Transformations of peroxide olefin ozonolysis products in methanol in the presence of water

Article abstract of DOI:10.1134/S1070428013100023

Transformations of peroxide products of ozonolysis of various olefins with different degrees of substitution at the double bond by the action of hydroxylamine and semicarbazide hydrochloride in methanol in the presence of water as co-solvent were studied.

Full text of DOI:10.1134/S1070428013100023

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2013, Vol. 49, No. 10, pp. 1415–1419. © Pleiades Publishing, Ltd., 2013.
Original Russian Text © G.Yu. Ishmuratov, Yu.V. Legostaeva, L.R. Garifullina, L.P. Botsman, R.R. Muslukhov, G.A. Tolstikov, 2013, published in Zhurnal
Organicheskoi Khimii, 2013, Vol. 49, No. 10, pp. 1439–1442.
Transformations of Peroxide Olefin Ozonolysis Products
in Methanol in the Presence of Water
a
a
a
a
G. Yu. Ishmuratov , Yu. V. Legostaeva , L. R. Garifullina , L. P. Botsman ,
a
†b
R. R. Muslukhov , and G. A. Tolstikov
a
Institute of Organic Chemistry, Ufa Research Center, Russian Academy of Sciences,
pr. Oktyabrya 71, Ufa, 450054 Bashkortostan, Russia
e-mail: insect@anrb.ru
b
Vorozhtsov Novosibirsk Institute of Organic Chemistry, Siberian Branch, Russian Academy of Sciences,
pr. Akademika Lavrent’eva 9, Novosibirsk, 630090 Russia
Received May 15, 2013
Abstract—Transformations of peroxide products of ozonolysis of various olefins with different degrees of
substitution at the double bond by the action of hydroxylamine and semicarbazide hydrochloride in methanol in
the presence of water as co-solvent were studied.
DOI: 10.1134/S1070428013100023
We previously showed [1–4] that hydroxylamine
and semicarbazide hydrochlorides are the most effi-
cient nitrogen-containing organic reducing agents
toward peroxide products of olefin ozonolysis in
methyl or isopropyl alcohol; as a result, the corre-
sponding carbonyl compounds and their derivatives are
formed. The structure of peroxide ozonolysis products
and products of their further transformation is deter-
mined by the conditions of ozonolysis, primarily by
the solvent nature [1]. We found [4] that ozonolysis of
olefins in the system isopropyl alcohol–water, fol-
lowed by treatment of peroxide products with semicar-
bazide or hydroxylamine hydrochloride, gives mainly
mixtures of isopropyl esters and carboxylic acids
whose ratio depends on the substrate structure and is
likely to be established at the stage of formation of iso-
propoxy or hydroxy hydroperoxides. In continuation of
studies in this line, in the present work we examined
transformations of peroxide products of ozonolysis of
olefins with different degrees of substitution at the
double bond by the action of the same reagents in
methanol containing water as co-solvent. As substrates
we used non-1-ene (I), cyclooctene (II), 1,5-dimethyl-
3
cycloocta-1,5-diene (III), ∆ -carene (IV, ee 100%),
and (–)-α-pinene (V, ee 86%).
Ozonolysis of non-1-ene (I) in methanol–water at
0°C, followed by treatment with hydroxylamine hydro-
chloride, gave a mixture of products, the major of
which being methyl octanoate VI. From the reaction
mixture we also isolated small amounts of dimethyl
acetal VII, octanal oxime VIII and octanenitrile (IX).
Under analogous conditions, ozonolysis of I and sub-
sequent treatment with semicarbazide hydrochloride
resulted in the formation of octanal semicarbazone (X)
Scheme 1.
O
OMe
(
(
1) O , MeOH–H O, 0°C
3
2
2) NH OH·HCl
2
C H
7
CH2
C H
7
OMe
+
C H
7
OMe
+
C H
7
NOH
+
C H
7 15
CN
15
15
15
15
I
VI
VII
VIII
IX
(
(
1) O , MeOH–H O, 0°C
H
N
3
2
NH2
2) H NC(O)NHNH ·HCl
2
2
C H
7
N
15
I
O
X
†
Deceased.
1
415

1
416
ISHMURATOV et al.
Scheme 2.
