Transformation of peroxide products of olefin ozonolysis under treatment with hydroxylamine and semicarbazide hydrochlorides in acetic acid

Article abstract of DOI:10.1134/S1070428014080016

Hydrochlorides of hydroxylamine and semicarbazide efficiently reduce peroxide products of olefin ozonolysis in a system CH₂Cl₂-AcOH leading to the formation of carboxylic acids and their derivatives. The application of water as the solvent component favors the increase in the fraction of nitrogen-containing organic compounds (semicarbazones, keto- and aldoximes, nitriles) and reduction in the yield of carboxylic acids.

Full text of DOI:10.1134/S1070428014080016

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2014, Vol. 50, No. 8, pp. 1075–1081. © Pleiades Publishing, Ltd., 2014.
Original Russian Text © G.Yu. Ishmuratov, Yu.V. Legostaeva, L.R. Garifullina, L.P. Botsman, R.R. Muslukhov, G.A. Tolstikov, 2014, published in
Zhurnal Organicheskoi Khimii, 2014, Vol. 50, No. 8, pp. 1095–1101.
Transformation of Peroxide Products of Olefin Ozonolysis
under Treatment with Hydroxylamine
and Semicarbazide Hydrochlorides in Acetic Acid
G. Yu. Ishmuratova, Yu. V. Legostaevaa, L. R. Garifullinaa, L. P. Botsmana,
R. R. Muslukhova, and G. A. Tolstikovb†
a Institute of Organic Chemistry, Ufa Scientific Center, Russian Academy of Sciences, Oktyabrya pr. 71, Ufa, 450054 Russia
е-mail: insect@anrb.ru
b Vorozhtsov Novosibirsk Institute of Organic Chemistry, Siberian Branch,
Russian Academy of Sciences, Novosibirsk, Russia
Received February 21, 2014
Abstract—Hydrochlorides of hydroxylamine and semicarbazide efficiently reduce peroxide products of olefin
ozonolysis in a system CH2Cl2–AcOH leading to the formation of carboxylic acids and their derivatives. The
application of water as the solvent component favors the increase in the fraction of nitrogen-containing organic
compounds (semicarbazones, keto- and aldoximes, nitriles) and reduction in the yield of carboxylic acids.
DOI: 10.1134/S1070428014080016
The olefin ozonolysis is widely utilized in synthetic
organic chemistry for the preparation of α,ω-
bifunctional oxygen-containing compounds used in
targeted syntheses of substances possessing desired
properties, in particular, of bioregulators of low
molecular weight [1]. Numerous studies showed that
the ozonolysis conditions, in particular, the solvent,
essentially affect the qualitative and quantitative
composition of the reaction products. In the course of
the ozonolysis in proton-donor solvents (alcohols,
carboxylic acids, or water) the arising bipolar ion is
stabilized as a rule forming α-substituted hydrope-
roxides. The part of the acetic acid consists in the
binding of the zwitter-ion into α-acetoxyhydro-
peroxides [2, 3].
the part of the carboxy derivatives. In this connection
we investigated the transformations of the peroxide
products of ozonolysis of versatile olefins
distinguished by the nature and the degree of the
double bond substitution under the treatment with the
same nitrogen organic reagents in the systems CH2Cl2–
AcOH, 5 : 1, and CH2Cl2–AcOH–H2O, 11 : 3 : 1. We
chose as substartes 1-nonene (I), castor oil (II), ∆3-
carene (ee 100%) (III), (–)-α-pinene (ee 86%) (IV).
After the ozonolysis of 1-nonene (I) in a mixture
CH2Cl2–AcOH (0°С) with the subsequent reduction of
the peroxides with hydroxylamine hydrochloride we
isolated from the reaction mixture octanoic acid (V),
and also nitrile VI and aldehyde VII. The ozonolysis
of compound I under the same conditions followed by
the treatment of the peroxides with semicarbazide
hydrochloride afforded in a high yield acid V as a
single reaction product (Scheme 1).
Hydrochlorides of hydroxylamine and semicarbazi-
de efficiently reduce peroxide products of olefin ozo-
nolysis to carbonyl compounds in alcohol solutions:
methanol [4], 2-propanol [5], in the methanol–water
mixture [6]. The application of water as the solvent
component in olefins ozonolysis and the subsequent
workup of the peroxides with semicarbazide and
hydroxylamine hydrochlorides increases the fraction of
nitrogen-containing organic compounds and reduces
The addition of water as the solvent component
under the same reaction conditions resulted in the
change in the ozonolysis products. At the reduction
with hydroxylamine hydrochloride the fractions of
nitrile VI and aldoxime VIII increased and the fraction
of acid V decreased. At the treatment of the peroxides
with semicarbazide hydrochloride semicarbazone IX
was isolated as the main product, and octanoic acid V
* Deceased
1075

ISHMURATOV et al.
