Ozonolytic transformations of (S)-(-)-limonene

Article abstract of DOI:10.1134/S1070428012010034

Partial ozonolysis of (S)-(-)-limonene in cyclohexane-methanol yields 1-methyl-4-(prop1-en-2-yl)-7,8,9-trioxabicyclo[4.2.1]nonane as a mixture of diastereoisomers at a ratio of 2 : 3. Nitrogen-containing organic compounds (semicarbazide and hydroxylamine

Full text of DOI:10.1134/S1070428012010034

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2012, Vol. 48, No. 1, pp. 18–24. © Pleiades Publishing, Ltd., 2012.
Original Russian Text © G.Yu. Ishmuratov, Yu.V. Legostaeva, L.P. Botsman, G.V. Nasibullina, R.R. Muslukhov, D.V. Kazakov, G.A. Tolstikov, 2012,
published in Zhurnal Organicheskoi Khimii, 2012, Vol. 48, No. 1, pp. 26–32.
Ozonolytic Transformations of (S)-(–)-Limonene
G. Yu. Ishmuratov, Yu. V. Legostaeva, L. P. Botsman, G. V. Nasibullina, R. R. Muslukhov,
D. V. Kazakov, and G. A. Tolstikov
Institute of Organic Chemistry, Ufa Research Center, Russian Academy of Sciences,
pr. Oktyabrya 71, Ufa, 450054 Bashkortostan, Russia
e-mail: insect@anrb.ru
Received February 24, 2011
Abstract—Partial ozonolysis of (S)-(–)-limonene in cyclohexane–methanol yields 1-methyl-4-(prop1-en-2-yl)-
7,8,9-trioxabicyclo[4.2.1]nonane as a mixture of diastereoisomers at a ratio of 2:3. Nitrogen-containing organic
compounds (semicarbazide and hydroxylamine hydrochlorides) favor cyclization of intermediate ozonolysis–
reduction products, whereas the reduction with dimethyl sulfide, NaBH4, and NaBH(OAc)3 follows conven-
tional pattern.
DOI: 10.1134/S1070428012010034
Ozonolytic cleavage of olefins is a widely used
method for functionalization of unsaturated com-
pounds. Variation of the conditions of ozonolysis (sol-
vent, temperature, amount of ozone) and reagents and
conditions for subsequent transformations (oxidation,
reduction, or cleavage) of peroxide compounds could
give rise to a broad spectrum of products containing
various functional groups. A promising line in organic
synthesis is ozonolysis of commercially available
natural cyclic olefins, including (S)-(–)-limonene,
which opens a way to α,ω-difunctional compounds.
Griesbaum et al. [1] described the structure of limo-
nene monoozonide and proposed several ways of
transformations of its peroxide ozonolysis products, in
particular by the action of oxidants (Jones’ reagent [2])
and reducing agents (PPh3 [1], Zn [3], electrolytic
reduction [4, 5]).
reducing agents. Partial ozonolysis of (S)-limonene (I)
in cyclohexane–methanol at 2–4°C gives a mixture of
diastereoisomeric ozonides IIa and IIb at a ratio of
2:3 (previously described [1] 1,2,4-trioxolane was
obtained at –45°C in pentane as a single stereoisomer),
and their structure was determined on the basis of the
13C NMR spectrum of the reaction mixture during the
ozonolysis. Peroxides IIa and IIb are fairly stable;
they are slowly converted into hemiketal III (by 30%
in 6 days at room temperature; Scheme 1). The forma-
tion of trioxolanes IIa and IIb rather than expected
methoxy hydroperoxide is likely to be related to the
structure of initial cyclic olefin I.
With a view to extend the synthetic potential of
(S)-limonene (I), we examined transformations of its
peroxide ozonolysis products by the action of semicar-
bazide and hydroxylamine hydrochlorides, dimethyl
sulfide, sodium triacetoxyhydridoborate, and sodium
tetrahydridoborate.
In the present article we report on the results of
our study on the transformations of peroxide ozonol-
ysis products of (S)-(–)-limonene (I, ee 50%) by the
action of nitrogen-containing organic and borohydride
We previously showed that semicarbazide hydro-
chloride is an efficient reagent for the transformation
Scheme 1.
