Reactions of epoxides prepared from some monoterpenes with acetic anhydride on aluminosilicate catalysts

Article abstract of DOI:10.1023/B:RUJO.0000010173.38389.06

Reactions of epoxides prepared from α-, β-pinenes and camphene with acetic anhydride on aluminosilicate catalysts (clay K-10, zeolite β) were investigated affording various products of skeleton rearrangements: mono- and diacetates with five- and six-membered rings, and also with norbornane and pinane cores.

Full text of DOI:10.1023/B:RUJO.0000010173.38389.06

Russian Journal of Organic Chemistry, Vol. 39, No. 8, 2003, pp. 1076 1082. Translated from Zhurnal Organicheskoi Khimii, Vol. 39, No. 8, 2003,
pp. 1147 1153.
Original Russian Text Copyright
2003 by Tatarova, Korchagina, Volcho, Salakhutdinov, Barkhash.
Reactions of Epoxides Prepared from Some Monoterpenes
with Acetic Anhydride on Aluminosilicate Catalysts
L. E. Tatarova, D. V. Korchagina, K. P. Volcho, N. F. Salakhutdinov, and V. A. Barkhash
Vorozhtsov Novosibirsk Institute of Organic Chemistry, Siberian Division, Russian Academy of Sciences,
Novosibirsk, 630090 Russia
Received November 15, 2002
Abstract Reactions of epoxides prepared from -, -pinenes and camphene with acetic anhydride on
aluminosilicate catalysts (clay K-10, zeolite ) were investigated affording various products of skeleton
rearrangements: mono- and diacetates with five- and six-membered rings, and also with norbornane and
pinane cores.
We have formerly investigated reactions of some
monoterpenes with acylating agents in the presence of
crystalline aluminosilicate catalysts (zeolites and
clays) [1]. The application of heterogeneous catalysts
in these reactions improved the ecological character-
istics of the processes and resulted in formation of
previously unknown compounds. We also obtained
good results in the study of reactions between mono-
terpenes epoxides and oxygen-containing compounds
(aldehydes, ketones, and alcohols) catalyzed by
zeolites and clays [2 4]. Bringing into reaction with
aldehydes and ketones terpene epoxides in the pres-
ence of clay furnished versatile products: acetals with
fuzed skeleton, keto-and aldoethers, acetals with a
spirocyclic skeleton, and polycyclic diethers. The
reactions of the - and -pinene epoxides with
aldehydes on aluminosilicate catalysts took un-
common paths [3] and under environmentally toler-
able conditions from simple initial compounds were
obtained complex polyheterocyclic compounds, in
particular, also with a previously unknown core:
The results obtained in the study of reaction
between monoterpenes with acetic anhydride and of
monoterpenes epoxides with oxygen-containing com-
pounds prompted us to combine both these fields of
research and to carry out an investigation on the
reactions of some monoterpenes epoxides with acetic
anhydride under catalysis with crystalline alumino-
silicates. We chose as substrates epoxides of - and
-pinenes and camphene since these terpenoids were
prone to deep rearrangements in acid media and as
showed our previous experience [1, 3] under condi-
tions of heterogeneous catalysis might provide
uncommon structures.
of montmorillonite clay K10 (1.5 h, 20 C) gave rise
to -campholene aldehyde (II) (19%) and its acylal,
1-acetoxy-2-(2,2,3-trimethylcyclopent-3-enyl)ethyl
acetate (III) (3%), and also compounds with a
p-menthane skeleton: trans-sobrerol diacetate (IV)
(22%) and in lesser amounts trans-carvyl acetate (V).
When the reaction time was prolonged to 8 h the
overall yield was reduced, and also diminished the
relative content of products with the -campholene
skeleton; therewith besides compounds II V the
product mixture contained small amounts of cis-
carvyl acetate (VI), 5,5-dimethyl-6-methylenebicyclo-
[2.2.1]hept-2-yl endo-acetate (VII), trans-pinocarvyl
acetate (VIII), and 1-acetoxy-2-(2,2,4-trimethylcyclo-
pent-3-enyl)ethyl acetate (IX). The sharp decrease in
The reaction of -pinene trans-epoxide (I) with
acetic anhydride in dichloromethane in the presence
1070-4280/03/3908-1076$25.00 2003 MAIK Nauka/Interperiodica

REACTIONS OF EPOXIDES FROM SOME MONOTERPENES
1077
Scheme 1.
content of -campholene aldehyde (II) in the reaction
mixture at prolonged reaction time was caused both
by its tarring and partial conversion into acylal III.