1076
Scheme 1.
1. O3, CH2Cl2_AcOH, 0oC
.
2. NH2OH HCl
CO2H
CN
+
V, 68%
VI, 10%
CHO
+
VII, 7%
1. O3, CH2Cl2_AcOH, 0oC
.
2. NH2C(O)NHNH2 HCl
V, 95%
V, 42%
1. O3, CH2Cl2_AcOH_H2O, 0oC
.
I
2. NH2OH HCl
VI, 28%
+
+
NOH
VIII, 18%
1. O3, CH2Cl2_AcOH_H2O, 0oC
.
2. NH2C(O)NHNH2 HCl
+
V, 8%
NNHC(O)NH2
IX, 68%
was present in small amount in the reaction mixture
(Scheme 1).
(XI) acids, and triacylglycerol XII, and at the
treatment with semicarbazide hydrochloride two latter
compounds formed (Scheme 2).
The treatment with hydroxylamine hydrochloride of
the peroxide products of castor oil (II) ozonolysis in
the mixture CH2Cl2–AcOH both in the absence and the
presence of water resulted in the formation in various
ratios of 8-cyanooctanoic (X), (R)-3-hydroxynonanoic
The ozonolysis of natural bicyclic monoterpenes
III and IV in the system CH2Cl2–AcOH followed by
workup of the peroxides with hydroxylamine hydroch-
loride afforded the corresponding ketoacids XIII and
Scheme 2.
1. O3, CH2Cl2_AcOH, 0oC
OH
.
CO2H
2. NH2OH HCl
NC(CH2)7CO2H
CH3(CH2)5
+
X, 63%
XI, 82%
O
H2C
OC(CH2)7CO2H
O
OH
C6H13
+
HC OC(CH2)7CO2H
O
OH
C6H13
H2C OC(CH2)7CO2H
(
)
C6H13
OH
7
XII, 31%
O
1. O3, CH2Cl2_AcOH, 0oC
O
O
.
2. NH2C(O)NHNH2 HCl
(
)
(
)
7
XI, 79% + XII, 85%
7
O
1. O3, CH2Cl2_AcOH_H2O, 0oC
O
O
.
2. NH2OH HCl
II
XI, 68%
X, 50%
XI, 74%
XII, 30%
+
+
1. O3, CH2Cl2_AcOH_H2O, 0oC
.
2. NH2C(O)NHNH2 HCl
XII, 77%
+
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 50 No. 8 2014

TRANSFORMATION OF PEROXIDE PRODUCTS OF OLEFIN OZONOLYSIS
1077
Scheme 3.
1. O3, CH2Cl2_AcOH
.
CO2H
2. NH2OH HCl
CO2H
+
N
O
HO
XIII, 27%
XIV, 30%
1. O3, CH2Cl2_AcOH
.
2. NH2C(O)NHNH2 HCl
XIII, 44%
XIII, 2%
1. O3, CH2Cl2_AcOH_H2O
.
2. NH2OH HCl
CH=NOH
III
XIV, 25%
CN
+
+
+
NOH
NOH
XVIII, 15%
1. O3, CH2Cl2_AcOH_H2O
XIX, 13%
.
2. NH2C(O)NHNH2 HCl
XIII, 40%
XV and hydroxyimino acids XIV and XVII. Besides
after the treatment of α-pinene (IV) peroxides oxo-
nitrile XVI was isolated. The treatment of peroxy pro-
ducts of compounds III and IV ozonolysis with semi-
carbazide hydrochloride in acetic acid furnished the
corresponding ketoacids XIII and XV (Schemes 3, 4).
The generalization of all experimental data obtain-
ned leads to the presumable Scheme 5. The main pero-
xide ozonolysis product is obviously acetoxyhydroper-
oxide XXII. In the course of the ozonolysis in the mix-
ture CH2Cl2–AcOH–H2O both acetoxy- (XXII) and/or
hydroxy- (XXIII) hydroperoxides may form whose
ratio depends in turn on the structure of initial olefins.
