Rearrangements of epoxides of linalool and nerolidyl acetate in acid media

Article abstract of DOI:10.1023/A:1016538920756

The behavior of epoxides of linalool and cis-nerolidyl acetate was comparatively investigated in acids of various strength with the goal of establishing the effect of the structure of the initial compound and the medium character on the main direction of cationoid rearrangement. Linalool epoxides undergo cyclization of solid acid catalysts affording oxygen-containing heterocyclic compounds whereas the nerolidyl acetate epoxides yield the ketones originating from the opening of the epoxy ring followed by 1,2-hydride shift. 10,11-Epoxy derivative of cis-nerolidyl acetate affords 7-oxanorbornane as a minor product.

Full text of DOI:10.1023/A:1016538920756

Russian Journal of Organic Chemistry, Vol. 38, No. 4, 2002, pp. 498 506. Translated from Zhurnal Organicheskoi Khimii, Vol. 38, No. 4, 2002,
pp. 523 531.
Original Russian Text Copyright
2002 by Khomenko, Tatarova, Korchagina, Barkhash.
Rearrangements of Epoxides of Linalool and Nerolidyl
Acetate in Acid Media
T. M. Khomenko, L. E. Tatarova, D. V. Korchagina, and V. A. Barkhash
Vorozhtsov Novosibirsk Institute of Organic Chemistry, Siberian Division, Russian Academy of Sciences, Novosibirsk,
630090 Russia
Received June 6, 2001
Abstract The behavior of epoxides of linalool and cis-nerolidyl acetate was comparatively investigated in
acids of various strength with the goal of establishing the effect of the structure of the initial compound
and the medium character on the main direction of cationoid rearrangement. Linalool epoxides undergo
cyclization of solid acid catalysts affording oxygen-containing heterocyclic compounds whereas the nerolidyl
acetate epoxides yield the ketones originating from the opening of the epoxy ring followed by 1,2-hydride
shift. 10,11-Epoxy derivative of cis-nerolidyl acetate affords 7-oxanorbornane as a minor product.
We investigated formerly the behavior of geraniol and
nerol epoxides in liquid and on solid superacids. By
an example of 2,3-epoxygeraniol we observed the
changing place of the cationic center formation
depending on the nature of the superacid; this fact
resulted in alteration of the main direction of
cationoid rearrangement [1]. Here we report on re-
actions with acids of 1,2- (I) and 6,7-epoxylinalool
(II). Epoxides Ia, b (a mixture of diastereomers in
cyclization reaction of hydroxyketone
(Scheme 2).
V
[2]
Scheme 2.
1
1: 0.2 ratio by H NMR data) on -zeolite at 20 C
isomerized into a mixture of 2-endo- (III) and 2-exo-
(IV) hydroxy-1-isopropyl-4-methyl-7-oxanorbornanes
(56 and 28% respectively; here and hereinafter the
content from GLC analysis of the reaction mixture).
The alcohols III and IV are presumably formed along
the following scheme (Scheme 1).
The opening of the epoxy ring should occur at the
C2 O bond of the intermediate compound VI for this
ring commonly opens from the side of the carbon
atom whose positive charge would be more delocaliz-
ed after the rupture of C O bond [3]. Likewise the
process proceeds on zeolites [4]. The cleavage of the
C1 O bond would provide very unstable primary
carbocation.
The heterocyclization of compounds Ia, b is
apparently similar to the previously described hetero-
Scheme 1.
1070-4280/01/3804-498$27.00 2002 MAIK Nauka/Interperiodica

REARRANGEMENTS OF EPOXIDES OF LINALOOL
499
Scheme 3.
Epoxides IIa, b (a mixture of diastereomers in
2.4 : 1 ratio by 1H NMR data) reacted with the
system HSO3F SO2FCl at 100 C; after quenching
with a mixture MeOH Et2O 2 -vinyl-5 -hydroxyiso-
propyl-2-methyltetrahydrofuran (VII) and 2 -vinyl-
5 -hydroxyisopropyl-2-methyltetrahydrofuran (VIII)
contained in the reaction mixture in 25 and 15%
respectively were obtained. When the isomerization
of epoxides IIa, b was performed in the presence of
ZrO2/SO24 the resulting oxides mixture is more
complicated. It contained compound VII (46% by
GLC), VIII (26%), 6-vinyl-3 -hydroxy-2,2,6 -tri-
methyltetrahydropyran (IX) (19%), and 6-vinyl-3 -
hydroxy-2,2,6 -trimethyltetrahydropyran (X) (9%)
(Scheme 3).
We previously pointed out by an example of
epoxygeraniol rearrangements the importance of the
reaction type leading to generation of the cationic
center (protonation of the olefin or opening of the
epoxy ring effected by the protic acid) for the direc-
tion of the rearrangement [1]. It turned out that the
behavior of linalool (XI) on the solid superacid sig-
nificantly differs from the rearrangements of its
epoxides. Thus, alcohol XI on ZrO2/SO24 at room
temperature afforded -terpineol (XII) in agreement
with the data on isomerization of compound XI in the
aqueous citric acid [5].
Note that dehydrolinalool (XIII) under the same
conditions furnishes a heterocyclization product,
Scheme 4.
A specific feature of reactions occurring with com-
pounds IIa, b on solid superacids is the opening of
the epoxy ring along a and b pathways providing
tertiary (A) and secondary (B) carbocations with
prevalence of the second pathway ( 7: 3); therewith
in the heterocyclization is used the hydroxy group of
the initial alcohol IIa, b.