Me
OH
Me
Me
Me
O
O
O
O3 (0.9 equiv), MeOH–cyclo-C6H12
2–4°C
OMe
CHO
O
6 days
O
O
+
IIa, IIb +
(S)
Me
CH2
Me
CH2
Me
CH2
IIb
Me
II : III = 7 : 3
CH2
III
I
IIa
18

OZONOLYTIC TRANSFORMATIONS OF (S)-(–)-LIMONENE
19
Scheme 2.
Me
OMe
Me
OMe
4
1
4
1
5
6
5
6
3
2
3
2
OMe
OMe
24 h
+
Me
OMe
Me
OMe
H2NCONHNH2·HCl, MeOH
O
OH
IIa, IIb
IV
9 : 1
V
48 h
IV
Scheme 3.
OH
Me
Me
OMe
δ+ δ–
OMe
CH2
HOMe
H2NCONHNH2·HCl, MeOH
[O], MeOH
IIa, IIb
IV
OMe
–H2O
Me
Me
R
R
III, VI
V, VII
III, VII, R = CHO; V, VI, R = HO(MeO)CH; [O] stands for products of oxidation of semicarbazide hydrochloride with ozonide II.
of peroxide products of olefin ozonolysis in methanol
into methyl esters which are formed through inter-
mediate hemiacetals [6]. In the present work we found
that controlled ozonolysis of limonene (I), followed by
reaction of peroxides with semicarbazide hydro-
chloride (reaction time 24 h), apart from the trans-
formation of hemiacetal into ester, resulted in ring
closure with formation of cyclohexane derivatives IV
and V at a ratio of 9:1 (Scheme 2).
The formation of substituted diastereoisomeric cy-
clohexanes IV and V from diastereoisomeric ozonides
IIa and IIb is confirmed by the presence in the
13C NMR spectra of two couples of downfield singlets
from quaternary C2 and C4 carbon atoms at δC 74–
77 ppm. Doublet signals from methylene protons on C3
(δ 1.73 and 1.91 ppm for IV and δ 1.83 and 1.96 ppm
for V) indicated the position of quaternary carbon
atoms in the ring. The NMR spectra of compounds IV
and V contained signals from two methoxy groups
(δC 49–52 ppm), as well as signals from two methyl
groups on C2 and C4, in keeping with the structure of
2,4-dimethoxy-2,4-dimethylcyclohexanes. In the
13C NMR spectrum of IV (or V) we observed sets of
signals corresponding to only one couple of diastereo-
isomers at a ratio of 3:1. When the reaction of perox-
ide products of ozonolysis of olefin I with semicar-
bazide hydrochloride was prolonged to 48 h, cyclic
ester IV was formed as the only product (yield 70%,
Scheme 2).
We presumed that compounds IV and V are formed
according to Scheme 3. Initially, ozonolysis products
IIa and IIb react with the reducing agent to give
unsaturated hemiketal III or VI in which electron-
deficient quaternary carbon atom undergoes attack by
electrons of the double bond with simultaneous sta-
bilization by methanol and elimination of water to
Scheme 4.
Me
Me
Me OH
OMe
CN
Me
OMe
O
NOH
COOMe
NH2OH·HCl, MeOH
IIa, IIb
IV
+
+
+
+
OMe
COOMe
Me
CN
Me
CH2
Me
CH2
Me
CH2
XI
VIII
IX
X
IV : VIII : IX : X : XI = 50 : 30 : 12 : 4 : 4
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 48 No. 1 2012

ISHMURATOV et al.
20
produce cyclohexane derivatives, hemiacetal V or
aldehyde VII. Further oxidative transformations of the
hemiacetal or aldehyde moiety into ester in IV confirm
our previous results [6].
Treatment of peroxide ozonolysis products IIa and
IIb with hydroxylamine hydrochloride gave a mixture
of ester IV and nitrile VIII, as well as unsaturated keto
ester IX, nitrile XI, and ketone oxime X (Scheme 4);
syn configuration of the oxime group in the latter
follows from the downfield position of the methyl
carbon signal (δC 24.86 ppm) [7].