The ozonolysis of olefins III and IV in the presence
of water as the solvent component followed by the
peroxides treatment with hydroxylamine hydrochloride
resulted in a sharp decrease in the fraction of ketoacids
XIII and XV and a simultaneous increase in the yield
of nitrogen-containing derivatives XIV, XVIII, XIX
and XVII, XX, XXI respectively. At the reduction with
semicarbazide hydrochloride the same ketoacids XIII
and XV were obtained but in lower yields (Schemes 3, 4).
The treatment of peroxides XXII and XXIII with
hydroxylamine hydrochloride leads to the formation either
of acids XXVIII or of easily hydrolysable esters XXVII.
Another reaction path consists in the reduction of peroxides
XXII and XXIII into aldehyde XXIV that under the action
of hydroxylamine hydrochloride is converted into indivi-
dual compounds or into mixtures along the route aldoxime
XXV → nitrile XXVI → acid XXVIII (Scheme 5).
Scheme 4.
HO
+
O
1. O3, CH2Cl2_AcOH
N
O
.
2. NH2OH HCl
+
CO2H
CO2H
CN
XVII, 22%
XVI, 24%
XV, 33%
1. O3, CH2Cl2_AcOH
.
2. NH2C(O)NHNH2 HCl
XV, 83%
1. O3, CH2Cl2_AcOH_H2O
NOH
NOH
.
2. NH2OH HCl
XV, 4%
XVII, 26%
+
+
CN
+
CH=NOH
IV
XXI, 21%
XX, 28%
1. O3, CH2Cl2_AcOH_H2O
.
2. NH2C(O)NHNH2 HCl
XV, 45%
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 50 No. 8 2014

ISHMURATOV et al.
1078
Scheme 5.
EXPERIMENTAL
OOH
OAc
OOH
NH2OH HCl
IR spectra were recorded on a spectrophotometer
IR Prestige-21 (Fourier Transform Spectrophotometer
– Shimadzu) from thin films. NMR spectra were
registered on high resolution spectrometers Bruker
AM-300 and Bruker Avance III 500 [operating
frequencies 300 and 500 MHz (1Н), 75.47 MHz (13С)]
in CDCl3, internal reference TMS. The assignment of
R
CH
R
CH
OH
XXIII
_H2O
R
CHO
XXIV
NH2OH HCl
XXII
_H2O
R
CH=NOH
XXV
_H2O
O
O
H2O_HCl
_AcOH
H2O
R
CN
R
C
R
OAc
1
signals in Н NMR spectra and measurement of spin-
OH
spin coupling constants were carried out using double
resonance methods and 2D homonuclear correlation
spectroscopy COSY (Н-Н). 13С NMR spectra were
registered in the modes with the wide-band decoupling
from protons and JMOD. GLC was performed on
chromatographs Chrom-5 [column 1.2 m long,
stationary phase silicone SE-30 (5%) on a carrier
Chromaton N-AW-DMCS (0.16–0.20 mm), ramp 50–
300°С] and Chrom-41 [column 2.4 m long, stationary
phase PEG-6000, ramp 50–200°С], carrier gas helium.
TLC monitoring was carried out on SiO2 of Sorbfil
grade (Russia). In column chromatography was used
SiO2 (70–230) Lancaster (England). The optical
rotation was measured on a polarimeter Perkin Elmer
241-MC. The elemental analysis data of all compounds
were consistent with the calculations. The output of the
ozonator was 40 mmol О3/h.
XXVII
XXVIII
XXVI
We believe that obtaining carboxy derivatives in
the presence of semicarbazide hydrochloride may be
due to the dehydration under the action of HCl of the
intermediately formed acetoxy- (XXII) or hydroxy-
(XXIII) hydroperoxides, or to their reduction into
aldehydes XXIV which are oxidized to the
corresponding carboxylic acids XXVIII with nitroso
oxide XXX, the product of the oxidation of
semicarbazide hydrochloride first with peroxide XXII
and then with oxygen through an intermediate stage of
nitrene XXIX formation [7]. In the event of the
monosubstituted olefin I evidently the aldehyde
condensation with semicarbazide in the presence of
water occurs faster than the oxidation with nitroso
oxide resulting in semicarbazone IX (Scheme 6).
Ozonolysis of olefins I–IV in the system CH2Cl2–
AcOH. Through a solution of 10.0 mmol of olefin in a
mixture of 20 mL of CH2Cl2 and 5.7 mL of AсОН at
0°С was bubbled the ozone-oxygen mixture in a
calculated amount: 1 mol of О3 per 1 mol of the double
bond.