Thus the key moment in the rearrangement of
1,2- and 6,7-epoxy derivatives of linalool on solid
catalysts (in contrast to isomerization of 2,3-epoxy-
geraniol [1]) is the heterocyclization stage at the
expense of the oxygen atom of the hydroxy group.
Therefore various oxygen-containing heterocycles
were obtained, among them new alcohols III, IV.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 38 No. 4 2002

500
KHOMENKO et al.
Scheme 5.
2,2,6 -trimethyl-6-ethynyltetrahydropyran
(XIV).
We earlier demonstrated [6] that cis-nerolidol
Thus is revealed the difference in behavior in the
presence of solid superacid of compounds XI and
XIII that differ in the structure by the multiplicity of
the 1,2 bond. At the attempt to prepare 6,7-epoxide
from dehydrolinalool by treating it with m-chloro-
perbenzoic acid a rearrangement occurs affording
3 -hydroxy-2,2,6 -trimethyl-6-ethynyltetrahydro-
pyran (XV) (Scheme 5). Apparently the intermediate-
ly arising epoxide is unstable in acid medium.
(XXI) quite differently undergoes isomerization both
in the system HSO3F SO2FCl at 110 C and in
formic acid (Scheme 7).
Initial epoxides IIa, b (a mixture of diastereomers
1
in 2.4 : 1 ratio by H NMR data) were prepared from
linalool (XI) by reaction with monoperphthalic acid
in a water solution of NaHCO3. 1,2-Epoxylinalool
(Ia, b, a mixture of diastereomers in 1: 0.2 ratio by
1H NMR data) was obtained by reaction of alcohol XI
with t-BuOOH + VO(acac)2 [7] (Scheme 8).
The isomerization of 10,11 epoxy derivative of cis-
nerolidyl acetate (XVI) analogous in structure to
epoxides IIa, b gives quite unlike results: on
TiO2/SO24 a mixture of 3-acetoxy-3,7.11-trimethyl-
dodeca-1,6-dien-10-one (XVII) and 2-(3-acetoxy-3-
methylpent-4-en-1-yl)-1,3,3-trimethyl-7-oxa-nor-
bornanes (XVIII) forms in 3: 1 ratio (GLC). Thus
after opening of the epoxy ring occur two processes:
1,2-hydride shift and heterocyclization; in the latter
process unlike the case of epoxides IIa, b takes part
the oxygen of the epoxide. Under the same conditions
the 6,7-epoxide of cis-nerolidyl acetate XIX on
TiO2/SO24 affords only the product of 1,2-hydride
shift, 3-acetoxy-3,7,11-trimethyldodeca-1,10-dien-6-
one (XX) (Scheme 6).
Epoxides XVI and XIX were obtained by oxidiz-
ing cis-nerolidyl acetate (XXII) with m-chloroper-
benzoic acid (Scheme 9).
The structure of all newly prepared substances was
established from 1H and 13C NMR spectra. Note
some specific features in determining the structure of
1
a number of compounds obtained. In the H NMR
spectrum of compound III the existence of remote W
coupling constant between protons H6k and H2 (4J6k,2
2 Hz) evidences the exo-position of the latter. In the
1H spectrum of compound IV only two coupling con-
stants for proton H2 are observed: the coupling
with protons H3k and H3n (J 7 and 2 Hz respectively),
Scheme 6.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 38 No. 4 2002

REARRANGEMENTS OF EPOXIDES OF LINALOOL
501
Scheme 7.
Scheme 8
therefore we attributed endo-position to H2 proton. It
is known [8] that in the spectra of norbornane and
related structures the values of vicinal coupling con-
stants are as a rule greater for cis,diexo-located
protons ( 8.8 10 Hz) than for cis,diendo-located ones
(J 6 9 Hz). The comparison of coupling constants
between cis-located protons H3 and H2 in compound
III (J3k,2 10 Hz) and IV (J3n,2 7 Hz) indicates the
exo-position of H2 proton in the former compound and
its endo-position in the latter.
The comparison of 13C NMR spectra of com-
pounds IX and X with the corresponding spectra
published in [9] shows that the hydroxy and vinyl
groups are in trans-configuration in compound IX and
in cis-configuration in compound X. We give the
NMR spectral data for these compounds since there is
no assignment of the signals in the published spectra.
results in appearance in the LRJMD spectrum along-
side triplets at 26.48 and 38.96 ppm belonging to
carbon atoms C4 and C5 and a singlet at 77.13 ppm
corresponding to C2 atom also of quartets at 29.74
and 19.27 ppm that may be assigned to gem-dimethyl
1
groups C9H3 and C10H3. From the 13C H correlation
spectrum on direct constants it was found that the
signal at 19.27 ppm in the 13C NMR spectrum cor-
responded to the methyl group peak at 1.40ppm in the
1H NMR spectrum; likewise the signal at 29.74 ppm
in the former spectrum corresponded to that at
1
1.19 ppm in the latter. In the double resonance 1H H
spectrum the decoupling from proton H3 at 3.32 ppm
caused narrowing of somewhat broadened signal of
methyl group at 1.40 ppm evidencing the remote
coupling between the axially located proton H3 and
the methyl group C10H3. The axial position of H3
proton follows also from the values of vicinal coupl-
ing constants with two protons H4 (J3a,4a 11.5 and
J3a,4e 4.5 Hz). The downfield shift of proton signals
1
The assignment of methyl group peaks in the H
and 13C NMR spectra of compound XV and establish-
ment of configuration for all substituents was done as
follows. The decoupling from proton H3 at 3.32 ppm
1
in H NMR spectrum from two methyl groups by
0.2 0.3 ppm as compared with the peak of the third
methyl group may be ascribed to the influence of the
triple bond C7 C8. As seen from Dreiding models,
the anisotropic effect for the C10H3 group may arise
only if the ethynyl group take the axial position in the
pyran ring. It may be concluded from the above
reasoning that in compound XV the methyl group
C10H3 and ethynyl group are in axial positions
whereas the methyl groups C9H3 and C11H3 and also
the OH group take the equatorial positions, and there-
fore the groups C H and OH are cis with respect to
each other.