Scheme 5 illustrates possible ways of formation of
compounds IV and VIII–XI. Hydroxylamine hydro-
chloride catalyzes formation of hemiketal functionality
from peroxides IIa and IIb, and cyclization of hemi-
ketal III and consecutive transformations following the
path aldehyde VII→oxime XII→nitrile VIII→ester
IV are consistent with the mechanism proposed by us
previously [8] for the transformation of aldehyde
moiety into ester by the action of hydroxylamine
hydrochloride. Some amount of hemiketal III does not
undergo cyclization but is converted into acyclic un-
saturated nitrile XI through intermediate aldehyde
oxime XIII. Compounds IX and X are likely to be
products of concurrent process which involves initial
transformation of the aldehyde group in ketoaldehyde
XIV while the terminal double bond remains intact.
The reduction of peroxide ozonolysis products II
with dimethyl sulfide gave 85% of expected ketoalde-
hyde XIV. Treatment of compound XIV with hy-
droxylamine hydrochloride in methanol at room tem-
perature led to its cyclization to ester IV (Scheme 6).
In addition, the reaction mixture contained a small
amount of hydroxyimino hemiacetal XVII. The pres-
ence of the latter suggests that the reaction follows two
concurrent pathways and that the cyclization process
Scheme 5.
Me OH
OMe
NOH
XI
–H2O
Me
CH2
XIII
Me
OMe
Me
MeOH/H+
III
VII
VIII
IV
OMe
–H2O
NOH
NH2OH·HCl
MeOH
XII
IIa, IIb
Me
Me
Me
O
O
O
IX
NH2OH·HCl
NOH
CHO
CN
Me
CH2
XIV
Me
CH2
Me
Me
CH2
XVI
XV
X
Scheme 6.
NOH
Me2S
85%
NH2OH·HCl, MeOH
OMe
IIa, IIb
XIV
IV +
OH
Me
85 : 15
CH2
XVII
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 48 No. 1 2012

OZONOLYTIC TRANSFORMATIONS OF (S)-(–)-LIMONENE
21
Scheme 7.
MeOH, H+
III
VII
XII
VIII
IV
–H2O
NH2OH·HCl, MeOH
XIV
Me
O
NH2OH·HCl
XVII
OMe
OH
CH2
Me
predominates over formation of oxime. Presumably,
compounds IV and XVII are formed from ketoalde-
hyde XIV according to Scheme 7. The formation of
cyclic ester IV follows the path shown in Scheme 5.
The concurrent path implies transformation of the al-
dehyde group in XIV into hemiacetal in methanol and
simultaneous oximation of the ketone group.
Thus the structure of peroxide products of ozonol-
ysis of (S)-(–)-limonene and products of their subse-
quent reduction is largely determined by the nature of
the substrate and reducing agent. Nitrogen-containing
organic compounds like semicarbazide and hydroxyl-
amine hydrochlorides favor cyclization of intermediate
products, whereas the reduction with dimethyl sulfide,
NaBH4, and NaBH(OAc)3 follows expected path.
In order to extend the series of difunctional deriva-
tives of limonene (I) and examine the effect of the
reducing agent on the structure of final products perox-
ide ozonolysis products obtained from diene I were
treated with NaBH(OAc)3 and NaBH4. The reduction
of ozonolysis products IIa and IIb with sodium tetra-
hydridoborate followed a conventional pattern with
formation of diol XVIII (Scheme 8). It is known that
the use of NaBH(OAc)3 as reducing agent for peroxide
ozonolysis products ensures selective reduction of al-
dehyde group while already existing or newly formed
keto group remains unchanged [9]. Controlled ozonol-
ysis of olefin I and subsequent reduction with sodium
triacetoxyhydridoborate afforded 75% of unsaturated
keto alcohol XIX which can be stored for a long time.