The reaction of -pinene trans-epoxide (2,10-ep-
oxy-cis-pinane) (X) with Ac2O in CH2Cl2 on the clay
K-10 (1.5 h, 20 C) gave rise to a reaction mixture
from which by column chromatography on Si2 were
isolated the following products:4-(1-acetoxy-1-meth-
ylethyl)cyclohex-1-enylmethyl acetate (XI), 4-iso-
propenylcyclohex-1-enylmethyl acetate (XII), (2-endo-
acetoxy-7,7-dimethylbicyclo[2.2.1]hept-1-yl)methyl
acetate (XIII), myrtenyl acetate (XIV), and acetoxy-
(3,3-dimethylbicyclo[2.2.1]hept-2-yl)-endo-methyl
acetate (XV) (Scheme 2). Although the main reaction
path provides compounds with the p-methane skeleton,
in the reaction mixture are present in sufficient
amount also substances with the bicyclic skeletons.
Probable mechanisms of compounds II IX forma-
tion are given in Scheme 1.
Whereas in the reaction of - and -pinenes with
the acetic anhydride on clay we obtained the same
reaction products [1] due to identity of cations arising
on protonation of these terpenes, the reactions with
acetic anhydride on clay of epoxides prepared from
these terpenes provided different reaction mixtures as
should be expected. Actually, although the cationic
center arising on protonation of epoxides is located on
the same carbon atom both for - and -pinene
epoxides, the hydroxy group is attached to different
carbons thus resulting in different products.
Compounds we isolated in the study of reaction
between and -pinene and acetic anhydride on clay
were optically active.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 39 No. 8 2003

1078
TATAROVA et al.
Scheme 2.
At the use of -zeolite instead of K-10 clay as
and XVII ( 2.3 : 1) in the presence of -zeolite in the
H+ -form (1 h, 20 C); from the latter reaction mixture
was also isolated 3,3-dimethybicyclo[2.2.1]heptane-
endo-carbaldehyde (XVIII) (Scheme 3).
catalyst of reactions between - and -pinenes and
acetic anhydride the rate of the process significantly
diminished (for instance, a notable conversion of the
-pinene epoxide in reaction with acetic anhydride on
-zeolite was attained only at 40 C). The reaction
mixture was also more complicated.
Aldehyde XVIII is unstable in air and is rapidly
oxidized into the corresponding acid; therefore di-
acetate XV can be regarded as a precursor of aldehyde
XVIII convenient for storage and use.
The - and -pinenes were previously reacted with
benzoic anhydride in polar solvents containing Cu2+
[5], and -pinene epoxide was brought into reaction
with acetic acid in the presence of sodium acetate and
ion-exchange resin [6]. On hydrolysis of the inter-
mediately formed benzoates and acetates the main
products obtained were trans-carveol and perillic
alcohol respectively; the structures of minor products
arising in these reactions were not determined. We
carried out a control experiment consisting in keeping
-pinene epoxide in acetic acid. The GC-MS method
revealed that under these conditions the reaction mix-
ture contained up to 10 compounds in comparable
amounts, and the main part thereof was different from
the substances forming at treating -pinene epoxide
with acetic anhydride on clay.
Although the initial mixture of epoxides XVI and
XVII is optically active, compounds XV and XVIII
obtained are racemic; thus the racemization of the
arising carbocation occurs faster than the formation
of neutral products.
A number of compounds III, IX, XIII, XV were
not previously described; compounds IV, V, VII,
VIII, XI, XII, XIV were obtained formerly by other
methods, mainly by oxidation of - or -pinene with
Hg(OAc)2 [7] or Pb(OAc)4 [8], and also by electro-
1
chemical procedure [9]; as a rule, complete H and
13C NMR spectra were not presented.