Scheme 9.
Analogously to compound XV was performed
the assignment of signals and determined the configur-
ation of substituents in compound XIV: we took into
account the similarity of chemical shifts of methyl
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 38 No. 4 2002

502
KHOMENKO et al.
Table 1. 13C NMR spectra of compounds Ia, b, IIa, b, III, IV, IX, X, XIV, XV, CDCl3 CCl4 (1: 1), C, ppm
Carbon
no.
Ia
Ib
IIa
IIb
III
1
2
3
4
5
6
7
8
9
42.90 d
57.46 d
69.00 s
41.24 t
22.16 t
124.24 d
131.42 s
17.61 q
25.66 q
22.76 q
43.91 t
57.64 d
68.76 s
38.67 t
21.91 t
124.39 d
131.42 s
17.61 q
26.09 q
22.76 q
111.94 t
144.73 d
72.47 s
38.60 t
23.44 t
64.28 d
58.81 s
18.65 q
24.75 q
28.11 q
111.81 t
144.75 d
72.47 s
38.53 t
23.45 t
64.18 d
58.44 s
18.62 q
24.77 q
27.88 q
89.83 s
77.54 d
42.06 t
84.54 s
33.33 t
29.28 t
33.15 d
18.00 q
17.65 q
19.20 q
10
11
1
Carbon
no.
IV
IX
X
XIV
XV, JC,H, Hz
1
2
3
4
5
6
7
8
9
88.40 s
76.72 d
45.37 t
85.46 s
32.56 t
32.85 t
75.07 s
70.96 d
24.34 t
27.70 t
73.27 s
147.16 d
110.17 t
27.33 q
26.37 q
30.90 q
75.89 s
73.42 s
36.48 t
17.56 t
38.30 t
67.04 s
89.08 s
71.31 d
33.11 q
25.25 q
32.66 q
77.13 s
74.84 d
25.90 t
32.67 t
73.27 s
146.61 d
110.44 t
29.64 q
20.77 q
31.83 q
74.82 d, 140
26.48 t, 129
38.96 t, 130
66.69 s
88.45 s
32.56 d
18.16 q
18.16 q
16.37 q
72.03 d, 248
29.74 q, 129
19.27 q, 126
32.13 q, 129
10
11
Table 2. 13C NMR spectra of compounds XVI, XVII, XVIIIa,b, XIX, XX, XXII, CDCl3, C, ppm
Carbon
no.
XVI
XVII
XVIIIa
XVIIIb
XIX
XX
XXII
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
113.04 t
141.64 d
82.65 s
39.77 t
22.00 t
125.03 d
134.44 s
28.30 t
27.25 t
63.91 d
58.17 s
18.57 q
24.77 q
23.17 q
23.50 q
169.79 s
22.00 q
113.00 t
141.63 d
82.63 s
39.66 t
21.94 t
125.22 d
134.18 s
25.79 t
38.53 t
214.14 s
40.73 d
18.08 q
18.08 q
23.02 q
23.53 q
169.79 s
21.94 q
87.92 s
56.98 d
41.66 s
86.07 d
26.59 t
28.57 t
87.92 s
56.94 d
41.66 s
86.07 d
26.59 t
28.57 t
113.44 t
141.18 d
82.42 s
36.53 t
23.02 t
64.46 d
60.88 s
32.73 t
23.98 t
123.60 d
131.90 s
17.51 q
25.57 q
22.14 q
23.55 q
169.79 s
22.03 q
113.51 t
141.03 d
82.21 s
33.51 t
35.41 t
213.64 s
45.81 d
32.88 t
25.58 t
123.65 d
132.13 s
17.57 q
25.58 q
16.33 q
23.63 q
169.71 s
22.03 q
112.91 t
141.67 d
82.68 s
39.92 t
21.97 t
124.38 d
135.35 s
31.74 t
20.78 t
39.61 t
20.78 t
39.63 t
26.39 t
82.84 s
141.52 d
113.21 t
21.31 q
32.40 q
19.71 q
23.36 q
169.74 s
22.04 q
82.84 s
141.58 d
113.17 t
21.31 q
32.40 q
19.71 q
23.36 q
169.74 s
22.04 q
124.15 d
131.36 s
17.44 q
25.54 q
23.20 q
23.39 q
169.72 s
21.97 q
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 38 No. 4 2002

REARRANGEMENTS OF EPOXIDES OF LINALOOL
503
1
groups resonances in the H NMR spectrum and the
Preparation methods for sulfated zirconium and
titanium oxides are described in [12] and [13] re-
spectively. The solvent was purified by passing
through a column packed with calcined alumina.
narrowing of the methyl group signal at 1.43 ppm in
1
1
the double resonance H H spectrum at decoupling
from proton H3a giving signal at 1.30 ppm.