(
(
1) O , MeOH–H O, 0°C
3
2
2) NH OH·HCl
COOMe
+
COOMe
COOMe
COOMe
2
+
CH(OMe)2
NOH
II
XI
XII
XIII
(
(
1) O , MeOH–H O, 0°C
3 2
2) H NC(O)NHNH ·HCl
2
2
II
XII + XIII
Scheme 3.
Me
OH
Me
OH
O
N
(
(
1) O , cyclo-C H –MeOH–H O, 4°C
3 6 12 2
Me
2) NH OH·HCl, MeOH–H O
2
2
N
OH
N
+
MeO
Me
Me
XIV
Me
XV
III
(
Scheme 1). The reduction with hydroxylamine hydro-
As shown in [4], the reduction of peroxide ozonol-
3
chloride of peroxide ozonolysis products derived from
cyclooctene (II) afforded methyl 8-hydroxyimino-
octanoate (XI), dimethyl octanedioate (XII), and
methyl 8,8-dimethoxyoctanoate (XIII). Compounds
XII and XIII were obtained when peroxide products of
ysis products obtained from Δ -carene (IV) and
α-pinene (V) in methanol with hydroxylamine hydro-
chloride gives in high yield the corresponding
hydroxyimino esters with trans configuration of the
oxime C=N bond. When the ozonolysis of IV and V
was carried out in methanol in the presence of water,
the products were the same hydroxyimino esters XVI
and XVII, but their yields were lower (Scheme 4).
ozonolysis of cyclooctene (II) in MeOH–H O were
treated with semicarbazide hydrochloride (Scheme 2).
The ozonolysis of 1,5-dimethylcycloocta-1,5-diene
2
The transformation of peroxide products of ozonol-
ysis monoterpenes IV and V in methanol by the action
semicarbazide hydrochloride afforded the correspond-
ing keto esters XVIII and XIX [4]. The same com-
pounds were obtained, though in lower yields, using
the system methanol–water, other conditions being
equal (Scheme 5).
Thus the results of the present study showed that
hydroxylamine and semicarbazide hydrochlorides ef-
fectively reduce peroxide products of olefin ozonolysis
(
III) was carried out in a mixture of cyclohexane with
methanol, and the subsequent treatment of peroxide
products with hydroxylamine hydrochloride in
MeOH–H O led to a mixture of syn/anti-oxime XIV
(
2
1 :1) and syn/anti-dioxime XV (1:1) which were
isolated by column chromatography (Scheme 3). When
the peroxide ozonolysis products derived from III
were treated with semicarbazide hydrochloride, an in-
tractable mixture of unidentifiable compounds was
obtained.
Scheme 4.
Me
(
(
1) O , MeOH–H O, 0°C
3
2
Me
HO
OMe
2) NH OH·HCl
2
N
O
Me
Me
Me
Me
IV
XVI
Me
O
(
(
1) O , MeOH–H O, 0°C
3
2
HO
N
OMe
2) NH OH·HCl
2
Me
Me
Me
Me Me
V
XVII
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 49 No. 10 2013

TRANSFORMATIONS OF PEROXIDE OLEFIN OZONOLYSIS PRODUCTS
1417
Scheme 5.
(
(
1) O , MeOH–H O, 0°C
3 2
2
Me
OMe
2) H NC(O)NHNH ·HCl
2
IV
O
O
Me
Me
XVIII
O
(
(
1) O , MeOH–H O, 0°C
3 2
O
OMe
2) H NC(O)NHNH ·HCl
2
2
V
Me
Me Me
XIX
in aqueous methanol to the corresponding carbonyl
compounds and their derivatives. Under these condi-
tions, the peroxide ozonolysis products are likely to be
methoxy hydroperoxides, whereas no hydroxy hydro-
peroxides are formed. This follows from the pre-
dominant formation of methyl esters after treatment
with semicarbazide or hydroxylamine hydrochloride.