Thus we investigated reactions of - and -pinene
and camphene epoxides with acetic anhydride in the
presence of crystalline aluminosilicates; the structure
of the reaction products, also that of the minor
components, was reliably established. Taking into
account the wide range of crystalline aluminosilicates
Compound XV, a minor component of products
of reaction between -pinene epoxide and acetic
anhydride, was also obtained in reaction with acetic
anhydride of a mixture of camphene epoxides XVI
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 39 No. 8 2003

REACTIONS OF EPOXIDES FROM SOME MONOTERPENES
1079
Scheme 3.
and the possibility of varying reaction conditions it is
possible further if necessary to adjust the preparation
conditions for obtaining from the epoxides we studied
the desired compounds chosen among we isolated
from the reaction mixture.
400.13 and 100.61 MHz respectively from solutions
of compounds in a mixture CDCl3 CCl4 ( 1: 1). The
chloroform signals served as internal references (
H
7.24 ppm,
76.90 ppm). The structure of com-
pounds was dCerived from the NMR spectra using the
values of coupling constants obtained from the double
The structure of all compounds obtained was
1
1
1
resonance H H spectra, and basing on the analysis
of the 13C NMR spectra. The signals in the latter
were assigned with the use of selective and off-
resonance decoupling from protons, of LRJMD
spectra with experimental conditions optimized for
remote constants of JC,H 10 Hz, and also using
proved by H and 13C NMR spectra. In compounds
IV and V as show the vicinal coupling constants of
protons H4 and H6 the former is located axially, the
latter pseudoequatorially, and thus they are placed
trans to each other. The exo-position of H5 in com-
pound VII is confirmed by the value of coupling
1
3
two-dimensional spectra 13C H of heteronuclear
constant J5k,4 equal to 4.5 Hz (at the endo-position
1
3
correlation (COSY, using the value JC,H 135 Hz).
the value J5n,4 should be less than 1 Hz), and by the
High-resolution mass spectra were measured on
Finnigan MAT 8200 instrument, GC-MS analyses
were carried out on HP G 1800A setup. The optical
rotation was recorded on spectrometer Polamat from
solutions in CHCl3, concentration expressed in gram
per 100 ml of solution.
lack of W-interaction with the proton H7c. The exo-
position of the proton H3 in the diacetate XV is con-
firmed by the observed W-coupling constant of the
1
proton in the H NMR spectrum with H5k (4J3k,5k
1.2 Hz), no such coupling with the proton H7an, and
also by the value of the vicinal coupling constant with
the proton H4 (3J3k,4 3.5 Hz).
The checking of the purity of the initial compounds
and analysis of the reaction products was carried out
by GLC on chromatograph Biochrom-1 equipped
with a flame-ionization detector, a quartz capillary
column 15000 0.22 mm, stationary phase SE-54,
carrier gas helium, excessive pressure 0.65 at.
Note that for compounds III and IX the data for
the cyclopentene parts of molecules are close to the
corresponding data published in [10] and correspond-
ing to aldehyde II and isocampholene aldehyde. The
1
chemical shifts of signals in the H NMR spectrum of
compound XIV are similar to the corresponding
proton signals of -pinene except the resonances of
H1 and H3 that deviate by 0.16 and 0.34 ppm because
of replaced substituent at the C2 atom [11].
The proton H4 in compound XII is located axially
as suggest its vicinal coupling constants with the
protons H3a and H5a.
The initial epoxides XVI and XVII were obtained
20
as in [12]. [ ]
+5.2 (c 17.5). As catalysts were
580
used -zeolite in the H+ -form, [Si]/[Al] = 40, pore
size 0.75 0.8 nm, containing the following oxides
(wt%): 0.04% Na2O, 5.14% Al2O3, 81.57% SiO2,
and montmorillonite clay K-10 (Fluka). Just before
use the zeolite was calcined for 2 h at 500 C, and the
clay was kept in a microwave oven for 20 min at a
power of 450W. The solvent was passed through a
column packed with calcined aluminum oxide. The
reaction products were separated by column
chromatography on silica gel (40 100 ).
NMR spectra of compound XVIII are described
in [4].
EXPERIMENTAL
1H and 13C NMR spectra were registered on
spectrometer Bruker AM 400 at operating frequencies
Epoxides of - and -pinenes. To a suspension
of 3.2 g of -pinene and 10 g of Na2CO3 in 10 ml of
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 39 No. 8 2003

1080
TATAROVA et al.