13C NMR spectra of compounds VII and VIII are
Rearrangements of diastereomers of 1,2-epoxy-
linalool (Ia, b). Initial alcohol XI was purified by
successive chromatography first on Al2O3 (II activity
grade, gradient elution with hexane containing from
1
consistent with published data [10]. According to H
and 13C NMR spectra acetate XVIII is a mixture of
compounds XVIIIa, b and XVIIIc, d in 4: 1 ratio.
These compounds presumably are exo- and endo-iso-
mers at carbon C2, and each of them is a mixture of
two diastereomers.
0 to 50% of ethyl ether), then on SiO2 (100 160 ,
17
580
the same eluent); [ ]
+15.45 (c 2.20, CHCl3).
To a solution of 0.82 g of alcohol XI in 7 ml of
benzene was added 0.02 g of VO(acac)2. At room
temperature while stirring was added 1 ml of
t-BuOOH (70%), then the mixture was boiled at
stirring for 14 h. The reaction mixture was treated
with water solution of NaHCO3, washed with water,
and dried with Na2SO4. On evaporating the solvent
0.65 g of residue was obtained containing 31% of
compound XI, and 37% of compounds Ia, b (GLC).
Chromatography of the residue on SiO2 (100 160 ,
eluent hexane containing from 10 to 50% of ethyl
ether) afforded 0.23 g of initial alcohol XI and
0.163 g of epoxides Ia, b in 1: 0.2 ratio according
Compounds XI, XIII, and XXII were identified
by comparing their NMR spectra with the published
data [11].
EXPERIMENTAL
1H and 13C NMR spectra were registered on
spectrometer Bruker AM-400 at operating frequencies
400.13 and 100.61 ppm respectively from solutions
of compounds in CDCl3 or CDCl3 CCl4, 1: 1. As
internal reference served the signals of chloroform (
1
18
580
7.24,
76.90 ppm). The structure of compounds
was estCablished from NMR spectra basing on the
coupling constants analysis with the use of double
to H NMR data. [ ]
+6.09 (c 2.30, CHCl3).
1
Spectrum H NMR of compound Ia, , ppm (J, Hz):
1.11 s (C10H3), 1.55 m (2H4), 1.57 br.d (C8H3, J8,6
1.5), 1.63 d.t (C9H3, J9,6 1.5, J9,5 1), 1.86 br.s
(OH), 2.05 m (2H5), 2.59 d.d (H1cis, J1cis,1trans 5.5,
J1cis,2cis 4) and 2.67 d.d (H1trans, J 5.5, J1trans,2cis 3)
system AB, 2.85 d.d (H2cis, J 4, 3), 5.04 t.q.q (H6,
J6,5 7, J 1.5, 1.5). For minor isomer Ib some signals
resonance spectra H H, and from the 13C NMR
spectra. The assignment of signals in the 13C NMR
spectra was carried out by selective and off-resonance
decoupling from protons. In some cases was perform-
ed registering of differential spectra modulated with
1
1
remote coupling 13C H (LRJMD, experimental
1
1
both in H and 13C NMR spectra coincide with the
conditions optimized for remote coupling constants
JCH 10 Hz). For compounds IX, XIV, XV were addi-
tionally recorded two-dimensional heteronuclear cor-
corresponding signals of the main isomer Ia; in the
1H NMR spectrum were individually observed only
the following signals, , ppm (J, Hz): 1.10 s (C10H3),
1
relation spectra 13C H (COSY, with the use of direct
1
1.47 m (2H4), 1.76 br.s (OH), 2.63 d.d (H1cis
,
coupling constant JCH 135 Hz). The 13C NMR
J1cis,1trans 5.5, J1cis,2cis 4), 2.76 d.d (H1trans, J 5.5,
J1trans,2cis 3), 2.80 d.d (H2cis, J 4, 3), 5.03 t.q.q (H6,
J6,5 7, J6,8 1.5, J6,9 1.5).
spectra are presented in Tables 1 and 2.
The purity of the initial compounds was checked
and the reaction products were analyzed by GLC on
Biokhrom-1 chromatograph equipped with flameioniz-
ation detector and two columns: (a) glass capillary
column 530000 0.26 mm, stationary phase XE-60;
(b) capillary quartz column 13000 0.22 mm, sta-
tionary phase SE-54, carrier gas helium, oven
temperature 80 180 C. Elemental composition of the
newly synthesized compounds was estimated from the
high resolution mass spectra obtained on Finnigan
MAT 8200 instrument. The GC/MS analysis was
carried out on Hewlett Packard 618100A instrument.
The optical rotation was measured on spectrometer
Polomat A in CHCl3.
A solution of 0.075 g of epoxides Ia, b in 10 ml of
CH2Cl2 and 0.145 g of -zeolite (preliminary calcined
for 2 h at 500 C) was stirred for 1 h at 20 C. After
workup we obtained 0.07 g of products mixture that
was applied to a column packed with Al2O3 of IV
activity grade (eluent ethyl ether). The residue after
evaporation of the solvent (0.035 g, 56% of III, 28%
of IV by GLC data) was subjected to column
chromatography on SiO2 (40 100 ), eluent hexane
containing from 0 to 50% of ethyl ether. We isolated
0.008 g of alcohol III and 0.004 g of alcohol IV.
22
580
Alcohol III, [ ]
+6.48 (c 1.06, CHCl3). Found
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 38 No. 4 2002

504
KHOMENKO et al.
