5x,6n 3.5), 1.53 d.d.d.d (H6n, J6n,6x
12.5, J6x,5n 9, J 3.5, J6n,7s 2.5), 1.65 d.m (H1, J1,6q
4), 1.93 d.d.d.d.d (H7s, J 10, 2.5, J7c,5n 2, J7s,1 1.5,
580
5.15 (CHCl3, c 17.45). Further in the experiments
was used the mixture containing epoxides II and III
in this ratio. Mass spectra of the isomers were
identical. Found: M 152.12034. C10H16O. Calculated:
J7s,4 1.5), 2.24 d.d.d.d (H4, J 5, 1.5, 1.5, J4,1 1.5),
3.10 s (OCH3).
1
M 152.12011. H NMR spectrum of compound II ( ,
Isomerization of epoxides II, III in formic acid.
To 4 ml of HCOOH was added 0.15 g of the mixture
of epoxides II, III. The reaction mixture was boiled
for 1 h on an oil bath, cooled, the reaction products
were extracted into hexane, the extract was washed
with a water solution of Na2CO3, and dried with
Na2SO4. The crude product weighed 0.128 g. Accord-
ing to GLC data the ratio of aldehydes VIIIa and IXa
in the mixture was 1:6. By chromatography on silica
ppm, J, Hz): 0.75 s and 0.78 s (C9H3, C10H3),
1.12 d.d.d (H7an, J7an,7c 10, J7an,1 1.5, J7an,4 1.5),
1.20 1.33 m (H5n, H6q), 1.50 m (H5x), 1.55
1.63 m (H1, H6n), 1.83 m (H4), 1.86 d.d.d.d.d (H7s,
J 10, J7s,6n 2.5, J7s,1 = J7s,4 = J7s,5n 1.5), 2.45 d and
2.47 d (2H8, J 4.5) AB system. H NMR spectrum of
1
compound III ( , ppm, J, Hz): 0.72 s and 0.89 s
(C9H3, C10H3), 1.21 d.d.d (H7an, J7an,7s 10, J7an,1
1.5, J7an,4 1.5), 1.28 1.78 m (5n), 1.82 d.d.d.d.d
(H7s, J 10, J7c,6n 2.5, J7s,1 = J7s,4 = J7s,5n = 1.5),
2.60 d and 2.63 d (2H8, J 5) AB system.
gel was isolated 0.84 g of aldehyde IXa with 15% of
20
580
compound VIIIa impurity, [ ]
3.24 (CHCl3, c
9.25). Found: M 152.11998. C10H16O. Calculated: M
152.12011.
Isomerization of epoxides II, III in HSO3F
SO2FCl at 90 C. To a solution of 2.9 g (1.7 ml) of
HSO3F in 6.8 ml of SO2FCl was added at 90 C a
solution of 0.36 g of the mixture of epoxides II and
III in 1.8 ml of CH2Cl2, and solution was vigorously
stirred for 5 min at the same temperature. The mix-
ture was poured into 25 ml of a mixture MeOH Et2O.
Yield of the crude product 0.314 g. From 0.1 g of
products mixture by chromatography on SiO2 was
isolated 0.04 g of compound VIIa. Mass spectrum:
fragment ion M OCH3; Found: m/z 167.14305.
1H NMR spectrum of compound IXa ( , ppm,
J, Hz): 0.98 s (C8H3), 1.13 d.d.d.d (H5n, J5n,5x 13,
J5n,6n 9, J5n,6x 5, J5n,7s 2.5), 1.14 s (C9H3),
1.24 d.d.d.d (H7an, J7an,7s 10, J7an,3n 2, J7an,1 1.5,
J7an,4 1.5), 1.35 d.d.d.d (H6x, J6x,6 13, J6x,5x 12, J 5,
J6x,1 4), 1.57 d.d.d.d (H5x, J5x,5n 13, J 12, J5x,4 5,
J5x,6n 4), 1.69 d.d.d.d (H6n, J 13, 9, 4, J6n,7s 2.5),
1.74 br.d (H1, J 4), 1.78 d.d (H3n, J3n,10 3.5, J3n,7an
2), 1.83 d.d.d.d.d (H7c, J 10, 2.5, 2.5, J7s,1 1.5, J7s,4
1.5), 2.42 br.d (H4, J 5), 9.54 d (H10, J 3.5).