20
CHCl3 cooled to 5 C was slowly added 0.053 mol of
peracetic acid in 48 ml of CHCl3. The mixture was
stirred for 2.5 h at 20 C, then poured into 30 ml of
water, the reaction product was extracted into chloro-
form, the extract was washed with saturated solution
of Na2CO3, with water, dried with MgSO4. After
Compound (IV), [ ] +10.9 (c 24.6). Found:
580
M 152.11969. C10H16O [M (CH3CO)2O]. Calculated:
1
M 152.12011. H NMR spectrum, , ppm (J, Hz):
1.32 s, 1.35 s (C9H3, C10H3), 1.37 d.d.d (H5a , J5a,5e
14, J5a,4a 13, J5a,6e 4), 1.60 d.d.d (C7H3, J7,3a 2.5),
J7,2 1.5, J7,3e 1.5), 1.75 m (H3a , J3a ,3e 17, J3a ,4a
11.5, J3a ,7 2.5, J3a ,2 2, J3a ,6 1.5), 1.86 d.d.d.d (H5e,
J 14, J5e,5a 2.5, J5e,6e 2, J5e,3e 2), 1.87 s, 1.97 s
removing the solvent we obtained 3.15 g of -pinene
20
epoxide (X), [ ] + 5 (c 34). In a similar way from
580
3.1 g of -pinene was obtained 2 g of -pinene
(C12H3, C14H3), 2.02 d.m (H3e , J 17, J3e ,2 5.5,
J3e ,4a 5, J 2, 1.5), 2.16 d.d.d.d (H4a, J 13, 11.5, 5,
2.5), 5.09 m (H6e , J 4, 2), 5.59 d.d.q (H2, J 5.5, 2,
1.5). 13C NMR spectrum,* , ppm: 131.04 s (C1),
127.22 d (C2), 26.49 t (C3), 37.31 d (C4), 29.57 t
(C5), 70.37 d (C6), 20.47 q (C7), 83.36 s (C8),
23.40a q (C9), 23.11a q (C10), 170.13 s (C11),
20.96b q (C12), 169.40 s (C13), 22.02b q (C14). Mass
spectrum, m/z (Irel, %): 152 (15.5), 134 (42), 119
(100), 109 (34), 93 (28.6), 43 (84.6).
20
epoxide (I), [ ] +24.6 (c 35).
580
Reaction of -pinene trans-epoxide (I) with
acetic anhydride. To a suspension of 1 g of clay in
9 ml of CH2Cl2 was added 3 ml of Ac2O, 2 min later
was added at stirring a solution of 0.60 g of epoxide
I in 2 ml of CH2Cl2. The mixture was stirred for 8 h
at 20 C, treated with a saturated solution of Na2CO3,
the reaction products were extracted into ethyl ether,
dried with magnesium sulfate. We obtained 0.64 g of
compounds mixture. By column chromatography on
SiO2 (gradient elution with hexane ethyl ether mix-
ture with content of the latter 0.5 80%) we isolated:
(1) 0.028 g of a mixture containing according to GC-
MS data 42.4% of aldehyde II, 11.2% of acetate
(VIII), 23.8% of acetates V and VI mixture; (2)
0.038 g of a mixture containing according to GC-MS
data 11.6% of aldehyde II, 54.6% of acetate V; after
the repeated chromatographing on SiO2 (eluent 1%
of ethyl ether in hexane) was isolated 0.017 g (2.2%)
of acetate V; (3) 0.073 g (7.3%) of diacetate III; (4)
0.024 g (2.4%) of diacetate III and IX mixture
( 1.7 : 1); (5) 0.165 g (16.5%) of diacetate IV; (6)
0.018 g (2.4%) of acetate VII.
20
580
Compound (V), [ ]
+20 (c 2.3). Found:
M 194.12976. C12H18O2. Calculated: M 194.13067.