EXPERIMENTAL
The IR spectra were recorded from thin films on
1
a IR-Prestige-21 instrument. The H and 13C NMR
spectra were measured on a Bruker AM-300 spectrom-
eter at 300.13 and 75.47 MHz, respectively, using
CDCl3 as solvent and tetramethylsilane as internal
1
reference. Signals in the H NMR spectra were as-
signed, and coupling constants were determined, using
double resonance and two-dimensional homonuclear
correlation (COSY H–H) techniques. GLC analysis
was performed on Chrom-5 [1.2-m column packed
with 5% of SE-30 on Chromaton N-AW-DMCS (0.16–
0.20 mm), oven temperature 50–300°C] and Chrom-41
instruments [2.4-m column packed with PEG-6000,
oven temperature 50–200°C]; carrier gas helium. Thin-
layer chromatography was performed on Sorbfil silica
gel plates (Russia). Silica gel (70–230 μm; Lancaster,
England) was used for column chromatography. The
optical rotations were measured on a Perkin–Elmer
241-MC polarimeter. Elemental compositions of the
isolated compounds were consistent with the calculat-
ed data. The efficiency of the ozonizer was 40 mmol of
O3 per hour.
Scheme 8.
Me
OH
NaBH4, MeOH, 20°C
IIa, IIb
OH
Me
CH2
XVIII, 80%
Me
(1) O3 (0.9 equiv), CH2Cl2–AcOH, 2°C
(2) NaBH(OAc)3
Ozonolysis of (S)-(–)-limonene (I). An ozone–
oxygen mixture was bubbled through a solution of
2.72 g (20 mmol) of (S)-(–)-limonene (I) in a mixture
of 30 ml of distilled cyclohexane and 1.6 ml
(40.0 mmol) of anhydrous methanol at 2–4°C until
18.0 mmol of ozone was absorbed. The mixture was
O
I
OH
Me
CH2
XIX, 75%
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 48 No. 1 2012

ISHMURATOV et al.
22
purged with argon, the cyclohexane layer was separat-
ed by decanting, 30 ml of anhydrous methanol was
added to the residue containing ozonolysis products II,
and the latter were subjected to subsequent treatment.
trum, δC, ppm: 18.48 (22.02) q (CH3), 25.06 (23.50) q
(CH3), 25.06 (24.95) t (C6), 34.53 (33.90) t
(CH2CO2CH3), 35.27 (35.03) t (C5), 41.75 (42.89) d
(C1), 43.32 (41.07) t (C3), 49.06 q (OCH3), 49.47 q
(OCH3), 51. 26 q (OCH3), 74. 37 (74. 29) s
[C(CH3)OCH3], 75.91 (75.09) s [C(CH3)OCH3],
174.05 (174.37) s (C=O).
A solution of ozonide II was kept for 6 days at
room temperature, and 13C NMR spectrum of the reac-
tion mixture was recorded every day. The conversion
of II into hemiketal III was 30% in 6 days.
2-[(1S)-2,4-Dimethoxy-2,4-dimethylcyclohexyl]-
1-methoxyethanol (V). Yield 0.28 g (6%), Rf 0.31
(petroleum ether–tert-butyl methyl ether, 2:1).
1H NMR spectrum, δ, ppm: 1.09 s (3H, CH3), 1.20 s
(3H, CH3), 1.41–1.68 m (2H, 5-Hax, 6-Hax), 1.74–
1.80 m (2H, 5-Heq, 6-Heq), 1.83 d (1H, 3-H, J =
11.8 Hz), 1.93 d.d [1H, CH2CH(OH)OCH3, J = 14.4,
5.6 Hz], 1.96 d (1H, 3-H, J = 11.8 Hz), 1.96–2.10 m
(1H, CH), 2.53 d.d [1H, CH2CH(OH)OCH3, J = 14.4,
5.6 Hz], 3.13 s (3H, OCH3), 3.19 s (3H, OCH3), 3.65 s
(3H, OCH3), 4.78 t [1H, CH(OH)(OCH3), J = 6.1 Hz],
5.1 br.s (1H, OH). 13C NMR spectrum, δC, ppm: 18.76
(23.41) q (CH3), 23.50 (22.06) q (CH3), 24.95 (22.52) t
(C6), 34.54 (33.82) t (C5), 35.43 (35.05) t (1-CH2),
42.88 (40.31) d (C1), 43.22 (41.06) t (C3), 50.76 q
(OCH3), 51.32 q (OCH3), 52.76 q (OCH3), 75.07
(76. 32) s [C(CH3)OCH3], 76. 57 (74. 26) s
[C(CH3)OCH3], 103.37 d [CH(OH)(OCH3].