1
C11H19O. Calculated: 167.14358. H NMR spectrum
of compound VIIa ( , ppm, J, Hz): 0.89 s (C9H3),
0.95 s (C8H3), 1.12 d.d.d (H7an, J7an,7s 9.5, J7an,1
1.5, J7an,4 1.5), 1.26 m (H6x), 1.31 m (2H5),
1.60 d.d.d (H3x, J3x,10 9.5, J3x,4 4, J3q,5q 1), 1.56
1.66 m (H7s, H6n), 1.71 m (H1), 2.16 m (H4, J 4,
J4,5x 3, J 1.5, J4,7s 1.5), 3.21 s and 3.26 s (2OCH3),
4.31 d (H10, J 9.5).
Reaction of epoxides II, III with acrolein on
askanite-bentonite clay. To 0.45 g of askanite-
bentonite clay calcined for 10 min in a microwave
oven at the power of 450 W and dispersed in 5 ml of
CH2Cl2 was added at stirring in succession 0.4 g
(7 mmol) of acrolein, and a solution of 0.3 g
(2 mmol) of the epoxides II and III mixture in 1 ml
of CH2Cl2. In 3 min the reaction mixture was filtered,
the clay was washed with ether, the solvents were
distilled off to afford 0.46 g of the crude product. The
product was subjected to chromatography in succes-
sion on SiO2 and SiO2/AgNO3 (gradient elution with
hexane containing from 0.5 to 2% of ethyl ether). We
isolated 0.19 g of a mixture of aldehydes VIIIa and
Isomerization of camphene I in HSO3F SO2FCl
at 90 C. To a solution of 1.3 g (0.7 ml) of HSO3F
in 2.8 ml of SO2FCl was added at 90 C a solution
of 0.1 g of compound I in 0.8 ml of CH2Cl2, and
solution was vigorously stirred for 5 min at the same
temperature. Then it was poured into 15 ml of a mix-
ture MeOH Et2O. Yield of the crude product 0.08 g.
By chromatography on SiO2 was isolated 0.055 g of
compound X. Found: M 168.15142. C11H20O. Cal-
culated: M 168.15141.
IXa in 7: 1 ratio, and 0.06 g of acetal XIIIa. The
20
580
specific rotation of the latter was [ ]
3.6 (CHCl3,
c 5.06). Found: M 208.14625. C13H O2. Calculated:
20
M 208.14632. The reaction was also carried out at 40
and 0 C, and the ratio of the isomerization products
1H NMR spectrum of compound X ( , ppm, J, Hz):
1
to the adduct was the same. H NMR spectrum of
0.86 s and 0.92 s (C8H3, C9H3), 0.93 d.d.d (H7an
,
compound XIIIa ( , ppm, J, Hz): 0.93 s and 0.97 s
(C8H3, C9H3), 1.10 m (H5n, J5n,5x 13, J5n,6n 9, J5n,6x
5, J5n,7s 2), 1.14 d.d.d (H7an, J7an,7s 10, J7an,1 1.5,
J7an,7s 10, J7an,1 1.5, J7an,4 1.5), 1.06 s (C10H3),
1.16 1.30 s (H5n, H6x), 1.40 d.d.d.d (H5x, J5x,5n 13,
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 38 No. 6 2002

ACID-CATALYZED REACTIONS OF CAMPHENE
819
J7an,4 1.5), 1.27 m (H6x), 1.50 d.d.d.d (H5x, J5x,5n 13,
J5x,6x 12, J5x,4 5, J5x,6n 3.5), 1.56 d.d.d.d (H6n, J6n,6x
12.5, J 9, 3.5, J6n,7s 2.5), 1.77 d.m (H1, J1,6x 4),
1.98 d.d.d.d.d (H7s, J 10, 2.5, 2, J7s,1 1.5, J7s,4 1.5),
2.16 d.d.d.d (H4, J 5, 1.5, 1.5, J4,1 1.5), 3.70 d and
3.87 d (2H10, J 9), 5.10 d.d.d (H11, J11,12 6,
J11,13trans 1, J11,13cis 1), 5.26 d.d.d (H13cids,
culated: M 222.16197. Compound XIIIc is unstable
and at storage transforms into an equilibrium mixture
with its geometrical isomer XVIb in the ratio 1: 1.
1H NMR spectrum of compound XIIIc ( , ppm, J,
Hz): 0.91 s and 0.96 s (C8H3, C9H3), 1.07 m (H5n),
1.12 d.d.d (H7an, J7an,7s 10, J7an,1 1.5, J7an,4 1.5),
1.25 d.d.d.d (H6x, J6x,6n 12.5, J6x,5x 12, J6x,5n 5, J6x,1
4), 1.48 d.d.d.d (H5x, J5x,5n 13, J 12, J5x,4 5, J5x,6n
3.5), 1.53 d.d.d.d (H6n, J 12.5, J6n,5n 9, J 3.5, J6n,7s
2.5), 1.73 d.d (C15H3, J15,13 6.5, J15,12 1.5), 1.75
br.d (H1, J 4), 1.95 d.d.d.d.d (H7c, J 10, 2.5, J7s,5n
2, J7s,1 1.5, J7c,4 1.5), 2.13 d.d.d.d (H4, J 5, 1.5,
1.5, J4,1 1.5), 3.66 d and 3.88 d (2H10, J 8.5), 5.06
d (H11, J11,12 7), 5.43 d.d.q (H12, J12,13 15.5, J 7,
J13cis,12 10, J13cis,13trans 1.5, J 1), 5.40 d.d.d (H13trans
,
J13trans,12 17, J 1.5, 1), 5.78 d.d.d (H12, J 17, 10, 6).