Lower yields of the final products as compared to the
reactions in methanol should be noted.
chloride (general procedure). An ozone–oxygen mix-
ture (1 mol of O per mole of double bond) was
3
bubbled at 0°C through a solution of 10.0 mmol of
olefin I, II, IV, or V in a mixture of 30 ml of distilled
methanol and 1.66 ml of water. The mixture was
purged with argon, 2.4 g (35.0 mmol) of hydroxyl-
amine hydrochloride was added under stirring at 0°C,
and the mixture was stirred at room temperature until
peroxide compounds disappeared according to iodine–
starch test. The solvent was distilled off, the residue
was dissolved in 50 ml of chloroform, and the solution
was washed with brine (4×25 ml), dried over Na SO ,
EXPERIMENTAL
2
4
The IR spectra were recorded on a Shimadzu IR
and evaporated.
Ozonolysis of non-1-ene (I). The residue, 1.32 g,
was subjected to chromatography to isolate 0.95 g
1
13
Prestige-21 instrument. The H and C NMR spectra
were measured on a Bruker AM-300 spectrometer at
3
00 and 75 MHz, respectively, using CDCl as solvent
3
(
60%) of ester VI (R 0.59), 0.10 g (6%) of 1,1-di-
f
and tetramethylsilane as internal reference. Signals in
methoxyoctane (VII, R 0.67), 0.06 g (4%) of oxime
1
f
the H NMR spectra were assigned, and spin–spin
VIII (R 0.53), and 0.04 g (3%) of nitrile IX. The IR
f
coupling constants were determined, with the aid of
double resonance and two-dimensional homonuclear
shift correlation techniques (COSY H–H). The
and NMR spectra of VI–VIII were identical to those
reported in [3, 5].
1
3
Octanenitrile (IX). R 0.26. IR spectrum (KBr):
f
C NMR spectra were recorded with broad-band
–
1
1
ν 2245 cm (CN). H NMR spectrum, δ, ppm: 0.88 t
decoupling from protons and J modulation (JMOD).
GLC analysis was performed using Chrom-5 [1.2-m
column packed with SE-30 (5%) on Chromaton
N-AW-DMCS (0.16–0.20 mm); oven temperature 50–
(
3H, CH , J = 6.7 Hz), 1.18–1.38 m (6H, 4-H, 5-H,
3
6
2
-H), 1.40–1.50 m (2H, 7-H), 1.54–1.62 m (2H, 3-H),
13
.25 t (2H, 2-H, J = 7.4 Hz). C NMR spectrum,
8
2
7
δ , ppm: 13.89 q (C ), 16.94 t (C ), 22.46 t (C ),
C
3
00°C] and Chrom-41 instruments (2.4-m column
3
5
4
6
2
1
4.91 t (C ), 28.86 t (C ), 29.22 t (C ), 31.58 t (C ),
packed with PEG-6000; oven temperature 50–200°C);
carrier gas helium. Sorbfil silica gel (Russia) was used
for TLC analyses (hexane–tert-butyl methyl ether,
19.68 s (CN).
Ozonolysis of cyclooctene (II). The residue,
1.12 g, was subjected to chromatography to isolate
0.56 g (30%) of hydroxyimino ester XI, 0.32 g (15%)
of diester XII, and 0.15 g (7%) of methyl 8,8-di-
methoxyoctanoate (XIII).
2
:1). Column chromatography was performed on silica
gel (70–230 μm; Lancaster, England) using the same
solvent system as eluent. The optical rotations were
measured on a Perkin Elmer 241-MC polarimeter. The
elemental compositions of all isolated compounds
were consistent with the calculated values. The
ozonizer efficiency was 40 mmol of ozone per hour.
Methyl (8Z)-8-(hydroxyimino)octanoate (XI).
–
1
R 0.41. IR spectrum (KBr), ν, cm : 3260 (NOH),
f
1
1
735 (C=O), 1662 (C=N). H NMR spectrum, δ, ppm:
Treatment of peroxide ozonolysis products of
olefins I, II, IV, and V with hydroxylamine hydro-
1.22–1.44 m (8H, 3-H, 4-H, 5-H, 6-H), 1.52–1.70 m
(2H, 2-H), 2.19 m (2H, 7-H), 3.65 s (3H, OCH ), 7.40 t
3
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 49 No. 10 2013

1
418
ISHMURATOV et al.