b. Semicarbazide hydrochloride, 7. 75 g
(70.0 mmol), was added under stirring at 0°C to
a solution of ozonide II, and the mixture was stirred
for 48 h at room temperature. The mixture was evap-
orated, the residue was dissolved in 100 ml of methyl-
ene chloride, and the solution was washed with water
(4×25 ml), dried over MgSO4, and evaporated to
isolate 2.95 g (70%) of ester IV which was identical to
a sample of IV isolated as described in a.
c. Hydroxylamine hydrochloride, 4.87 g
(70.0 mmol) was added under stirring at 0°C to
a solution of ozonide II, and the mixture was stirred
for 48 h at room temperature. The mixture was evap-
orated, the residue was dissolved in 100 ml of methyl-
ene chloride, and the solution was washed with water
(4×25 ml), dried over MgSO4, and evaporated. Ac-
cording to the GLC data, the residue (2.30 g) contained
compounds IV and V II I–X I at a ratio of
50:30:12:4:4. The products were separated by chro-
matography on silica gel using petroleum ether and
petroleum ether–tert-butyl methyl ether (10:1 and 5:1)
as eluents.
(4S)-1-Methyl-4-(prop-1-en-2-yl)-7,8,9-trioxabi-
cyclo[4.2.1]nonane (II). 13C NMR spectrum (MeOH,
C6D6), δC, ppm: 17.91 q (CH3), 19.30 (20.48)* q
(CH3), 28.05 (28.34) t (CH2), 41.25 (40.82) t (CH2),
42.00 (41.63) d (CH), 47.69 (48.30) t (CH2), 97.99
(99.02) d (CHOO), 106.68 (108.44) s (COO), 112.26 t
(CH2=C), 147.24 s (CH2=C).
(3S)-[6-Hydroxy-6-methoxy-3-(prop-1-en-2-yl)-
heptanal (III). 13C NMR spectrum (MeOH, C6D6), δC,
ppm: 17.83 (17.95) q (CH3), 19.40 (20.69) q (CH3),
27.80 (27.17) t (CH2), 40.97 (40.88) t (CH2), 41.35
(41.26) t (CH2), 43.22 (43.08) d (CH), 53.99 (54.43) q
(OCH3), 108.67 (106.53) s [C(OH)OCH3], 113.09 t
(CH2=C), 147.23 (146.39) s (CH2=C), 202.63 d (C=O).
Treatment of peroxide products obtained by
ozonolysis of limonene (I). a. Semicarbazide hydro-
chloride, 7.75 g (70 mmol), was added under stirring at
0°C to a solution of ozonide II, and the mixture was
stirred for 24 h at room temperature. The mixture was
evaporated, the residue was dissolved in methylene
chloride (100 ml), and the solution was washed with
water (4×25 ml), dried over MgSO4, and evaporated.
According to the GLC data, the residue (2.44 g)
contained ester IV and hemiacetal V at a ratio of 9:1,
which were separated by chromatography on silica gel
using petroleum ether and petroleum ether–tert-butyl
methyl ether (10:1 and 5:1) as eluents.
Methyl [(1S)-2,4-dimethoxy-2,4-dimethylcyclo-
hexyl]acetate (IV). Yield 1.64 g (40%), Rf 0.53 (pe-
troleum ether–tert-butyl methyl ether, 2:1). IR spec-
trum (KBr), ν, cm–1: 2827 (OCH3), 1735 (C=O), 1080
1
(C–O). H NMR spectrum, δ, ppm: 1.12 (1.15) s (3H,
CH3), 1.14 (1.22) s (3H, CH3), 1.25–1.33 m (2H,
5-Hax, 6-Hax), 1.43–1.60 m (2H, 5-Heq, 6-Heq), 1.73 d
(1H, 3-Hax, J = 11.0 Hz), 1.91 d (1H, 3-Heq, J =
11.0 Hz), 1.85–1.96 m (1H, 1-H), 2.50 d.d [1H,
CH2C(O)OCH3, J = 9.2, 6.4 Hz], 2.61 d.d [1H,
CH2C(O)OCH3, J = 9.2, 6.3 Hz], 3.10 s (3H, OCH3),
3.17 s (3H, OCH3), 3.63 s (3H, OCH3). 13C NMR spec-
Compound IV. Yield 0.98 g (22%), Rf 0.53
(petroleum ether–tert-butyl methyl ether, 2:1). The
product was identical to a sample of IV isolated as
described in a.