Thus the results of the research show that
hydroxylamine and semicarbazide hydrochlorides are
effective reagents for converting peroxy products of
olefin ozonolysis into carboxylic acids and their
derivatives in mixtures CH2Cl2–AcOH and CH2Cl2–
AcOH–H2O. At the use of water as the solvent
component the growth of the content of nitrogen
organic compounds (semicarba-zones, keto- and
aldoximes, nitriles) and decreasing yield of carboxylic
acids was observed.
Treatment of peroxide ozonolysis products with
hydroxylamine hydrochloride. The reaction mixture
was flushed with argon, and at stirring and cooling to
0°С 2.43 g (35.0 mmol) of NH2OH·HCl per one
Scheme 6.
HCl
_H2O
XXIII
or
H2O_HCl
_AcOH
HCl
_H2O
XXVIII
XXVII
XXII
.
NH2C(O)NHNH2 HCl
XXX
XXIV
.
NH2C(O)NHNH2 HCl
IX
O2
XXII
.
.
.
NH2C(O)NHNH2 HCl
NH2C(O)NHNOO
NH2C(O)NHN
XXX
XXIX
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 50 No. 8 2014

TRANSFORMATION OF PEROXIDE PRODUCTS OF OLEFIN OZONOLYSIS
1079
double bond was added, the reaction mixture was
stirred at room temperature till the absence of peroxi-
des (iodine-starch test), CH2Cl2 and AсОH were distil-
led off, the residue was dissolved in CHCl3 (150 mL),
the solution was washed with water (4 × 15 mL), dried
with Na2SO4, and evaporated.
NMR spectrum, δ, ppm: 24.71 t (3С7Н2), 24.88 t
(3С3Н2), 28.84 t (3С6Н2), 29.16 t (3С5Н2), 29.63 t
(3С4Н2), 33.91 t (3С8Н2), 34.59 t (3С2Н2), 62.06 t
(С1'Н2, C3'Н2), 68.06 d (С2'Н), 172.63 s (С9'О2), 173.26
s (С9О2, С9''О2), 178.77 s (3СООН).
The ozonolysis of (+)-3-carene (III) after
chromatographing the residue (1.32 g) (SiO2, hexane–
tert-butyl methyl ether, 5 : 1→1 : 1) afforded 0.5 g
(27%) of ketoacid XIII and 0.60 g (30%) of
hydroxyimino acid XIV.
The ozonolysis of 1-nonene (I) after
chromatographing the residue (1.28 g) afforded 0.97 g
(68%) of octanoic acid (V), 0.12 g (10%) of nitrile VI,
and 0.09 g (7%) of octanal (VII).
Octanoic acid (V). Rf 0.25 (hexane–tert-butyl
methyl ether, 2 : 1). 1H NMR spectrum, δ, ppm: 0.87 t
(3H, С8H3, J 6.6 Hz), 1.20–1.37 m (6H, С4–6H2), 1.43–
1.58 m (2H, С7H2), 1.56–1.69 m (2H, С3H2), 2.24 t
[2,2-Dimethyl-3-(2-oxopropyl)cyclopropyl]acetic
acid (XIII). Rf 0.19 (hexane–tert-butyl methyl ether,
4 : 1), [α]D20 –14° (CH2Cl2, с 2.23). IR spectrum, ν, cm–1:
1
3331 (OH), 1712 (С=О). Н NMR spectrum, δ, ppm:
13
(2Н, С2Н2, J 6.7 Hz), 11.45 br.s (1Н, ОН). IR and С
0.94 s (3Н, cis-СН3), 0.98 d.d (1Н, C1Н, J 10.2, 6.3 Hz),
1.09 d.d (1Н, C3Н, J 10.2, 5.1 Hz), 1.10 s (3Н, trans-
СН3), 2.04 s (3Н, СН3СО), 2.11–2.20 m (2Н,
СН2СООН), 2.30–2.38 m (2Н). 13С NMR spectrum, δ,
ppm: 14.12 q (cis-СН3), 17.09 s (С2), 20.90 d (С1H),
22.27 d (С3), 28.41 q (trans-СН3), 30.78 t (CH2CO·
CH3), 30.78 q (CH2COCH3), 32.96 t (СН2СООН),
177.02 s (COOН), 212.38 s (С=О).
NMR spectra are identical to previously described [8].
Octanonitrile (VI). Rf 0.26 (hexane–tert-butyl
methyl ether, 2 : 1). IR and NMR spectra are identical
to previously described [6].
Octanal (VII). IR spectrum, ν, cm–1: 1718 (С=O).