Reaction of epoxides II, III with methacrolein on
askanite-bentonite clay. To 0.45 g of askanite-
bentonite clay calcined for 10 min in a microwave
oven at the power of 450 W was added at stirring in
succession a solution of 0.4 g (5.7 mmol) of meth-
acrolein in 5 ml of CH2Cl2, and a solution of 0.3 g
(2 mmol) of the epoxides II and III mixture in 1 ml
of CH2Cl2. After workup the crude product (0.4 g)
was subjected to chromatography in succession on
SiO2 and SiO2/AgNO3 (gradient elution with hexane
containing from 0.5 to 2.5% of ethyl ether). We
isolated 0.14 g of a mixture of aldehydes VIIIa and
1.5), 5.85 d.q (H13, J 15.5, 6.5). The isomer mixture
of XIIIc and XVIc (0.2 g) was subjected to chromato-
graphy on SiO2 with gradient elution by hexane
containing from 0,5 to 2% of ethyl ether,. Thus was
separated 0.06 g of racemic compound XVIc. Found:
M 222.15995. C14H22O2. Calculated: M 222.16197.
1H spectrum of compound XVIc ( , ppm, J, Hz):
0.91 s and 0.98 s (C8H3, C9H3), 1.09 m (H5n),
IXa, and 0.05 g of acetal XIIIb. The specific rotation
20
580
of the latter was [ ] +4.0 (CHCl3, c 3.5). Found:
M 222.15984. C14H22O2. Calculated: M 222.16197.
1H NMR spectrum of compound XIIIb ( , ppm, J,
Hz): 0.89 s and 0.99 s (C8H3, C9H3), 1.13 d.d.d
1.11 d.d.d (H7an, J7an,7s 10, J7an,1 1.5, J7an,4 1.5),
1.23 d.d.d.d (H6x, J6x,6n 12.5, J6x,5x 12, J6x,5n 5, J6x,1
4), 1.48 m (H5x), 1.51 d.d.d.d (H6n, J 12.5, J6n,5n 9,
J6n,5x 3.5, J6n,7s 2.5), 1.71 d.d (C15H3, J15,13 6.5,
J15,12 1.5), 1.74 d.m (H1, J 4), 1.96 d.d.d.d.d (H7s,
J 10, 2.5, J7s,5n 2, J7s,1 1.5, J7s,4 1.5), 2.10 d.d.d.d
(H4, J4,5x 5, J4,1 1.5, J 1.5, 1.5), 3.75 d and 3.80 d
(2H10, J 9) AB system, 5.13 d (H11, J11,12 7),
5.41 d.d.q (H12, J12,13 15.5, J 7, 1.5), 5.80 d.q.d
(n13, J 15.5, 6.5, J13,11 0.5).
(H7an, J7an,7s 10, J7an,1 1.5, J7an,4 1.5), 1.14 m
(H5n), 1.26 d.d.d.d (H6x, J6x,6n 12.5, J6x,5x 12, J6x,5n
5, J6x,1 4), 1.50 m (H5x, J5x,5n 13, J 12, J5x,4 5, J5x,6n
3.5), 1.53 d.d.d.d (H6n, J 12.5, J6n,5n 9, J 3.5, J6n,7s
2.5), 1.70 d.d (C14H3, J14,13 1.5, J14,13 1.2),
1.76 d.m (H1, J 4), 1.96 d.d.d.d.d (H7s, J 10, 2.5,
J7s,5n 2, J7s,1 1.5, J7s,4 1.5), 2.18 d.d.d.d (H4, J 5,
1.5, 1.5, J4,1 1.5), 3.74 d and 3.79 d (2H10, J 8.5)
AB system, 4.94 d.q (H13, J13,13 2, J 1.5), 5.04 s
(H11), 5.09 m (H13 , J 2, 1.2, J13 ,11 1).