1
3
(
1H, 8-H), 9.75 s (OH). C NMR spectrum, δ , ppm:
spectrum, δ, ppm: 1.66 s (3H, 4-CH ), 1.78 s (3H,
C
3
3
6
5
4
9
2
2
4.70 t (C ), 26.31 t (C ), 28.20 t (C ), 28.71 t (C ),
C H ), 1.90–2.20 m (6H, 2-H, 3-H, 6-H), 2.20–2.35 m
3
7
2
3
8.95 t (C ), 33.97 t (C ), 51.50 q (OCH ), 151.97 d
(2H, 7-H), 3.50 s (3H, OCH ), 5.03 t (1H, 5-H, J =
3
3
8
13
(
C ), 174.25 s (C=O).
6.9 Hz), 8.00 br.s (1H, OH). C NMR spectrum, δ ,
C
9
6
ppm: 13.35 q (C ), 23.06 q (4-CH ), 24.40 t (C ),
3
Dimethyl octanedioate (XII). R 0.42. The IR and
NMR spectra of diester XII were identical to those
f
3
2
7
3
2.24 t (C ), 35.68 t (C ), 43.53 t (C ), 51.58 q
5 4 8
(
OCH ), 124.63 d (C ), 134.36 s (C ), 157.85 s (C ),
3
given in [2].
1
73.67 s (C=O).
Methyl 8,8-dimethoxyoctanoate (XIII). R 0.52.
f
–
1
(
1Z,4Z,8Z)-8-Hydroxyimino-4-methylnon-4-enal
IR spectrum (KBr), ν, cm : 1735 (C=O), 1080
–1
1
oxime (XV). R 0.56. IR spectrum (KBr), ν, cm : 3260
(
(
2
3
C–O–C). H NMR spectrum, δ, ppm: 1.22–1.44 m
f
1
(
NOH), 1662 (C=N). H NMR spectrum, δ, ppm:
8H, 3-H, 4-H, 5-H, 6-H), 1.52–1.70 m (2H, 7-H),
9
1
.65 s (3H, 4-CH ), 1.77 s (3H, C H ), 2.10–2.21 m
.25 m (2H, CH COOCH ), 3.30 s (6H, 8-OCH ),
3
3
2
3
3
1
3
(
4H, 3-H, 6-H), 2.27–2.33 m (2H, 2-H), 2.35–2.40 m
.65 s (3H, OCH ), 4.24 t (1H, 8-H). C NMR spec-
3
3
3
6
4
(
2H, 7-H), 5.09 t (1H, 5-H, J = 6.7 Hz), 7.30 t (1H,
trum, δ , ppm: 24.70 t (C , C ), 28.73 t (C ), 29.06 t
C
3
13
5
7
2
1
-H, J = 5.0 Hz), 8.20 br.s (2H, NOH). C NMR
9
(
5
C ), 32.40 t (C ), 33.96 t (C ), 51.49 q (COOCH ),
3
8
spectrum, δ , ppm: 13.74 q (C ), 22.69 q (4-CH ),
2.60 q (8-OCH ), 104.46 d (C ), 174.20 s (C=O).
C
3
3
6
3
2
2
4.72 t (C ), 32.66 t (C ), 35.72 t (C ), 43.75 t
7 5 4 1
Ozonolysis of 3-carene (IV). The residue, 1.50 g,
(
C ), 124.60 d (C ), 134.43 s (C ), 151.35 d (C ),
was subjected to chromatography to isolate 1.36 g
8
1
58.20 s (C ).
(
64%) of methyl {(1R,3S)-3-[(2E)-2-(hydroxyimino)-
Treatment of peroxide ozonolysis products of
propyl]-2,2-dimethylcyclopropyl}acetate (XVI),
2
3
R 0.29, [α] = –5° (c = 0.23, CH Cl ). The IR and
olefins I, II, IV, and V with semicarbazide hydro-
f
D
2
2
NMR spectra of compound XVI were identical to
chloride (general procedure). An ozone–oxygen mix-
those given in [4].
ture (1 mol of O per mole of double bond) was passed
3
at 0°C through a solution of 10.0 mmol of olefin I, II,
IV, or V in a mixture of 30 ml of distilled methanol
and 1.66 ml of water. The mixture was purged with
argon, 3.90 g (35.0 mmol) of semicarbazide hydro-
chloride was added at 0°C under stirring, and the
mixture was stirred at room temperature until peroxide
compounds disappeared according to iodine–starch
test. The solvent was distilled off, the residue was
dissolved in 50 ml of chloroform, and the solution was
washed with brine (4×25 ml), dried over Na SO , and
Ozonolysis of α-pinene (V). The residue, 1.45 g,
was subjected to chromatography to isolate 1.34 g
(
63%) of methyl {(1R,3R)-3-[(1E)-hydroxyimino-
ethyl]-2,2-dimethylcyclobutyl}acetate (XVII), R 0.33,
f
2
3
[
α] = –3.7° (c = 0.93, CH Cl ). The IR and NMR
spectra of XVII were identical to those given in [4].