NMR spectra are identical to those described in [9].
The ozonolysis of castor oil (II) after
chromatographing the residue (10.25 g) (SiO2, hexane–
tert-butyl methyl ether, 5 : 1→1 : 1) gave 3.17 g (63%)
of mononitrile X, 4.2 g (82%) of hydroxyacid XI, 1.86 g
(31%) of triacylglycerol XII.
{3-[(2Е)-2-(Hydroxyimino)propyl]-2,2-dimethyl-
cyclopropyl}acetic acid (XIV). Rf 0.17 (hexane–tert-
butyl methyl ether, 4 : 1). IR spectrum, ν, cm–1: 3334
(OH), 1714 (С=О), 1633 (C=N). 1Н NMR spectrum, δ,
ppm: 0.76 d.d.d (1Н, C1Н, J 9.2, 7.2, 1.8 Hz), 0.94
d.d.d (1Н, C3Н, J 9.2, 7.7, 2.1 Hz), 0.95 s (3Н, cis-
СН3), 1.09 s (3Н, trans-СН3), 1.93 s (3Н, СН3), 2.27–
2.33 m (1Н, СНАСО2Н), 2.28 d.d (1Н, СНАСNOH, J –
13.1, 5.2 Hz), 2.31 d.d (1Н, СНВСNOH, J –13.1,
7.1 Hz), 2.48 d.d (1Н, СНВСО2Н, J 15.7, 6.9 Hz), 8.00
br.s (2Н, 2ОН). 13С NMR spectrum, δ, ppm: 13.49 q
(СН3С=NOH), 14.90 q (СН3), 17.42 s (С2), 21.79 d
(С1H), 22.38 d (С3H), 28.53 q (СН3), 29.66 t (CH2CO·
OН), 30.88 t (CH2CNOH), 158.74 s (C=NOH), 175.05
s (COOН).
8-Cyanooctanoic acid (X). Rf 0.28 (hexane–tert-
butyl methyl ether, 1 : 1). IR spectrum, ν, cm–1: 2220
(С≡N), 1700 (С=О). 1H NMR spectrum, δ, ppm: 1.10–
1.40 m (8H, С3–6H2), 1.57–1.65 m (2H, С7H2), 2.31–
2.42 m (4H, С8Н2, С2Н2), 9.80 br.s (COOH). 13С NMR
spectrum, δ, ppm: 17.00 t (С8Н2), 24.70 t (С3Н2), 25.24
t (С7Н2), 28.41 t (С6Н2) 28.81 t (С5Н2), 29.09 t (С4Н2),
33.99 t (С2Н2), 119.76 s (СN), 177.77 s (СООН).
(R)-3-Hydroxynonanoic acid (XI). Rf 0.14
(hexane–tert-butyl methyl ether, 1 : 1). [α]D20 –5°
(CH2Cl2, с 1.4). IR spectrum, ν, cm–1: 3420 (ОН),
1701 (С=О). NMR spectra are identical to previously
described [10].
The ozonolysis of (–)-α-pinene (IV) after
chromatographing the residue (1.60 g) (SiO2, hexane–
tert-butyl methyl ether, 20 : 1→1 : 1) provided 0.61 g
(33%) of ketoacid XV, 0.4 g (24%) of ketonitrile XVI,
and 0.43 g (22%) of hydroxyimino acid (XVII).
9,9',9"-(Propane-1,2,3-triyltrioxy)tris(9-oxono-
nanoic acid) (XII). Rf 0.07 (hexane–tert-butyl methyl
1
ether, 1 : 1). H NMR spectrum, δ, ppm: 1.15–1.77 m
(3-Acetyl-2,2-dimethylcyclobutyl)acetic acid
(XV) [11]. Rf 0.21 (hexane–tert-butyl methyl ether, 4 : 1),
[α]D20 –39.8º (CH2Cl2, с 0.8164). IR spectrum, ν, cm–1:
3330 (OH), 1715 (С=О). 1Н NMR spectrum δ, ppm: 0.83
s (3Н, cis-СН3), 1.29 s (3Н, trans-СН3), 1.83–1.92 m
(1Н, cis-С4Н2), 1.94 d.d (1Н, trans-С4Н2, J 10.1,
(12Н, 3С3Н2, 3С7Н2), 1.16–1.40 m (18Н, 9СН2,
3С4–6Н2), 2.15 t (6Н, 3С8Н2, J 6.7 Hz), 2.35 t (6Н,
3С2Н2, J 6.6 Hz), 4.15 d.d (2Н, С1'НА , С3'НА , J 11.9,
2
2
4.1 Hz), 4.28 d.d (2Н, С1'НВ , С3'НВ , J 11.9, 5.7 Hz),
2
2
5.27–5.32 m (1Н, С2'H), 9.81 s (3Н, СООН). 13C
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 50 No. 8 2014

ISHMURATOV et al.