* Hereinafter, signals of the second diastereoisomer are given in
parentheses.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 48 No. 1 2012

OZONOLYTIC TRANSFORMATIONS OF (S)-(–)-LIMONENE
23
4 3 . 3 0 d ( C H ) , 5 1 . 3 5 q ( O C H 3 ) , 1 0 8 . 5 3 s
[C(OH)(OCH3)], 112.46 t (CH2=C), 119.75 s
(CH2CN), 145.17 s (CH2=C).
[(1S)-2,4-Dimethoxy-2,4-dimethylcyclohexyl]-
acetonitrile (VIII). Yield 0.61 g (15%), Rf 0.45 (pe-
troleum ether–tert-butyl methyl ether, 2:1). H NMR
1
spectrum, δ, ppm: 1.11 s (3H, CH3), 1.15 s (3H, CH3),
1.34–1.78 m (2H, 5-Hax, 6-Hax), 1.82–2.10 m (2H,
5-Heq, 6-Heq), 1.89–2.03 m (1H, CH), 1.94 d (1H, 3-H,
J = 11.2 Hz), 2.01 d (1H, 3-H, J = 11.2 Hz), 2.05 d.d
(1H, CH2CN, J = 8.1, 4.5 Hz), 2.27 d.d (1H, CH2CN,
J = 8.1, 5.4 Hz), 3.18 s (3H, OCH3), 3.20 s (3H,
OCH3). 13C NMR spectrum, δC, ppm: 18.19 (18.50) t
(CH2CN), 18.50 q (CH3), 25.43 (21.67) q (CH3), 26.12
(25.05) t (C6), 35.27 (34.84) t (C5), 42.75 d (CH),
43.19 (41.66) t (C3), 49.08 q (OCH3), 49.52 q (OCH3),
74.41 (74.19) s [C(CH3)OCH3], 75.51 (75.34) s
[C(CH3)OCH3], 119.75 s (CN).
d. Dimethyl sulfide, 6.0 ml (80 mmol), was added
under stirring at 0°C to a solution of ozonide II, and
the mixture was stirred for 16 h at room temperature.
The mixture was evaporated, the residue was dissolved
in 100 ml of methylene chloride, and the solution was
washed with water (4×25 ml), dried over MgSO4, and
evaporated to isolate 2.56 g (85%) of ketoaldehyde
XIV. Rf 0.30 (petroleum ether–tert-butyl methyl ether,
2:1). IR spectrum (KBr), ν, cm–1: 2725 [C(O)H], 1710
1
(C=O), 1645 (C=CH2). The H and 13C NMR spectra
of the product were identical to those reported in [1].
Compound XIV, 1.6 g (9.5 mmol), was dissolved
in 30 ml of methanol, 2.3 g (33.3 mmol) of hydroxyl-
amine hydrochloride was added, and the mixture was
stirred for 48 h at room temperature. The mixture was
evaporated, the residue was dissolved in 100 ml of
methylene chloride, and the solution was washed with
water (4×25 ml), dried over MgSO4, and evaporated.
According to the GLC data, the residue (1.3 g) con-
tained ester IV and oxime XVII at a ratio of 85:15.
The products were separated by chromatography on
silica gel using petroleum ether and petroleum ether–
tert-butyl methyl ether (10:1 and 5:1) as eluents.
Methyl (3S)-6-oxo-3-(prop-1-en-2-yl)heptanoate
(IX). Yield 0.25 g (7%), Rf 0.37 (petroleum ether–tert-
1
butyl methyl ether, 2:1). H NMR spectrum, δ, ppm:
1.43–1.60 m (2H, CH2), 1.66 s (3H, CH3), 1.89–2.43 m
(2H, CH2), 2.08–2.39 m (2H, CH2), 2.12 s [3H,
CH3C(O)], 2.43–2.55 m (1H, CH), 3.64 s [3H,
C(O)OCH3], 4.48 d (2H, C=CH2, J = 1.7 Hz).