D
2
2
Ozonolysis of 1,5-dimethylcycloocta-1,5-diene
III). An ozone–oxygen mixture was bubbled at 4°C
(
through a solution of 1.50 g (11.0 mmol) of compound
III in a mixture of 13.5 ml of cyclohexane and 0.8 ml
of anhydrous methanol until 10.0 mmol of ozone was
absorbed. The mixture was purged with argon, a solu-
tion of 2.41 g (35 mmol) of hydroxylamine hydro-
chloride in a mixture of 45.3 ml of methanol and 20 ml
of water was added at 0°C, and the mixture was stirred
at room temperature until peroxide compounds disap-
peared according to iodine–starch test. The mixture
was evaporated, the residue was dissolved in 50 ml of
chloroform, the solution was washed with water (4×
2
4
evaporated.
Ozonolysis of non-1-ene (I). The residue, 0.94 g,
was subjected to chromatography to isolate 0.85 g
(
45%) of octanal semicarbazone (X), R 0.11, mp 99–
f
1
00°C [6]. The IR and NMR spectra of X were
identical to those given in [7].
Ozonolysis of cyclooctene (II). The residue,
1.20 g, was subjected to chromatography to isolate
1.00 g (50%) of dimethyl octanedioate (XII) and
0.10 g (5%) of methyl 8,8-dimethoxyoctanoate (XIII)
whose IR and NMR spectra were identical to those
given above.
2
5 ml), dried over Na SO , and evaporated, and the
2
4
residue, 2.10 g, was subjected to chromatography to
isolate 1.49 g (70%) of hydroxyimino ester XIV and
0
.50 g (25%) of dioxime XV.
Ozonolysis of 3-carene (IV). The residue, 1.47 g,
Methyl (4Z,8Z)-8-hydroxyimino-4-methylnon-4-
was subjected to chromatography to isolate 1.29 g
–
1
enoate (XIV). R 0.66. IR spectrum (KBr), ν, cm :
(65%) of methyl [(1R,3S)-2,2-dimethyl-3-(2-oxo-
f
1
20
3
260 (NOH), 1735 (C=O), 1662 (C=N). H NMR
propyl)cyclopropyl]acetate (XVIII), R 0.36, [α]
=
f
D
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 49 No. 10 2013

TRANSFORMATIONS OF PEROXIDE OLEFIN OZONOLYSIS PRODUCTS
1419
–
21° (c = 0.009, CH Cl ). The IR and NMR spectra of
3. Ishmuratov, G.Yu., Legostaeva, Yu.V., Botsman, L.P.,
Muslukhov, R.R., Yakovleva, M.P., and Talipov, R.F.,
Vestn. Bash. Gos. Univ., 2009, no. 1, p. 27.
2
2
XVIII were identical to those given in [4].
Ozonolysis of α-pinene (V). The residue, 1.53 g,
4
. Ishmuratov, G.Yu., Legostaeva, Yu.V., Botsman, L.P.,
Yakovleva, M.P., Shakhanova, O.O., Muslukhov, R.R.,
and Tolstikov, G.A., Khim. Prirodn. Soedin., 2009, no. 3,
p. 272.
was subjected to chromatography to isolate 1.37 g
(
69%) of methyl [(1R,3R)-3-acetyl-2,2-dimethylcyclo-
23
butyl]acetate (XIX), R 0.44, [α] = –24.8° (c = 0.73,
f
D
CH Cl ). The IR and NMR spectra of XIX were
identical to those given in [4].
2
2
5
. Ishmuratov, G.Yu., Legostaeva, Yu.V., Garifullina, L.R.,
Botsman, L.P., Idrisova, Z.I., Muslukhov, R.R., Ishmu-
ratova, N.M., and Tolstikov, G.A., Russ. J. Org. Chem.,
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