Reaction of epoxides II, III with allyl alcohol on
askanite-bentonite clay. To 1.5 g of clay in 3 ml of
CH2Cl2 was added at stirring 1 g of allyl alcohol
(preliminary dried by boiling with K2CO3 and
distilled through a Vigreux column, bp 96 C) and
after that 0.84 g of epoxides II, III mixture. The
stirring was continued for 2 3 min, the reaction
mixture was diluted with ether and filtered. The
weight of the reaction mixture was 1.46 g. By
chromatography on SiO2 were separated in succession
0.29 g of acetal XVIIIa, 0.066 g of hydroxyether
XVIIa, and 0.437 g of isomerization products of
epoxides II and III (aldehydes VIIIa, IXa) contain-
ing compounds XVIIIa, XVIIa as impurities. Com-
Reaction of epoxides II, III with crotonic alde-
hyde on K-10 clay. To 0.8 g of K-10 clay calcined
for 10 min in a microwave oven at the power of
450 W was added at stirring in succession a solution
of 0.7 g (0.01 mol) of crotonic aldehyde in 8 ml of
CH2Cl2, and a solution of 0.5 g (0.033 mol) of the
epoxides II and III mixture in 2 ml of CH2Cl2. After
workup the crude product (1.18 g) was subjected to
chromatography in succession on SiO2 and SiO2/
AgNO3 (gradient elution with hexane containing from
0.5 to 2.5% of ethyl ether). We isolated 0.14 g of
aldehydes VIIIa and IXa in 7: 1 ratio, 0.127 g of a
pound XVIIa. Found: M 210.1617. C13H22O2. Cal-
mixture of isomers XIIIc and XIVc in 1: 1 ratio, and
20
20
580
culated: M 210.16197. [ ]
5.8 (CHCl3, c 6.9).
0.08 g of individual acetal XIIIc, [ ]
3.9
580
1H NMR spectrum of compound XVIIa ( , ppm, J,
(CHCl3, c 8.7). Found: M 222.15994. C14H O2. Cal-
22
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 38 No. 6 2002

820
YAROVAYA et al.
Hz): 1.03 s and 1.05 s (C8H3, C9H3), 1.03 d.d.d
(H7an, J7an,7s 10, J7an,1 1.5, J7an,4 1.5), 1.14 d.d.d.d
(H5n, J5n,5x 13, J5n,6n 9, J5n,6x 5, J5n,7s 2), 1.24 d.d.d.d
(H6x, J6x,6n 12.5, J6x,5x 12, J 5, J6x,1 4), 1.40 d.d.d.d
(H5x, J 13, 12, J5x,4 5, J5x,6n 3.5), 1.59 d.d.d.d (H6n,
J 12.5, 9, 3.5, J6n,7s 2.5), 1.69 br.d (H1, J 4),
1.98 d.d.d.d.d (H7s, J 10, 2.5, 2, J7s,1 1.5, J7s,4 1.5),
2.30 d.d.d.d (H4, J 5, 1.5, 1.5, J4,1 1.5), 3.65 d and
3.74 d (2H10, J 12) AB system, 3.79 d.d.d.d (H11,
J11,11 13, J11,12 5, J11,13cis 1.5, J11,13trans 1.5),
3.94 d.d.d.d (H11 , J 13, J11 ,12 5, J11 ,13cis 1.5,
J11 ,13trans 1.5), 5.08 d.d.t (H13cis, J13cis,12 10,
C9H3), 0.96 d.d.d (H7an, J7an,7s 10, J7an,1 1.5, J7an,4
1.5), 1.07 d.d.d.d (H5n, J5n,5x 13, J5n,6n 9, J5n,6x 5,
J5n,7s 2), 1.18 d.d.d.d (H6x, J6x,6n 12.5, J6x,5x 12, J 5,
J6q,1 4), 1.34 d.d.d.d (H5x, J 13, 12, J5x,4 5, J5x,6n
3.5), 1.53 d.d.d.d (H6n, J 12.5, 9, 3.5, J6n,7s 2.5),
1.60 d.m (H1, J1,6x 4), 1.86 d.d.d.d.d (H7s, J 10, 2.5,
2, J7s,1 1.5, J7s,4 1.5), 2.00 br.s (OH), 2.26 d.d.d.d
(H4, J 5, 1.5, 1.5, J4,1 1.5), 3.11 s (OCH3), 3.60 d
and 3.65 br.d (2H10, J 12) AB system.
