Ozonolysis of alkenes and study of reactions of polyfunctional compounds: LXVIII. Investigation of transformations of peroxide products of olefins ozonolysis treated with hydroxylamine hydrochloride

Article abstract of DOI:10.1134/S1070428007080039

Hydroxylamine hydrochloride efficiently reduces peroxide products of olefins ozonolysis into carbonyl compounds. Depending on the substrate character, solvent, and the treatment conditions the arising aldehydes transformed along the route aldehyde→aldoxime→nitrile→ester into individual compounds or their mixtures, or give the corresponding acetals.

Full text of DOI:10.1134/S1070428007080039

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2007, Vol. 43, No. 8, pp. 1114−1119. © Pleiades Publishing, Ltd., 2007.
Original Russian Text © G.Yu. Ishmuratov, A.Kh. Shayakhmetova, M.P. Yakovleva, Yu.V. Legostaeva, O.V. Shitikova, E.G. Galkin, G.A. Tolstikov,
2
007, published in Zhurnal Organicheskoi Khimii, 2007, Vol. 43, No. 8, pp. 1125−1129.
Ozonolysis of Alkenes and Study of Reactions of Polyfunctional
Compounds: LXVIII.* Investigation of Transformations
of Peroxide Products of Olefins Ozonolysis Treated with
Hydroxylamine Hydrochloride
G. Yu. Ishmuratov, A. Kh. Shayakhmetova, M. P. Yakovleva, Yu. V. Legostaeva,
O. V. Shitikova, E. G. Galkin, and G. A. Tolstikov
Institute of Organic Chemistry, Ufa Scientific Center, Russian Academy of Sciences, Ufa, 450054 Russia
e-mail: insect@anrb.ru
Received May 30 2007
Abstract—Hydroxylamine hydrochloride efficiently reduces peroxide products of olefins ozonolysis into carbonyl
compounds. Depending on the substrate character, solvent, and the treatment conditions the arising aldehydes
transformed along the route aldehyde→aldoxime→nitrile→ester into individual compounds or their mixtures, or
give the corresponding acetals.
DOI: 10.1134/S1070428007080039
The conversion of peroxide products of olefins ozono-
with hydroxylamine hydrochloride in methanol the
ozonolysis products first formed aldehydes converted
further into aldoximes which suffered cleavage by
Beckmann reaction into the corresponding nitriles whose
cyano group transformed into methoxycarbonyl group.
lysis into carbonyl compounds (aldehydes, ketones) is
extensively used in preparative organic synthesis. The
most often applied traditional reducers are dimethyl
sulfide, triphenylphosphine, thiourea, sodium bisulfite,
zinc powder, sodium thiosulfate, lower metal salts, and
alkali metals iodides. The chemoselective hydrogenation
catalyzed by platinum group metals is an efficient method
for ozonoysis products reduction [2, 3]. Oxidative decom-
position of ozonolysis products into carboxylic acids and
their derivatives is carried out under the action of oxygen
at elevated temperature or under the treatment of
oxidation catalysts (ozone, compounds of variable
valence metals, amino acids etc.). Other oxidants employ-
ed are silver oxide suspension in an alkaline solution,
potassium permanganate, chromic and nitric acids, and
especially often hydrogen peroxide in the presence of
selenium dioxide [2–5].
To prove this assumption we carried out the reaction
with hydroxylamine hydrochloride of peroxide ozono-
lysis products obtained from a series of disubstituted (I,
IIa, IIb, and III), trisubstituted (IV), and tetrasubstituted
(V) olefins (Scheme 1).
The oxidation of cyclooctene (I) with equimolar
amount of ozone in methanol at 0°C followed by the
treatment with hydroxylamine hydrochloride (0°C,
0.5 h; boiling, 10 h) provided a mixture of dimethyl
octanedioate (VI) and nitriloester VII, 1:1. A similar
treatment of the castor oil (IIa) (~85% of ricinoleic acid)
and its acetate IIb led to the formation of mixtures of
hydroxyester VIII, dimethyl nonanedioate (IX), and its
monocyano derivative X, 1.6:4.9:1 and 1:4.6:2.4 respec-
tively. The ozonolysis of homoallyl alcohol III obtained
from castor oil (IIa) [10] after the treatment with the
hydroxylamine hydrochloride yielded a mixture of the
same hydroxyester VIII, nitrile XI, and methyl nonanoate
XII in a ratio 1:1:1.6. The treatment of peroxide products
of olefins IV and V ozonolysis confirmed the low
reactivity of keto group as compared with aldehyde
We applied hydroxylamine hydrochloride to the
conversion of peroxide ozonolysis products obtained
from a series of olefin compounds. The reactions were
performed in methanol and depending on the substrate
character we obtained aldehydes [6], aldoxime [7, 8],
and ester [9]. It was presumable that at the treatment
*
For Communication LXVII, see [1].
1114