170.13050. C10H18O2. Calculated: M 170.13067. hexane containing from 0 to 30% of ethyl ether. We
+
M
1H NMR spectrum, , ppm (J, Hz): 0.891 d and
0.893 d (C9H3, C10H3, J 7), 1.24 d.d (H3n, J3n,3k 13,
J3n,2k 4), 1.34 d.d.d.d (H6k, J6k,6n 12, J6k,5k 12, J6k,5n
5.5, J6k,2q 2), 1.35 s (C11H3), 1.59 d.d.d.d (H5k,
J5k,5n 12, J 12, J5k,6n 5.5, J5k,3k 3), 1.63 m (H5n),
1.81 br.s (OH), 1.91 septet (H8, J 7), 2.00 d.d.d.d
(H3k, J 13, J3k,2k 10, J 3, 1), 2.27 d.d.d (H6n, J 12,
J6n,5n 8, J 5.5), 3.86 d.d.d (H2k, J 10, 4, 2). Alcohol
isolated 0.022 g of oxide VII, 0.003 g of oxide VIII,
0.025 g of oxide IX, 0.009 g of oxide X, and 0.026 g
of
a
mixture of compounds VII and VIII.
20
Compound VII, [ ]
1.55 (c 1.93, CHCl3).
580
1H NMR spectrum, , ppm (J, Hz): 1.07 s and 1.18
s (C7H3, C8H3), 1.28 s (C11H3), 1.68 m (H3), 1.72
1.85 m (2H4), 1.85 m (H3 ), 1.89 br.s (OH), 3.71 t
(H5, J5,4 7), 4.93 d.d (H10cis, J10cis,9cis 10.5,
J10cis,10trans 1.5), 5.13 d.d (H10trans, J10trans,9cis 17.5,
J 1.5), 5.80 d.d (H9cis, J 17.5, 10.5).
24
22
+
IV, [ ]
2.47 (c 0.46, CHCl3). Found M
580
170.13067. C10H18O2. Calculated M 170.13067.
1H NMR spectrum, , ppm (J, Hz): 0.93 d, 0.95 d
(C9H3, C10H3, J 7), 1.32 d.d.d (H3k, J3k,3n 13, J3k,5k
3, J3k,2n 2), 1.38 s (C11H3), 1.36 1.59 m (2H5, 2H6),
2.02 d.d (H3n, J 13, J3n,2n 7), 2.03 septet (H8, J 7),
3.66 d.d (H2n, J 7, 2).
Compound VIII, [ ]
+2.63 (c 1.33, CHCl3).
580
1H NMR spectrum, , ppm (J, Hz): 1.09 s, 1.20 s
(C7H3, C8H3), 1.29 s (C11H3), 1.76 m (H3), 1.80
1.89 m (2H4), 1.90 m (H3 ), 3.80 t (H5, J5,4 7),
4.97 d.d (H10cis, J10cis,9cis 11, J10cis,10trans 1.5), 5.15
d.d (H10trans, J10trans,9cis 17.5, J 1.5), 5.93 d.d (H9,
J 17.5, 11).
Rearrangements of diastereomers of 6,7-epoxy-
linalool (IIa, b). To a mixture of 1.04 g of alcohol
XI and 195 ml of 0.25 M water solution of NaHCO3
was added 66 ml of 0.15 M water solution of mono-
perphthalic acid. The mixture was stirred for 2 h at
0 C. After common workup 0.56 g of products mix-
ture was obtained (69% of epoxides IIa, b by GLC
data). The mixture was subjected to column chromato-
graphy on SiO2 (Czechia, 40 100 ), eluent hexane
containing from 0 to 50% of ethyl ether. We isolated
23
580
Compound IX, [ ]
8.60 (c 2.21, CHCl3).
1H NMR spectrum, , ppm (J, Hz): 1.13 s, 1.17 s
(C9H3, C10H3), 1.15 s (C11H3), 1.63 m (H4), 1.67
1.73 m (2H5), 1.81 br.s (OH), 1.88 m (H4 ), 3.30 m
(H3), 4.88 d.d (H8cis, J8cis,7cis 11, J8cis,8trans 1.2),
4.95 d.d (H8trans, J8trans,7cis 18, J 1.2), 5.85 d.d
(H7cis, J 18, 11).
1
0.22 g of epoxides IIa, b (2.4: 1, H NMR data).
25
Compound X, [ ]
3.70 (c 1.08, CHCl3).
1H NMR spectrum of epoxide IIa, , ppm (J, Hz):
1.20 s (C10H3), 1.22 s, 1.23 s (C8H3, C9H3), 1.41
1.72 m (2H4, 2H5), 2.16 br.s (OH), 2.63 m (H6),
4.98 d.d (H1cis, J1cis,2cis 10.5, J1cis,1trans 1.5), 5.15 d.d
(H1trans, J1trans,2cis 17.5, J 1.5), 5.79 d.d (H2,
580
1H NMR spectrum, , ppm (J, Hz): 1.11 s (C11H3),
1.12 s (C10H3), 1.18 s(C9H3), 1.53 m (H5), 1.59
1.69 m (2H4), 2.08 m (H5 ), 3.35 m (H3), 4.93 d.d
(H8trans, J8trans,7cis 18, J8trans,8cis 1), 4.94 d.d (H8cis
,
J
8cis,7cis 11, J 1), 5.92 d.d. (H7cis, J 18, 11).
1
J 17.5, 10.5). H NMR spectrum of epoxide IIb, ,
ppm (J, Hz): 1.20 s (C10H3), 1.22 s, 1.23 s (C8H3,
C9H3), 1.41 1.72 m (2H4, 2H5), 1.94 br.s (OH),
2.63 m (H6), 4.97 d.d (H1cis, J1cis,2cis 10.5, J1cis,1trans
1.5), 5.14 d.d (H1trans, J1trans,2cis 17.5, J 1.5),
5.82 d.d (H2, J 17.5, 10.5).