1H NMR spectrum, , ppm (J, Hz): 1.59 d.d.d (H5a,
J5a,5e 14, J5a,4a 13, J5a,6e 4), 1.65 d.d.d (C7H3, J7,3a
2.5, J7,3e 1.5, J7,2 1.5), 1.70 br.s (C10H3), 1.82 m
(H3a , J3a ,3e 17, J3a ,4a 11, J 2.5, J3a ,2 2, J3a ,6e
1.5), 1.88 d.d. d.d (H5e, J 14, J5e,4a 2.5, J5e,3e 1.5,
J5e,6e 1.5), 2.02 s (C12H3), 2.16 m (H3e , J 17, J3e ,2
5.5, J3e ,4a 5, J 1.5, 1.5), 2.25 d.d.m (H4a, J 13, 11,
5, 2.5, J4a,9 0.5), 4.66 m (H9, J9,9 1.5, J9,10 1, J0.5),
4.69 m (H9 , J 1.5, J9 ,10 1.5), 5.19 m (H6e , J 4,
1.5, 1.5), 5.65 d.m (H2, J 5.5, 2, 1.5). 13C NMR
spectrum, , ppm: 131.12 s (C1), 127.51 d (C2),
30.88 t (C3), 35.80 d (C4), 33.70 t (C5), 70.20 d
(C6), 20.67 q (C7), 148.21 s (C8), 109.52 t (C9),
20.88 q (C10), 169.95 s (C11), 21.15 q (C12). Mass
spectrum, m/z (Irel, %): 194 (2) [M]+ , 152 (60),
134 (28.6), 119 (72), 109 (80), 93 (38), 91 (50.6), 84
(63), 43 (100).
20
Compound III, mp 68.5 70 C, [ ] + 2 (c 8).
580
Found: M 152.11984. C10H16O [M (CH3CO)2O].
Calculated: M 152.12011. 1H NMR spectrum, , ppm
(J, Hz): 0.75 s, 0.96 s (C8H3, C9H3), 1.58 d.d.d
(C10H3, J10,5 2.5, J10,5 1.5, J10,4 1.5), 1.68 d.d.d (
H6, J6,6 13, J6,1 11, J6,7 4.5), 1.77 d.d.d.d (H11,
J 11, J1,5 9, J1,5 7, J1,6 2.5), 1.84 d.d.d (H6 , J 13,
J6 ,7 7, J 2.5), 1.92 d.d.q.d (H5, J5,5 15, J 9, 2.5,
J5,4 1.5), 2.04 s, 2.05 s (C12H3, C14H3), 2.29 d.d.d.q
(H5 , J 15, 7, J5 ,4 3, J 1.5), 5.17 d.d.q (H4, J 3, 1.5,
1.5), 6.73 d.d (H7, J 7, 4.5). 13C NMR spectrum,*
, ppm: 45.04 d (C1), 46.90 s (C2), 147.73 s (C3),
121.95 d (C4), 35.51 t (C5), 33.79 t (C6), 90.43 d
(C7), 25.47a q (C8), 19.72a q (C9), 12.63 q (C10),
168.28b s (C11), 20.79c q (C12), 168.23b s (C13),
20.70c q (C14). Mass spectrum, m/z (Irel, %): 152
(6.6), 109 (35), 108 (100), 93 (26.5), 43 (66).
20
580
Compound (VII), [ ]
17.1 (c 1.75). Found:
M 194.13053. C12H18O2. Calculated: M 194.13067.
1H NMR spectrum, , ppm (J, Hz): 1.06 s (C8H3),
1.08 s (C9H3), 1.33 d.d.d (H7an, J7an,7c 10, J7an,1 1.5,
J7an,4 1.5), 1.58 d.d.d (H6n, J6n,6k 13.5, J6n,7c 4,
J6n,5k 2.5), 1.76 d.d. d.d (H7c, J 10, 4, J7c,1 1.5, J7c,4
1.5), 1.82 d.d.d (H6k, J 13.5, J6k,5k 10, J6k,1 3.5),
1.85 br.d (H1, J 3.5), 1.93 s (C12H3), 3.02 d.d.d.d
(H4, J4,5k 4.5, J 1.5, 1.5, J4,1 1.5), 4.67 s, 4.71 s
(2H10), 4.84 d.d.d (H5k, J 10, 4.5, 2.5). 13C NMR
spectrum, , ppm: 47.53 d (C1), 41.85 s (C2),
158.03 s (C3), 50.66 d (C4), 74.16 d (C5), 31.10 t
*
Here and hereinafter the chemical shifts values marked with
the same letters (a c) should probably be exchanged.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 39 No. 8 2003

REACTIONS OF EPOXIDES FROM SOME MONOTERPENES
1081
(C6), 36.43 t (C7), 29.97 q (C8), 24.90 q (C9),
104.49 t (C10), 170.16 s (C11), 21.07 q (C12).