-Fenchene (IV). To 24.5 g of -fenchol in 70 ml
of dry pyridine was added 36.5 g of toluenesulfonyl
chloride in 70 ml of dry pyridine. The mixture was
left standing in a refrigerator for 48 h, then was dilut-
ed with 450 ml of water, the precipitate was filtered
off, washed with a mixture water hydrochloric acid
(1: 1), with water, Na2CO3 solution, and dried on
MgSO4. We obtained 37 g of -fenchol tosylate
(mp 103. C, publ. 99 C [3]). A mixture of 37 g of
tosylate and 24.9 g of anhydrous sodium acetate in
440 ml of dry acetic acid was heated for 48 h to
90 C. The reaction mixture was washed with Na2CO3
solution, the reaction products were extracted into
pentane, and the extract was dried on MgSO4. We
isolated 12 g of substance containing 95% of com-
pound IV (GLC). After separation from impurities by
J13cis,13trans 1.5, J13cis,11 1.5), 5.28 d.d.t (H13trans
,
J13trans,12 17, J 1.5, J13trans,11, 1.5), 5.87 d.d.d.d
(H12, J 17, 10, 5, 5). Compound XVIIIa. Found
(fragment ion M OCH2CH= CH2): m/z 193.15845.
20
C13H21O. Calculated: 193.15923. [ ] 1.6 (CHCl3,
580
1
c 47.0). H NMR spectrum of compound XVIIIa ( ,
ppm, J, Hz): 0.89 s (C9H3), 0.95 s (C8H3),
1.10 d.d.d (H7an, J7an,7s 9.5, J7an,1 1.5, J7an,4 1.5),
1.23 m (H6x, J6x,6n 12.5, J6x,5x 12, J6x,5n 6, J6x,1 4),
1.25 1.36 m (2H5), 1.58 d.m (H7s, J 9.5), 1.61 m
(H6n), 1.67 d.d.d (H3x, J3x,10 9.5, J3x,4 4, J3x,5x 1.2),
1.70 br.s (H1), 2.19 m (H4), 3.89 d.d.d.d and
4.11 d.d.d.d (2H11 or 2H14, J 13, 5, 1.5, 1.5),
3.96 d.d.d.d and 4.00 d.d.d.d (2H14 or 2H11, J 13,
5, 1.5, 1.5), 4.56 d (H10, J 9.5), 5.06 d.d.t and
5.07d.d.t (H13cis and H16cis, J 10, 1.5, 1.5), 5.21 d.d.t
and 5.23 d.d.t (H13trans and H16trans, J 17, 1.5, 1.5),
5.84 d.d.t and 5.86 d.d.t (H12 and H15, J 17, 10, 5).
column chromatography on SiO2 we obtained 7.5 g of
20
580
-fenchene (IV), [ ]
c 8.7).
+26.4
(CHCl3,
Epoxidation of -fenchene (IV) with peracetic
acid. A mixture of 3.04 g of olefin IV (20 mmol),
25 ml (25 mmol) of a solution of CH3COOOH in
CH2Cl2 (extracted from a mixture of 200 ml of
CH3COOH, 200 ml of 30% H2O2, and 10 ml of
concn. H2SO4 and titrated with sodium thiosufate),
and 7 g of anhydrous Na2CO3 was vigorously stirred
for 2 h. The reaction mixture was treated with
saturated solution of Na2CO3, with water till neutral
washings, and dried with Na2SO4. We isolated
3.51 g of epoxides V, VI mixture at a ratio 1: 0.75.
In further experiments was used the mixture with this
Reaction of epoxides II, III with methanol on
askanite-bentonite clay. To 1.5 g of clay in 2.5 ml of
CH2Cl2 was added at stirring 0.8 g of methanol
(preliminary dried by passing through a calcined
alumina) and after that 0.65 g of epoxides II, III
mixture. The stirring was continued for 2 3 min, the
reaction mixture was diluted with ether and filtered.
The weight of the reaction mixture was 0.735 g. By
isomers ratio. optical rotation measured for the mix-
chromatography on SiO2 were separated in succession
20
580
20
580
ture was [ ]
+18.6 (CHCl3, c 10.1). Mass
0.23 g of acetal XVIIIb, [ ]
+1.9 (CHCl3, c
spectra of the isomers were identical. Found: M
152.12028. C10H16O. Calculated: M 152.12011.
NMR spectra were recorded for the isomers mixture
11.3) that was identical to compound VIIa, 0.17 g of
hydroxyether XVIIb, and 0.17 g of isomerization
products of epoxides II and III (aldehydes VIIIa,
IXa) containing compounds XVIIIb, XVIIb as
1
with the ratio close to 1: 0.75. H NMR spectrum of
prevailing isomer ( , ppm, J, Hz): 0.95 s (C9H3),
1.09 s (C10H3), 1.19 d (H4, J4,5x 4), 1.21 d (H2n,
J2n,2x 13.5), 1.36 d.d.d (H6n, J6n,6x 12, J6n,5n 8.5,
J6n,5x 3), 1.64 d.d (H1, J1,2x 4, J1,6x 4), 1.71 1.86 m
impurities. Compound XVIIb. Found: M 184.14634.