A solution of 0.077 g of epoxides IIa, b in 0.3 ml
of SO2FCl was added at 100 C to a solution of
0.87 g of HSO3F in 1.7 ml of SO2FCl. The reaction
mixture was treated with a mixture of 10 ml of
methanol and 4 ml of ethyl ether, neutralized with
17% water solution of Na2CO3, the reaction products
were extracted with ethyl ether, the extract was dried
on MgSO4, and the solvent was evaporated. The
residue was passed through a column packed with
Al2O3 (of IV activity grade, eluent ethyl ether). We
obtained 0.055 g of products mixture containing 27%
of compound VII and 16% of compound VIII accord-
ing to GC/MS data.
To a suspension of 0.32 g of ZrO2/SO24 (pre-
liminary calcined for 2 h at 500 C) in 10 ml of
CH2Cl2 was added a solution of 0.18 g of epoxides
IIa, b in 2 ml of CH2Cl2. The stirring at 0 C
continued for 0.5 h. After workup of the reaction
mixture and passing of the residue through a column
packed with Al2O3 (of IV activity grade, elution with
hexane ethyl ether, 1: 1) we obtained 0.148 f of
mixture containing by GLC data: compound VII,
46%; compound VIII, 26%; compound IX, 19%,
and compound X, 9%. The mixture was subjected
to column chromatography on SiO2 (40 100 ), eluent
Linalool (XI) rearrangements. To a suspension
of 0.3 g of ZrO2/SO24 (preliminary calcined for 2 h
at 500 C) in 5 ml of CH2Cl2 was added a solution of
0.15 g of linalool (XI) in 1 ml of CH2Cl2, and the
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 38 No. 4 2002

REARRANGEMENTS OF EPOXIDES OF LINALOOL
505
mixture was stirred for 1 h at 20 C. After a workup
and chromatography on a column packed with Al2O3
(of IV activity grade, eluent ethyl ether) we obtained
0.108 g of products mixture containing 55% of com-
pound XII (GLC). The latter was subjected to
chromatography on SiO2 (40 100 ), eluent hexane
(C15H3), 1.58 br.s (C12H3), 1.65 m and 1.66 br.s
(C13H3, C14H3), 1.73 m and 1.79 m (2H4), 1.90
2.06 m (2H5, 2H8, 2H9), 1.97 s (C17H3), 5.06 t.m
(H6, J6,5 7), 5.08 t.m (H10, J10,9 7), 5.08 d.d
(H1cis, J1cis,2cis 11, J1cis,1trans 1.2), 5.11 d.d (H1trans
,
J
1trans,2cis 17.5, J 1.2), 5.93 d.d (H2, J 17.5, 11).
containing from 0 to 50% of ethyl ether. We isolated
25
580
To 2 g of acetate XXII, 15 ml of CH2Cl2, and
0.017 g of compound XII, [ ]
2.38 (c 1.68,
40 ml of 7% water solution of NaHCO3 at room
temperature while stirring was added 2.15 g of 80%
m-ClC6H4CO3H. The stirring was continued for 1.5 h,
and the reaction mixture was poured into a water
ether mixture. After a common workup we obtained
1.92 g of a mixture containing the original acetate,
10,11-epoxide XVI, 6,7-epoxide XIX, and a mixture
of diepoxides in a ratio 1: 3.2 : 2.1 : 1.6 (GLC). By
column chromatography on silica gel (40 100 ,
eluent pentane containing from 1 to 5% of ethyl
ether) was afforded 1.03 g (49%) of a mixture of
epoxides XVI and XIX in 2.2 : 1 ratio (GLC), 0.4 g
(17.6%) of diepoxides mixture, and 0.24 g (12%) of
original acetate (XXII). The repeated chromatography
of the monoepoxides mixture on SiO2 under the same
conditions we isolated compounds XVI and XIX in
CHCl3).
Dehydrolinalool (XIII) rearrangements. To a
suspension of 0.34 g of ZrO2/SO24 (preliminary
calcined for 2 h at 500 C) in 10 ml of CH2Cl2 was
added a solution of 0.17 g of dehydrolinalool (XIII)
in 2 ml of CH2Cl2, and the mixture was stirred for
0.5 h at 20 C. After a workup and chromatography
on a column packed with Al2O3 (of IV activity grade,
eluent ethyl ether) we obtained 0.155 g of products
mixture containing 57% of compound XIV (GLC).
The latter was subjected to chromatography on SiO2
(40 100 ), eluent hexane containing from 0 to 50%
of ethyl ether. We isolated 0.032 g of oxide XIV.
1H NMR spectrum, , ppm (J, Hz): 1.15 s (C9H3),
1.30 d.d.d.q (H3a, J3a,3e 13, J3a,4a 13, J3a,4e 3.5,
J3a,10 1), 1.35 d.d.d (H5a, J5a,5e 13, J5a,4a 13, J5a,4e
3.5), 1.42 s (C11H3), 1.43 br.s (C10H3), 1.52 d.d.d.d
(H3e, J 13, 3.5, J3e,4e 3.5, J3e,5e 1.5), 1.59 d.d.d.d.d
(H4e, J 13, 3.5, 3.5, 3.5, J4e,5e 3.5), 1.81 d.d.d.d.d
(H5e, J 13, 3.5, 1.5, J5e,4a 3.5), 1.98 d.d.d.d.d (H4a,
J 13, 13, 13, 3.5, 3.5), 2.28 s (H8).