1080
10.7 Hz), 2.03 s (3Н, СН3СО), 2.12–2.36 m (1Н, С1Н,
2Н, СН2СООН), 2.83 d.d (1Н, С3Н,J 10.1, 7.5 Hz), 9.70
Ozonolysis of olefins I–IV in the system CH2Cl2–
AcOH–H2O. Through a solution of 10.0 mmol of
olefin in a mixture of 20 mL of CH2Cl2, 5.7 mL of
AсОН, and 1.8 mL of Н2О at 0°С was bubbled the
ozone-oxygen mixture in a calculated amount: 1 mol
of О3 per 1 mol of the double bond.
13
br.s (1Н, СООН). С NMR spectrum, δ, ppm: 16.78 q
(cis-СН3), 22.12 t (С4Н2), 29.68 q (СН3СО), 30.26 q
(trans-СН3), 35.95 t (CH2COОН), 37.10 d (C1Н), 42.94 s
(С2), 52.88 d (С3Н), 178.28 s (COOН), 208.27 s (С=О).
(3-Acetyl-2,2-dimethylcyclobutyl)acetonitrile
(XVI) [11]. Rf 0.33 (hexane–tert-butyl methyl ether,
3 : 2), [α]D20 –131.16° (CHCl3, с 1.02) [11]. IR
Treatment of peroxide products of olefins I–IV
ozonolysis in the system CH2Cl2–AcOH–H2O with
hydroxylamine hydrochloride. The reaction mixture
was flushed with argon, and at stirring and cooling to
0°С 2.43 g (35.0 mmol) of NH2OH·HCl per one
double bond was added, the reaction mixture was
stirred at room temperature till the absence of peroxi-
des (iodine-starch test), CH2Cl2 and AсОН were distil-
led off, the residue was dissolved in CHCl3 (150 mL),
the solution was washed with water (4 × 15 mL), dried
with Na2SO4, and evaporated.
1
spectrum, ν, cm–1: 2220 (СN). Н NMR spectrum, δ,
ppm: 0.95 s (cis-CH3), 1.40 s (trans-CH3), 1.94 d.t
(1Н, cis-С4Н2, J –11.0, 9.5 Hz), 2.03 d.t (1Н, trans-
С4Н2, J –11.0, 8 Hz), 2.08 s [3Н, СН3С(О)], 2.32 d.d
(1Н, СН2СN, J 15.2, 8.00 Hz), 2.32 d.d (1Н, СН2СN,
J 15.2, 7.8 Hz), 2.37–2.43 m (1Н, С1Н), 2.90 d.d (1Н,
С3Н, J 9.5, 8.0 Hz). 13С NMR spectrum, δ, ppm: 16.54
q (СН3), 17.25 t (СН2), 22.89 t (С4Н2), 29.86 q (СН3),
30.27 q [СН3С(О)], 38.16 d (С1Н), 42.97 s (С2), 53.81
d (С3Н), 118.56 s (CN), 206.63 s (C=O).
The ozonolysis of 1-nonene (I) after
chromatographing the residue (1.30 g) afforded 0.61 g
(42%) of octanoic acid (V), 0.35 g (28%) of nitrile VI,
and 0.26 g (18%) of octanaloxime (VIII).
{3-[(Е)-2-(Hydroxyimino)ethyl]-2,2-dimethyl-
cyclobutyl}acetonitrile (XVII). Rf 0.30 (hexane–tert-
butyl methyl ether, 3 : 2). IR and NMR spectra are
identical to previously described [5].
Octanaloxime (VIII). Rf 0.53 (hexane–tert-butyl
methyl ether, 2 : 1). IR and NMR spectra are identical
to previously described [5].
Treatment of peroxide products of olefins I–IV
ozonolysis with semicarbazide hydrochloride. The
reaction mixture was flushed with argon, and at
stirring and cooling to 0°С 3.90 g (35.0 mmol) of NH2·
C(O)NHNH2·HCl per one double bond was added, the
reaction mixture was stirred at room temperature till
the absence of peroxides (iodine-starch test), CH2Cl2
and AсОН were distilled off, the residue was dissolved
in CHCl3 (150 mL), the solution was washed with
water (4 × 15 mL), dried with Na2SO4, and evaporated.