20
C11H20O2. Calculated: M 184.14632. [ ]
2.7
580
1
(CHCl3, c 15.7). H NMR spectrum of compound
XVIIb ( , ppm, J, Hz): 0.90 s and 0.98 s (C8H3,
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 38 No. 6 2002

ACID-CATALYZED REACTIONS OF CAMPHENE
821
(2H5, H6x), 2.10 d.d.d (H2x, J 13.5, 4, J2x,6x 3),
for 1 h on an oil bath, cooled, the reaction products
were extracted into hexane, the extract was washed
with a water solution of Na2CO3, and dried with
Na2SO4. The crude product weighed 0.8 g. According
1
2.63 d and 2.80 d (2H8, J 5). H NMR spectrum of
minor isomer ( , ppm, J, Hz): 0.93 s (C9H3), 1.15 s
(C10n3), 1.14 m (H4), 1.11 1.33 m and 1.71 1.86 m
(2H5, 2H6), 1.43 d (H2n, J2n,2x 13.5), 1.69 d.d
(H1, J1,2x 4, J1,6x 4), 1.95 m (H2x, J 13.5, 4, J2x,6x 3),
2.54 d and 2.59 d (2H8, J 5) AB system.
1
to H NMR data the ratio of aldehydes VIIIb and
IXb in the mixture was 1: 1. We failed to isolate
aldehyde IXb as an individual compound, therefore
the NMR spectra were registered from the mixture
of aldehydes VIIIb and IXb in nearly equimolar
Isomerization of epoxides V, VI mixture on
askanite-bentonite clay. To 0.15 g of clay in 1 ml
of dry CH2Cl2 was added a solution of 0.15 g of
epoxides V, VI mixture in CH2Cl2. In 2 min the
reaction mixture was separated from clay by passing
through a layer of Al2O3. Weight of the crude reac-
1
ratio. H NMR spectrum of compound IXb ( , ppm,
J, Hz): 0.71 s (C9H3), 0.92 s (C8H3), 1.11 1.24 m
and 1.63 1.89 m (2H5, 2H6), 1.61 d.d (H1, J1,2x 4,
J1,6x 4), 2.08 d (H4, J4,5x 4), 1.41 m (H2n) and 2.08
2.15 m (H2x, H3n) ABΠsystem, 9.64 s (H10).
1
tion product was 0.11 g. According to H NMR spec-
Reaction of epoxides V, VI with acrolein on
askanite-bentonite clay. To 0.45 g of askanite-
bentonite clay calcined for 3 h at 110 C and dispersed
in 5 ml of CH2Cl2 was added at stirring in succession
0.4 g (7 mmol) of acrolein, and a solution of 0.3 g
(2 mmol) of the epoxides V and VI mixture in 1 ml
of CH2Cl2. In 5 min the reaction mixture was filtered,
the clay was washed with ether, the solvents were
distilled off to afford 0.404 g of the crude product.
According to GLC data the ratio of sum of isomeriz-
ation products VIIIb and IXb to the acrolein adduct
XIIId was 1.6 : 1. The chromatography in succession
on SiO2 and SiO2/AgNO3 (gradient elution with
hexane containing from 0.5 to 2% of ethyl ether)
provided 0.21 g of aldehydes VIIIb and IXb mixture,
trum, the ratio of aldehydes VIIIb to IXb was 7: 1.
Aldehyde VIIIb was isolated by column chromato-
graphy on SiO2, gradient elution with hexane contain-
ing from 0.5 to 3% of ethyl ether. We obtained 0.8 g
20
580
of compound VIIIb, [ ] +22.0 (CHCl3, © 8.7).
Found: M 152.12028. C10H16O. Calculated: M
152.12011. 1H NMR spectrum of compound VIIIb ( ,
ppm, J, Hz): 0.96 s (C8H3), 1.01 s (C9H3), 1.15 m
(H6n), 1.17 m (H5n), 1.55 d.d (H1, J1,2x 4, J1,6x 4),
1.58 1.77 m (2H2, H5x, H6x), 1.98 d.d.d (H4, J4,3x 4,
J4,5x 4, J4,1 1), 2.88 m (H3x), 9.68 br.s (H10).