1
the individual state. H NMR spectrum of epoxide
XVI, , ppm (J, Hz): 1.24 s, 1.28 s (C12H3, C13H3),
1.51 s (C15H3), 1.53 1.65 m (2H9), 1.66 d.t (C14H3,
J14,6 1.5, J14,5 1.5), 1.73 m and 1.84 m (2H4),
1.96 m (2H5), 1.97 s (C17H3), 2.05 2.19 m (2H8),
2.67 t (H10, J10,9 6.5), 5.09 d.d (H1cis, J1cis,2cis 11,
J1cis,1trans 1), 5.11 br.t (H6, J6,5 7), 5.12 d.d (H1trans
,
To 0.092 g of dehydrolinalool (XIII), 4 ml of
CH2Cl2, and 2 ml of saturated water solution of
NaHCO3 at 0 C was added 0.14 g of 80%
m-ClC6H4CO3H [14], and the mixture was stirred at
0 C for 1 h. After workup we obtained 0.078 g of
compounds XIII and XV in 1: 1 ratio (GLC). By
column chromatography on silica gel (40 100 ,
eluent hexane containing from 0 to 30% of ethyl
ether) was isolated 0.13 g of initial alcohol XIII and
0.014 g of tetrahydropyran derivative XV. Com-
pound XV. Found M+ 168.11486. C10H16O2. Cal-
culated: M 168.11502. 1H NMR spectrum, , ppm (J,
Hz): 1.19 s (C9H3), 1.40 br.s (C10H3), 1.41 s
(C11H3), 1.58 d.d.d (H5a, J5a,5e 13, J5a,4a 13, J5a,4e
3.5), 1.72 d.m (H4e, J4e,4a 13, J4e,3a 4.5, J4e,5a 3.5,
J4e,5e 3.5), 1.93 d.d.d.d (H4a, J 13, 13, J4a,3a 11.5,
J4a,5e 3.5), 1.97 m (H5e), 2.28 s (H8), 3.32 d.d (H3a,
J 11.5, 4.5).
J1trans,2cis 17.5, J 1), 5.93 d.d (H2, J 17.5, 11).
1H NMR spectrum of epoxide XIX, , ppm (J, Hz):
1.27 s (C14H3), 1.44 d.d.d (H8, J8,8 13.5, J8,9 9,
J8,9 7), 1.51 m (2H5), 1.54 s (C15H3), 1.60 br.s
(C12H3), 1.67 br.s (C13H3), 1.89 m and 1.97 m
(2H4), 1.98 s (C17H3), 2.08 mm(2H9), 2.66 t (H6,
J6,5 6.5), 5.09 t.q.q (H10, J10,9 7, J10,12 1.5, J10,13
1.5), 5.11 d.d (H1cis, J1cis,2cis 11, J1cis,1trans 1),
5.14 d.d (H1trans, J1trans,2cis 17.5, J 1), 5.91 d.d (H2,
J 17.5, 11).
A mixture of 0.038 g of epoxide XIX, 0.07 g of
TiO2/SO24 , and 5 ml of CH2Cl2 was stirred for
15 min at 20 C. After common workup we obtained
0.019 g of a mixture containing ketone XX and
original compound XIX in 8: 1 ratio (GLC). By
column chromatography on silica gel (40 100 ,
eluent pentane containing from 3 to 4% of ethyl
Rearrangements of cis-nerolidyl acetate (XXII)
epoxides. Original acetate XXI was prepared from
cis-nerolidol (XXI) by procedure from [15] in 97%
1
ether) was isolated 0.012 g of ketone XX. H NMR
spectrum, , ppm (J, Hz): 1.04 d (C14H3, J14,7 7),
1.32d.m (H8, J8,8 13.5), 1.56 br.s (C12H3), 1.66 br.s
1
yield. H NMR spectrum, , ppm (J, Hz): 1.51 s
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 38 No. 4 2002

506
KHOMENKO et al.
(C13H3), 1.67 d.m (H8 , J 13.5), 1.92 m (2H9),
1.96 m and 2.11 m (2H4), 1.99 s (C17H3), 2.33
2.48 m (2H5), 2.50 d.d.q (H7, J7,8 7, J7,8 7, J 7),
5.04t.q.q (H10, J10,9 7, J10,12 1.5, J10,13 1.5), 5.11 d.d
and 113.10 t (C12), 141.61 d and 141.64 d (C11).
13C NMR spectra of isomers XVIIIa, b are given in
Table 2.
(H1cis, J1cis,2cis 11, J1cis,1trans 1), 5.12 br.d (H1trans
J1trans,2cis 17.5), 5.89 d.d (H2, J 17.5, 11).
,
REFERENCES
To a suspension of 0.1 g of TiO2/SO24 (pre-
liminary calcined for 3 h at 400 C) in 3.5 ml of
CH2Cl2 was added 0.06 g of epoxides XVI and XIX
mixture (2.6: 1, GLC), and stirring was carried on
for 15 min at 20 C. The catalyst was filtered off, the
solvent was distilled off, an 0.056 g of raw product
was obtained. The product was passed through a
column packed with SiO2 (40 100 , eluent pentane
containing from 10% of ethyl ether) to afford 0.04 g
of a mixture containing acetates XVIII, ketone XVII,
and ketone XX in 1: 3.1 : 1.8 ratio (GLC). The mix-
ture was subjected to repeated chromatography on
SiO2 (40 100 , eluent pentane containing from 5 to
7% of ethyl ether) to yield individual compounds
XVII and XX and a mixture of acetates XVIII.