13C NMR spectrum, δC, ppm: 18.20 q (CH3), 29.89 q
(CH3), 26.14 t (CH2), 34.57 t (CH2), 41.07 t (CH2),
43.03 d (CH), 51.34 s (COOCH3), 112.82 t (CH2=C),
145.23 s (CH2=C), 172.64 s (COOCH3), 208.34 s
(C=O).
Compound IV. Yield 0.95 g (41%), Rf 0.53 (petro-
leum ether–tert-butyl methyl ether, 2:1). The product
was identical to a sample isolated as described in a.
Methyl (3S,6Z)-6-hydroxyimino-3-(prop-1-en-2-
yl)heptanoate (X). Yield 0.07 g (2%), Rf 0.13 (petro-
1
leum ether–tert-butyl methyl ether, 2:1). H NMR
(3S)-6-Hydroxyimino-1-methoxy-3-(prop-1-en-2-
yl)heptan-1-ol (XVII). Yield 0.12 g (6%), Rf 10.22 (pe-
troleum ether–tert-butyl methyl ether, 2:1). H NMR
spectrum, δ, ppm: 1.35–1.70 m (2H, CH2), 1.65 s (3H,
CH3), 1. 82 s (3H, CH3), 2. 15–2. 25 m [1H,
CH2CH(OH)(OCH3)], 2.21–2.35 m (1H, CH), 2.23 t
(2H, CH2, J = 7. 0 Hz), 2. 25–2. 40 m [1H,
CH2CH(OH)(OCH3)], 3.62 s (3H, OCH3), 4.65 t [1H,
CH2CH(OH)(OCH3), J = 6.5 Hz], 4.65–4.93 m
(2H, C=CH2), 5.17 s (1H, OH), 8.2 br.s (1H, NOH).
13C NMR spectrum, δC, ppm: 17.05 q (CH3), 21.60 q
(anti-CH3), 28.49 t (CH2), 38.66 t (CH2), 40.86 t
(CH2), 42.81 d (CH), 51.17 q (OCH3), 101.52 d
[CH(OH)(OCH3)], 112.72 t (CH2=C), 145.19 s
(CH2=C), 157.83 s (C=N).
spectrum, δ, ppm: 1.40–1.81 m (2H, CH2), 1.72 s (3H,
CH3), 1.79 s (3H, CH3), 1.85–2.18 m (2H, CH2), 1.90–
2.50 m (2H, CH2COOCH3), 1.90–2.50 m (1H, CH),
3.65 s (3H, COOCH3), 4.41–4.53 m (2H, C=CH2, J =
13
1.7 Hz), 7.40 br.s (1H, NOH). C NMR spectrum, δC,
ppm: 18.08 q (CH3), 24.65 t (CH2), 24.86 q (anti-CH3),
33.03 t (CH2), 34.08 t (CH2), 42.59 d (CH), 50.83 s
(COOCH3), 112.07 t (CH2=C), 144.95 s (CH2=C),
155.63 s (C=NOH), 173.59 s (COOCH3).
(3S)-6-Hydroxy-6-methoxy-3-(prop-1-en-2-yl)-
heptanenitrile (XI). Yield 0.068 g (2%), Rf 0.10 (pe-
1
troleum ether–tert-butyl methyl ether, 2:1). H NMR
spectrum, δ, ppm: 1.03 s (3H, CH3), 1.42–1.82 m (2H,
CH2), 1.85–2.10 m (2H, CH2), 2.14 s (3H, CH3),
2.43 d.d (1H, CH2CN, J = 12.3, 6.1 Hz), 2.61 d.d (1H,
CH2CN, J = 12.3, 5.7 Hz), 2.60–2.71 m (1H, CH),
3.53 s (3H, OCH3), 3.80 s (1H, OH), 4.30–5.00 m
(2H, C=CH2). 13C NMR spectrum, δC, ppm: 17.68 t
(CH2CN), 18.20 (18.52) q (CH3), 29.88 (29.54) q
(CH3), 26.14 (25.32) t (CH2), 41.07 (36.07) t (CH2),
e. Sodium tetrahydridoborate, 1.89 g (50.0 mmol),
was added under stirring at 10°C to a solution of
ozonide II, and the mixture was stirred for 3 h at room
temperature. A solution of 0.54 ml of acetic acid in
5.4 ml of water was added, the mixture was stirred for
3 h and filtered, and the filtrate was evaporated. The
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 48 No. 1 2012

ISHMURATOV et al.