Isomerization of epoxides V, VI mixture in
HSO3F SO2FCl at 90 C. To a solution of 1.3 g
(0.7 ml) of HSO3F in 2.8 ml of SO2FCl was added at
90 C a solution of 0.1 g of epoxides V, VI mixture
in 0.3 ml of CH2Cl2, and solution was vigorously
stirred for 5 min at the same temperature. Then it was
poured into 15 ml of a mixture MeOH Et2O. Yield
of the crude product 0.088 g. By chromatography on
SiO2 was isolated 0.05 g of compound VIIb. Mass
spectrum of the fragment ion M OCH3. Found: M
167.14305. C11H19O. Calculated: M 167.14358.
1H NMR spectrum of compound VIIb ( , ppm, J,
and 0.056 g of spiroacetal XIIId. For compound
20
580
XIIId [ ]
13.2 (CHCl3, c 6.8). Found: M
208.14605. C13H20O2. Calculated: M 208.14632.
1H NMR spectrum of compound XIIId ( , ppm, J,
Hz): 0.95 s (C8H3), 1.02 m (H6n), 1.10 m (H5x),
1.20 s (C9H3), 1.42 d (H2n, J2n,2x 13), 1.62 m (H1,
H4), 1.65 1.77 m (H5x, H6x), 2.13 d.d.d (H2x, J 13,
J2x,1 5, J2x,6x 2.5), 3.76 s (2H10), 5.08 d (H11, J11,12
6), 5.21 d.d.d (H13cis, J13cis,12 10, J13cis,13trans 1.5,
J13cis,11 0.5), 5.35 d.d.d (n13trans, J13trans,12 17, J 1.5,
J13trans,11 0.5), 5.74 d.d.d (H12, J 17, 10, 6). This
Hz): 0.85 d.d (H2n, J2n,2x 13, J2n,3x 5), 0.96 s (C8H3),
1.01 s (C9H3), 1.07 d.d.d (H6n, J6n,6x 12, J6n,5n 9.5,
J6n,5x 4.5), 1.44 d.d.d (H5n, J5n,5x 13, J 9.5, J5n,6x 4),
1.47 d.d (H1, J1,2x 4, J1,6x 4), 1.51 d.d (H4, J4,3x 4,
J4,5q 4), 1.63 d.d.d.d.d (H5q, J 13, J5x,6x 12, J 4.5,
4, J5x,3x 2), 1.75 d.d.d.d.d (H6x, J 12, 12, 4, 4, J6x,2x
3.5), 1.89 d.d.d.d (H2x, J 13, J2x,3x 11.5, J 4, 3.5),
2.36 d.d.d.d.d (H3x, J 11.5, J3x,10 9, J 5, 4, 2),
3.23 x and 3.25 x (2OCH3), 4.21 d (H10, J 9).
reaction was also carried out at 40 and 0 C, and
the ratio of isomerization products to spiroacetal
remained the same.
Reaction of epoxides V, VI with allyl alcohol on
askanite-bentonite clay. To 0.55 g of clay in 2 ml of
CH2Cl2 was added at stirring 0.35 g of allyl alcohol
(preliminary dried by boiling with K2CO3 and distill-
ed through a Vigreux column, bp 96 C) and after that
0.25 g of epoxides V, VI mixture. The stirring was
continued for 5 min, the reaction mixture was diluted
Isomerization of epoxides V, VI in formic acid.
To 2 ml of HCOOH was added 0.15 g of the mixture
of epoxides V, VI. The reaction mixture was boiled
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 38 No. 6 2002

822
YAROVAYA et al.
with ether and filtered. The weight of the reaction
mixture was 0.29 g. By chromatography on SiO2
were separated in succession 0.44 g of acetal XVIIIc,
0.018 g of hydroxyether XVIIc, and 0.1 g of pro-
ducts of epoxides isomerization VIIIb and IXb.
2. Huckel, W., Rothenwoehrer, W., and Vogt, O.,
Suom. Remistilehti., 1964, vol. 42, no. 4, pp. 213 216.
3. Huckel, W. and Scheel, J., Lieb. Ann., 1963, vol. 664,
p. 61.
4. Lipp, P. and Stutsinger, G., Ber., 1932, vol. 65,
p. 241.
5. Haseltine, R., Huang, E., Ranganayakulu, K., and
Sorensen, T.S., Canad. J. Chem., 1975, vol. 53,
no. 7, pp. 1056 1066.
6. Huang, E., Ranganayakulu, K., and Sorensen, T.,
J. Am. Chem. Soc., 1972, vol. 94, pp. 1779 1780.
7. Tatarova, L.E., Volcho, K.P., Yarovaya, O.I., Kor-
chagina, D.V., Salakhutdinov, N.F., and Bar-
khash, V.A., Zh. Org. Khim., 1995, vol. 31, no. 7,
pp. 982 995.
Compound XVIIc. Found: M 210.1617. C13H22O2.