1H NMR spectrum of ketone XVII, , ppm (J, Hz):
1.06 d (C12H3, C13H3, J 7), 1.49 s (C15H3), 1.62 d.t
(C14H3, J14,6 1.5, J14,5 1.2), 1.72 m and 1.82 m
(2H4), 1.93 s (2H5), 1.96 s (C17H3), 2.21 m (2H8),
1. Khomenko, T.M., Korchagina, D.V., and Bar-
khash, V.A., Zh. Org. Khim., 2001, vol. 37, no. 6,
pp. 841 848.
2. Gavrilyuk, O.A., Korchagina, D.V., and Bar-
khash, V.A., Zh. Org. Khim., 1992, vol. 28, no. 1,
pp. 111 121.
3. Temnikova, T.I. and Semenova, S.N., Molekulyar-
nye peregruppirovki v organicheskoi khimii (Mole-
cular Rearramgement in Organic Chemistry), Lenin-
grad: Nauka, 1983.
4. Downing, R.S., Bekkum, H.V., and Sheldon, R.A.,
Cat. Tech., 1997, no. 2, pp. 95 109.
5. Baxter, R.L., Laurie, W., and McHale, D., Tetra-
hedron, 1978, vol. 34, no. 14, pp. 2195 2199.
6. Polovinka, M.P., Ungur, N.D., Perutskii, V.B., Kor-
chagina, D.V., Gatilov, Yu.V., Bagryanskaya, I.Yu.,
Mamatyuk, V.I., Cal,nikov, G.E., Vlad, P.F., and
Barkhash, V.A., Zh. Org. Khim., 1991, vol. 27,
no. 10, pp. 2116 2132.
7. Mori, K., Erata, T., and Takeuchi, S., Tetrahedron,
1984, vol. 40, no. 10, pp. 1761 1766.
8. Stereochemistry, Kagan, H.B., Ed., Stuttgart: Thieme
Publishers, 1977, vol. 1, pp. 108 110.
9. Vidari, G., di Rosa, A., Zanoni, G., and Bicchi, C.,
Tetrahedron:Asymmetry, 1999, no. 10, pp. 3547 3557.
10. Francisco, C.G., Freire, R., Hernandez, R., Sala-
zar, J.A., Suarez, E., and Cortes, M., OMR, 1984,
vol. 22, no. 1, pp. 34 38.
11. Standart NMR Spectra. Sadtler Research Labora-
tories; Sadtler Standart Spectra: C-13 Nuclear Mag-
netic Resonance Spectra.
12. Khomenko, T.M., Zenkovets, G.A., and Bar-
khash, V.A., Zh. Org. Khim., 1997, vol. 33, no. 5,
pp. 655 659.
13. Polovinka, M.P., Korchagina, D.V., Gatilov, Yu.V.,
Vyglazov, O.G., Zenkovets, G.A., and Bar-
khash, V.A., Zh. Org. Khim., 1998, vol. 34, no. 9,
pp. 1342 1349.
14. McDonald, R.N., Steppel, R., and Dorsey, J., Org.
Synth., 1970, vol. 50, p. 15.
2.45 s (2H9), 2.57 septet (H11, J 7), 5.07 d.d (H1cis
,
J1cis,2cis 11, J1cis,1trans 1), 5.08 br.t (H6, J6,5 7), 5.11
d.d (H1trans, J1trans,2cis 17.5, J 1), 5.92 d.d (H2, J
1
17.5, 11). H NMR spectrum of acetates XVIIIa, b,
, ppm (J, Hz): 0.844 s and 0.841 s (C15H3), 1.033 s
(C14H3), 1.348 s and 1.345 s (C13H3), 1.512 s
(C16H3), 1.985 s (C18H3), 3.75 d (H4, J4,5q 5),
5.107 d.d and 5.103 d.d (H12cis, J12cis,11cis 11,
J12cis,12trans 1), 5.123 d.d and 5.125 d.d (H12trans
,
J12trans,11cis 17.5, J 1), 5.926 d.d and 5.929 d.d (H11,
J 17.5, 11), 1.07 1.20 m and 1.43 2.05 s (other
protons). 1H NMR spectrum of acetates XVIIIc, d,
, ppm (J, Hz): 0.869 s, 0.876 s, 1.014 s (C14H3,
C15H3), 1.282 s (C13H3), 1.503 s (C16H3), 1.975 s
(C18H3), 3.68 d (H4, J4,5 5), 5.092 d.d (H12cis
J12cis,11cis 11, J12cis,12trans 1), 5.117 d.d (H12trans
,
,
J12trans,11cis 17.5, J 1), 5.930 d.d and 5.934 d.d (H11,
J 17.5, 11). In the 13C NMR spectrum of isomers
XVIIIc, d we failed to separate and attribute all
signals, C, ppm: 18.75 q, 21.37 t, 21.48 q, 23.17 q,
23.29, 25.61 t, 26.00 q, 38.81 t, 39.75, 55.94 d (C2),
83.00 s (C10), 85.98 d (C4), 86.59 s (C1), 112.98 t
15. Goryaev, M.I. and Pliva, I., Metody issledovaniya
efirnykh masel (Investigation Methods of Essential
Oils), Alma-Ata: Akad. Nauk Kaz. SSR, 1962,
p. 328.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 38 No. 4 2002