The ozonolysis of castor oil (II) after
chromatographing the residue (9.46 g) (SiO2, hexane–
tert-butyl methyl ether, 5 : 1→1 : 1) gave 2.52 g (50%)
of mononitrile X, 3.48 g (68%) of hydroxyacid XI,
1.68 g (30%) of triacylglycerol XII.
The ozonolysis of (+)-3-carene (III) after
chromatographing the residue (1.30 g) (SiO2, hexane–
tert-butyl methyl ether, 20 : 1→1 : 1) afforded 0.50 g
(25%) of hydroxyimino acid XIV, 0.23 g (13%) of
hydroxyiminonitrile XVIII, 0.3 g (15%) of dioxime
XIX, and 0.04 g (2%) of ketoacid XIII.
By the ozonolysis of 1-nonene (I) we obtained 1.37 g
(95%) of octanoic acid (V).
The ozonolysis of castor oil (II) after
chromatographing the residue (9.84 g) (SiO2, hexane–
tert-butyl methyl ether, 5 : 1→1 : 1) yielded 4.05 g
(79%) of hydroxyacid XI and 5.12 g (85%) of
triacylglycerol XII.
{3-[(Е)-2-(Hydroxyimino)propyl]-2,2-dimethyl-
cyclopropyl}acetonitrile (XVIII). Rf 0.32 (hexane–
tert-butyl methyl ether, 3 : 2). IR spectrum, ν, cm–1:
1
2220 (СN), 1642 (С=N). Н NMR spectrum, δ, ppm:
0.78 d.d.d (1Н, C1Н, J 9.1, 7.4, 1.8 Hz), 0.96 d.d.d
(1Н, C3Н, J 9.1, 7.7, 2.1 Hz), 0.93 s (3Н, cis-СН3),
1.30 s (3Н, trans-СН3), 1.95 s [3Н, СН3С(NОH)],
2.00–2.20 m (2Н, СН2СN), 2.29–2.35 m (2Н), 6.80
br.s (1Н, NOH). 13С NMR spectrum, δ, ppm: 14.63 q
(СН3), 14.70 q [С(NOH)СН3], 17.51 s (С2Н), 17.66 t
(CH2CN), 22.14 d (С1Н), 22.68 d (С3Н), 28.35 q
(СН3), 30.62 t (CH2CNOH), 118.57 s (CN), 158.21 s
(C=NOH).
The ozonolysis of (+)-3-carene (III) after
chromatographing the residue (1.63 g) (SiO2, hexane–
tert-butyl methyl ether, 5 : 1→1 : 1) afforded 0.815 g
(44%) of ketoacid XIII.
The ozonolysis of (–)-α-pinene (IV) after
chromatographing the residue (2.03 g) (SiO2, hexane–
tert-butyl methyl ether, 5 : 1→1 : 1) provided 1.75 g
(83%) of ketoacid XV.
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TRANSFORMATION OF PEROXIDE PRODUCTS OF OLEFIN OZONOLYSIS
1081
{3-[(Е)-2-(Hydroxyimino)propyl]-2,2-dimethyl-
cyclopropyl}ethanaloxime (XIX). Rf 0.26 (hexane–
tert-butyl methyl ether, 4 : 1). IR spectrum, ν, cm–1: 3272
(OH). 13С NMR spectrum, δ, ppm: 14.10 q (СН3), 14.63
q [С(NOH)СН3], 16.93 s (С2Н), 17.56 t (CH2C=NОН),
21.58 d (С1Н), 22.72 d (С3Н), 28.49 q (СН3), 30.15 t
(CH2CNOH), 151.59 s (CN), 157.13 s (C=NOH).
In ozonolysis of castor oil (II) after
chromatographing the residue (9.32 g) (SiO2, hexane–
tert-butyl methyl ether, 5 : 1→1 : 1) we obtained 3.82 g
(74%) of hydroxyacid XI and 4.66 g (77%) of
triacylglycerol XII.
In ozonolysis of (+)-3-carene (III) after
chromatographing the residue (1.22 g) (SiO2, hexane–
tert-butyl methyl ether, 5 : 1→1 : 1) we obtained 0.74 g
(40%) of ketoacid XIV.
In ozonolysis of (–)-α-pinene (IV) after
chromatographing the residue (1.70 g) (SiO2, hexane–
tert-butyl methyl ether, 20 : 1→1 : 1) we isolated
0.51 g of hydroxyiminonitrile (28%) XX, 0.51 g (26%)
of hydroxyimino acid XVII, 0.43 g (21%) of dioxime
XXI, 0.07 g (4%) of ketoacid XV.