20
580
Calculated: M 210.16197. [ ]
+25.0 (CHCl3, c
2.3). 1H NMR spectrum of compound XVIIc ( ,
ppm, J, Hz): 0.96s (C8H3), 0.99m (H6n), 1.04d(H2n,
J2n,2x 13), 1.20 s (C9H3), 1.29 m (H5n), 1.63 d.d.d
(H1, J1,2x 4.5, J1,6x 4, J1,4 1.2), 1.67 m (H5x), 1.73 m
(H6x), 1.81 d.d (H4, J4,5x 4.5, J 1.2), 2.03 d.d.d.d
(H2x, J 13, 4.5, J2x,6x 2.5, J2x,10 0.5), 3.45 d.d (H10,
J 12, 0.5) and 3.52 d (H10 , J10 ,10 12) AB system,
3.81 d.d.d (2H11, J11,12 5, J11,13cis 1.5, J11,13trans 1.5),
5.06 d.d.t (H13cis, J13cis,12 10.5, J13cis,13trans 2, J 1.5),
5.22 d.d.t (H13trans, J13trans,12 17, J 2, 1.5), 5.83 d.d.t
(H12, J 17, 10.5, 5). Compound XVIIIc. Found:
8. Barkhash, V.A., Neklassicheskie karbokationy (Non-
Classic Carbocations), Novosibirsk: Nauka, 1984,
p. 50.
9. Kheifits, L.A., Doctoral Sci. (Chem.) Dissertation,
Moscow, 1986, p. 11.
(fragment ion M OCH2CH= CH2), m/z 193.15845.
20
580
10. Yandovskii, V.N., Karavan, V.S., ahd Temniko-
va, T.I., Usp. Khim., 1970, no. 4, pp. 571 604.
11. Solid Supports and Catalists in Organic Synthesis,
Smith, K., Ed., Prentece Hall, 1992, p. 83.
12. Fomenko, V.V., Korchagina, D.V., Yarovaya, O.I.,
Gatilov, Yu.V., Salakhutdinov, N.F., Ione, K.G.,
and Barkhash, V.A., Zh. Org. Khim., 1999, vol. 35,
no. 7, pp. 1031 1041.
C13H21O. Calculated: 193.15923. [ ]
2.7 (CHCl3,
1
c 2.9). H NMR spectrum of compound XVIIIc ( ,
ppm, J, Hz): 0.89 d.d (H2n, J2n,2x 13, J2n,3x 5),
0.97 s (C8H3), 1.02 s (C9H3), 1.08 d.d.d (H6n, J6n,6x
12, J6n,5n 9, J6n,5x 4.5), 1.47 d.d (H1, J1,2x 4.5, J1,6x
4), 1.47 d.d.d (H5n, J5n,5x 13, J 9, J5n,6x 4), 1.54 d.d
(H4, J4,3x 4, J4,5x 4), 1.63 d.d.d.d.d (H5x, J 13, 4.5,
4, J5x,6x 12, J5x,3x 2), 1.74 d.d.d.d.d (H6x, J 12,
12, 4, 4, J6x,2x 3.5), 1.89 d.d.d.d (H2x, J 13, 4.5, 3.5,
J2x,3x 11), 2.40 d.d.d.d.d (H3x, J 11, J3x,10 9, J 5, 4,
2), 3.90 4.03 m (2H11, 2H14), 4.43 d (H10, J 9),
5.06 d.d.d.d (H13cis, H16cis, J 10.5, 2, 1.5, 1.5),
5.20 d.d.t and 5.21 d.d.t (H13trans and H16trans, J 17,
2, 1.5), 5.82 d.d.t (H12, H15, J 17, 10.5, 5).
13. Ionin, B.I., Ershov, B.A., and Kol,tsov, A.I.,
YaMR-spektroskopiya v organicheskoi khimii (NMR
Spectroscopy in Organic Chemistry), Lenungrad:
Khimiya, 1983, p. 139.
14. Kalinowski, H.O., Berger, S., and Braun, S., 13CNMR
Spektroskopie, Stuttgart: Georg Thieme Verlag, 1984,
pp. 156 165.
15. Buchbauer, G., Haslinger, E., Robien, W., and
Vitek, R., Monatsh. Chem., 1983, vol. 114, pp. 113
122; Lysenkov, V.I., Zh. Org. Khim.. 1988, vol. 24,
no. 8, pp. 1677 1684.
REFERENCES
1. Sethi, S.C. and Natu, A.D., Indian J. Chem., 1988,
16. Stothers, J.B., Carbon-13 NMRSpectroscopy, London:
Academic Press, Inc., 1972, p. 324.
vol. 27B, pp. 974 980.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 38 No. 6 2002