Compound (XII). 13C NMR spectrum, , ppm:
132.71 s (C1), 125.59 d (C2), 30.41 t (C3), 40.82 d
(C4), 27.29 t (C5), 26.41 t (C6), 68.10 t (C7),
148.85 s (C8), 109.22 t (C9), 20.79 q (C10), 169.73 s
(C11), 20.75 q (C12).
1
Compound (IX). H NMR spectrum, , ppm (J,
Hz): 0.77 s, 0.99 s (C8H3, C9H3), 1.63 br.s (C10H3),
1.65 m (H6), 1.77 1.88 m (H1, H6 ), 2.05 m (H5),
20
580
2.05 s, 2.06 s (C12H3, C14H3), 2.27 d.d.m (H5 , J5 ,
5
Compound (XIII), [ ]
27 (c 2.8). Found:
16, J5 ,1 7.5, J5 ,3 1.2), 5.08 (H3, J3,5 2.5, J 1.2,
J3,10 1), 6.71 d.d (H7, J7,6 7, J7,6 4.5). 13C NMR
spectrum,* , ppm: 44.43 d (C1), 46.18 s (C2),
135.85 d (C3), 136.60 s (C4), 41.93 t (C5), 33.64 t
(C6), 90.45 d (C7), 27.85a q (C8), 22.15a q (C9),
16.69 q (C10), 168.46b s (C11), 20.77c q (C12),
168.38b s (C13), 20.69c q (C14).
M 254.15175. C14H22O4. Calculated: M 254.15180.
1H NMR spectrum, , ppm (J, Hz): 0.93 s, 0.99 s
(C8H3, C9H3), 0.97 d.d (H3n, J3n$),3k 13.5, J3n,2k
3.5), 1.27 d.d.d (H5n, J5n,5k 12.5, J5n,6n 9, J5n,6k 4.5),
1.41 d.d.d.d (H6k, J6k,6n 12.5, J6k,5k 12, J 4.5, J6k,2k
2.2), 1.63 d.d (H4, J4,3k 4.5, J4,5k 4.5), 1.77 m
(H5k, J 12.5, 12, 4.5, J5k,6n 4.5, J5k,3k 3), 1.92 d.d.d
(H6n, J 12.5, 9, 4.5), 1.97 s (C14H3), 2.00 s (C12H3),
2.37 d.d.d.d (H3k, J 13.5, J3k,2k 10, J 4.5, 3), 3.97 d
and 4.00 d (2H10, J 12) system Ac, 5.14 d.d.d (H2k,
J 10, 3.5, 2.2). 13C NMR spectrum, , ppm: 51.23 s
(C1), 75.08 d (C2), 36.56 t (C3), 45.92 d (C4),
27.70 t (C5), 23.32 t (C6), 48.06 s (C7), 20.24a q
(C8), 19.90a q (C9), 62.94 t (C10), 170.16 s (C11),
21.05 q (C12), 170.08 s (C13), 20.67 q (C14). Mass
spectrum, m/z (Irel, %): 254 (2.6), 152 (25.9), 134
(68), 119 (33.2), 108 (58), 93 (35.2), 92 (52.7), 43
(100).
A suspension of 0.25 g of clay, 0.5 ml of Ac2O,
0.1 g of epoxide I in 3.5 ml of CH2Cl2 was stirred for
1.5 h at 20 C. After the workup the product mixture
was separated on a column packed with SiO2 (gradient
elution with ethyl ether hexane mixture containing
from 0.25 to 80% of the latter). We isolated 0.019 g
(19%) of aldehyde II; 0.02 g of mixture containing
according toGC-MS data15.5% of aldehydeII, 25.5%
of acetate V, and 3% of acetate VIII; 0.005 g (3%) of
diacetate III, and 0.037 g (22%) of diacetate IV.