In ozonolysis of (–)-α-pinene (IV) after
chromatographing the residue (1.61 g) (SiO2, hexane–
tert-butyl methyl ether, 5 : 1→1 : 1) we obtained 0.84 g
(45%) of ketoacid XV.
{(1S,3S)-3-[(Е)-2-(Hydroxyiminoethyl]-2,2-di-
mehylcyclobutyl}acetonitrile (XX). Rf 0.30 (hexane–
tert-butyl methyl ether, 3 : 2). IR and NMR spectra are
identical to previously described [5].
In the study the equipment was used of the Center
of joint application “Khimiya” of the Institute of
Organic Chemistry, Ufa Scientific Center, Russian
Academy of Sciences.
(1Е)-{3-[(Е)-2-(Hydroxyimino)ethyl]-2,2-dimet-
hylcyclobutyl}acetaldoxime (XXI). Rf 0.25 (hexane–
tert-butyl methyl ether, 4 : 1). IR spectrum, ν, cm–1:
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1
3330 (OH). Н NMR spectrum, δ, ppm: 0.82 s (3Н,
cis-СН3), 1.18 s (3Н, trans-СН3), 1.70–1.78 m [2Н,
CH2CH(NOH)], 1.77 с [3Н, СН3С(NOH)], 2.15–2.23
m (1Н, cis-С4Н2), 2.17–2.20 m (1Н, С1Н), 2.32–2.44 m
(1Н, trans-С4Н2), 2.55–2.64 m (1Н, С3Н), 6.20 t (1Н,
CH=NOH, J 6.1 Hz), 6.50 br.s (trans-NOH), 9.60 br.s
(trans-NOH). 13С NMR spectrum, δ, ppm: 16.48 q
(СН3С=NOH), 16.86 q (СН3), 17.32 t (CH2CН=N·
ОН), 24.58 t (С4Н2), 30.19 q (СН3), 39.46 d (C1Н),
42.85 s (С2), 47.87 d (С3Н), 118.58 d (CН=NОН),
156.93 s (C=NOH).
Treatment of peroxide products of olefins I–IV
ozonolysis in the system CH2Cl2–AcOH–H2O with
semicarbazide hydrochloride. The reaction mixture
was flushed with argon, and at stirring and cooling to
0°С 3.90 g (35.0 mmol) of NH2C(O)NHNH2·HCl per
one double bond was added, the reaction mixture was
stirred at room temperature till the absence of peroxi-
des (iodine-starch test), CH2Cl2 and AсОН were distil-
led off, the residue was dissolved in CHCl3 (150 mL),
the solution was washed with water (4 × 15 mL), dried
with Na2SO4, and evaporated.
6. Ishmuratov, G.Yu., Legostaeva, Yu.V., Garifullina, L.R.,
Botsman, L.P., Muslukhov, R.R., Ishmuratova, N.M., and
Tolstikov, G.A., Russ. J. Org. Chem., 2013, vol. 49, p. 1415.
7. Brinen, J.B., and Singh, B., J. Am. Chem. Soc., 1971,
vol. 93, p. 6623.
8. Arivazhagan, G., Parthipan, G., and Thenappan, T.,
Spectrochim. Acta, Part A, 2009, vol. 74, p. 860.
9. Tietze, L.-F. and Eicher, T., Reactions and Syntheses in
the Organic Chemistry Laboratory, Mill Valley,
California: University Science Books, 2009.
10. Ruth, K., Grubelnik, A., Hartmann, R., Egli, Th., Zinn, M.,
and Ren, Q., Biomacromolecules, 2007, vol. 8, p. 279.
11. Makaev, F.Z., Radul, O.M., and Gudima, A.P., Russ.
Chem Bull., 2008, vol. 57, p. 1571.
12. Ishmuratov, G.Yu., Legostaeva, Yu.V., Botsman, L.P.,
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p. 1272.
In ozonolysis of 1-nonene (I) after chromatogram-
phing the residue (1.4 g) we obtained 1.26 g (68%) of
semicarbazone VIII, 0.12 g (8%) of octanoic acid (V).
Octanal semicarbazone (VIII). Rf 0.4 (hexane–tert-
butyl methyl ether, 2 : 1), mp 99–100°С [9]. IR and
NMR spectra are identical to previously described [12].
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 50 No. 8 2014