24
residue was dissolved in 200 ml of methylene chloride,
and the solution was washed with a saturated solution
of sodium chloride (4×25 ml), dried over MgSO4, and
evaporated to isolate 2.30 g (80%) of (3S)-3-(prop-
1-en-2-yl)heptane-1,6-diol (XVIII), Rf 0.34 (ethyl
(KBr), ν, cm–1: 3415 (OH), 1712 (C=O), 1643
(CH=CH2). H NMR spectrum, δ, ppm: 1.52–1.73 m
1
(2H, CH2), 1.58 s (3H, CH3), 2.09 s (CH3), 2.11–
2.29 m (1H, CH2CH2OH), 2.29 t (2H, CH2, J =
7.1 Hz), 2.45–2.51 m (1H, CH2CH2OH), 2.45–2.73 m
(1H, CH), 3.55 t (2H, CH2, J = 6.9 Hz), 4.10 s (1H,
OH), 4.72 d (CH2=C, J = 1.9 Hz). 13C NMR spectrum,
δC, ppm: 17.15 q (CH3), 26.25 t (CH2), 29.60 q (CH3),
35.72 t (CH2), 40.95 t (CH2), 43.15 d (CH), 60.16 t
(CH2OH), 112.30 t (CH2=C), 145.95 s (CH2=C),
209.21 s (C=O).
1
acetate). H NMR spectrum, δ, ppm: 1.24 s (3H, CH3,
J = 7.3 Hz), 1.29–1.70 m (2H, CH2), 1.60–1.71 m (1H,
CH2CH2OH), 1.67 s (3H, CH3), 1.83–2.10 m (2H,
CH2), 2.11–2.18 m (1H, CH), 2.21–2.28 m (1H,
CH2CH2OH), 3.61 s (2H, OH), 3.64–3.80 m (2H,
CH2OH), 3.65–3.80 m (1H, CHOH), 4.76 d (CH2=C,
J = 1.82 Hz). 13C NMR spectrum, δC, ppm: 17.63 q
(CH3), 23.15 (23.08) q (CH3), 29.30 (28.67) t (CH2),
35.94 t (CH2), 36.86 (36.40) t (CH2), 43.95 (43.34) d
(CH), 60.46 t (CH2OH), 67.78 (67.11) d (CHOH),
111.82 t (CH2=C), 146.89 s (CH2=C).
This study was performed under financial support
by the Russian Foundation for Basic Research (project
no. 09-03-00831-a) and by the President of the Rus-
sian Federation (program for support of young Russian
doctors of sciences, project no. MD-3852.2009.3).
Treatment of peroxide products of ozonolysis of
limonene (I) with sodium triacetoxyhydridoborate.
An ozone–oxygen mixture was bubbled through a so-
lution of 1.0 g (7.4 mmol) of olefin I and 0.86 g
(14.8 mmol) of glacial acetic acid in 20 ml of cyclo-
hexane under stirring at 0–2°C until 6.7 mmol of
ozone was absorbed. The mixture was purged with
argon, the cyclohexane layer was separated, and the
residue was diluted with 20 ml of methylene chloride
and added under stirring at 10°C to a suspension of
NaBH(OAc)3 prepared preliminarily by adding a solu-
tion of 5.45 g (90.7 mmol) of glacial acetic acid in
10 ml of methylene chloride to a suspension of 1.12 g
(29.5 mmol) of NaBH4 in 46 ml of methylene chloride
and subsequent stirring for 2 h. The mixture was
allowed to warm up to room temperature, stirred for
3 h, and cooled to 10°C, a solution of 2.25 g of sodium
hydroxide in 50 ml of water was added, and the
organic phase was separated, washed in succession
with a saturated solution of ammonium chloride and
water, dried over Na2SO4, and evaporated to isolate
0.8 g (75%) of ketoalcohol XIX.
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RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 48 No. 1 2012