Reaction of -pinene trans-epoxide (X) with
acetic anhydride. A suspension of 1.5 g of clay, 5 ml
of Ac2O, 1 g of epoxide X in 12 ml of anhydrous
CH2Cl2 was stirred for 1.5 h at 20 C. After the work-
up we obtained 1.28 g of the product mixture which
was separated on a column packed with SiO2 (gradi-
ent elution with ethyl ether hexane mixture contain-
ing from 0.5 to 50% of the latter). We isolated 0.05 g
(3%) of diacetate XV, 0.390 g (23%) of diacetate XI,
0.086 g (5%) of diacetate XIII, 0.225 g (17.7%) of
acetate XII, and 0.038 g of a mixture containing
according to GC-MS analysis 20% of acetate XIV.
The latter mixture was subjected to repeated chromato-
graphy on SiO2 to isolate 0.005 g of individual
acetate XIV fit for recording NMR spectra.
20
1
Compound (XV), [ ]
18.6 (c 2.8). H NMR
580
spectrum, , ppm (J, Hz): 0.87 s (C9H3), 1.00 s
(C8H3), 1.19 d.d.d (H7an, J7an,7c 10, J7an,1 1.5, J7an,4
1.5), 1.28 m (H5k, H6k), 1.55 m (H5n), 1.62 d.m
(H7c, J 10), 1.67 m (H6n), 1.78 d.d.d (H3k, J3k,10 10,
J3k,4 3.5, J3k,5kyy 1.2), 1.78 br.s (H1), 2.01 s, 2.05 s
(C12H3, C14H3), 2.09 m (H4), 6.87 d (H10, J 10).
13C NMR spectrum,* , ppm: 49.59 d (C1), 36.96 s
(C2), 53.61 d (C3), 40.02 d (C4), 21.12 t (C5),
24.66 t (C6), 37.31 t (C7), 32.52 q (C8), 21.54 q
(C9), 90.24 d (C10), 168.34a s (C11), 20.89b q (C12),
167.50a s (C13), 20.75b q (C14).
Reaction of camphene cis- and trans-epoxides
(XVI, XVII) with acetic anhydride. A solution of
0.12 g of epoxides XVI and XVII mixture in 3 ml of
anhydrous Ac2O was added to a suspension of 0.12 g
of zeolite in 5 ml of Ac2O, and the mixture was
stirred for 1 h at 20 C. By column chromatography
on silica gel (eluent pentane) was isolated 0.21 g
(18%) of aldehyde XVIII and 0.185 g of a mixture
that after repeated chromatography on SiO2 with
gradient elution by mixture pentane ethyl ether (2
15%) provided 0.025 g (13%) of diacetate XV.
20
580
Compound (XI), [ ]
28.4 (c 16.6). Found:
M 211.13499. C12H19O (M CH3CO). Calculated:
3
1
M 211.13341. H NMR spectrum, , ppm (J, Hz):
1.12 m (H5a), 1.22 s, 1.25 s (C9H3, C10H3),
1.66 d.m (H5e, J5e,5a 12), 1.74 s (C14H3), 1.83 s
(C12H3), 1.68 1.94 m (2H3, H4, 2H6), 4.18 br.d and
4.21 br.d (2H7, J 12, J7,3a 1.5, J7,344e 1.5) system
AB, 5.50 m (H2). 13C NMR spectrum,* , ppm:
132.64 s (C1), 124.85 d (C2), 25.76 t (C3), 42.01 d
(C4), 22.97 t (C5), 26.38 t (C6), 67.38 t (C7), 83.38 s
(C8), 22.90a q (C9), 22.72a q (C10), 168.93 s (C11),
20.24 q (C12), 168.55 s (C13), 21.72 q (C14). Mass
spectrum, m/z (Irel, %): 211 (2.9), 134 (48.4), 119
(30.3), 93 (30.3), 92 (100), 43 (71.4).
The authors express they gratitude to the Russian
Foundation for Basic Research for granting permis-
sion to use Databases STN (grant no. 00-03-32721)
through the STN-Center of the Novosibirsk Institute
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 39 No. 8 2003

1082
TATAROVA et al.
of Organic Chemistry, Siberian Division, Russian
Academy of Sciences.
vol. 92, no. 181428.
6. US Patent US5994598, 1999; Chem. Abstr., 1999,
vol. 132, no. 3478.
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RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 39 No. 8 2003