1
115
OZONOLYSIS OF ALKENES: LXVIII.
Scheme 1.
а, b
а, b
MeO C(CH ) CO Me + NC(CH ) CO Me
2
2 6
2
2 6
2
VI
VII
I
RO CH2
RO CH
OH
CO Me + MeO C(CH ) CO Me + NC(CH ) CO Me
2
2
2 7
2
2 7
2
CH (CH )
3
2 5
RO CH2
VIII
X
IX
IIа, IIb
[10]
OH
а, b
VIII + CH (CH ) CN + CH (CH ) CO Me
3
2 7
3
2 7
2
CH (CH )
3
2 5
(CH ) CH
2
7
3
III
XI
XII
CO Me
2
а, b
O
IV
XIII
O
а, b
O
V
XIV
OH
OAc
*
(IIa) CH (CH )
,
3 2 5
(IIb).
R = CH (CH )
3
2 5
(CH ) CO
(CH ) CO
2 7
2
7
Reagents: (a) O /MeOH; (b) NH OH·HCl/MeOH.
3
2
function with respect to hydroxylamine. These cyclo-
olefins were in high yield converted into formerly
described [11, 12] ketoester XIII and diketone XIV.
The main feature of the mass spectrum of compound
XI with a linear carbon chain [13] is the presence of two
homologous ion series [here and hereinafter on Schemes
+
m/z (I , %)]: (1) [N≡CC H ] 40 (8), 64 (48), 68 (11),
The identification of compounds obtained was
performed by NMR spectroscopy and GC-MS method.
rel
n
2n
+
8
4
2 (94), 96 (98), 110 (47), 124 (10); (2) [N≡CC H2n+1]
1 (100), 55 (42), 69 (38), 83 (58), 111 (11).
n
Compound XI was identified as nonanenitrile. The
interpretation of its mass spectrum was performed
applying a hunt system HPChem Station that used the
spectral library NISTO2. The identity index of the
registered spectrum and that from the library (002243-
In the mass spectra of compounds VII and X both
homologous ion series typical of nitriles were registered:
(1) [N≡CC H ] , (2) [N≡CC H2n+1]+ (Scheme 2).
+
n
2n
n
+
Besides ion peaks [(CH ) COOMe] , m/z 59, 73, 87, 101,
2
n
2
7-8 CAS) was 95%.
115 were present characteristic of carboxylic acids esters
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 43 No. 8 2007

1116
ISHMURATOV et al.
[
13]. The main decomposition directions of esters molec-
point of the carbon chain branching is preferable for bond
cleavage. The most abundant peak in the mass spectrum
of compound VIII was that of ion m/z 103 (100%), and
its formation was possible only for the 3-hydroxy-
substituted derivative (Scheme 3).
ular ions are well known to occur by bond cleavage on
both sides of the carbonyl group [13, 14]. Therewith the
acyl ions peaks [M – OMe] , m/z (I , %): 138 (57) (VII);
+
rel
1
52 (39) (X) are as a rule more intensive than those of
+
ions [M – COOMe] 110 (31) (VII); 124 (21) (X). The
maximum abundance was found for the rearranged frag-
ments with odd electrons number [CH C(OH)OMe] ,
The presence in the molecule of compound VIII of
hydroxy and ester groups governed the directions of the
molecular ion decomposition. The alcohols [13] char-
.
+
2
m/z 74 (100%) (Scheme 2). Thus the presence of nitrile
and ester functions separated by methylene groups in
compounds VII and X results in the formation of
diagnostic ion series.
acteristically eliminate water [m/z 170 (1) (M – H O)],
2
methyl esters, methoxy and methoxycarbonyl groups,
occurring after water elimination (Scheme 3). As was
presumed [13], the intensity of acyl ion peak [m/z 139
(
1
8)] was higher than that of hydrocarbon ion peak [m/z
11 (0.6)].
In the spectrum of methyl (3R)-3-hydroxynonano-
ate (VIII) peaks of ions belonging to alcohol series
+
were observed [(CH ) OH] , [m/z (I , %): 31 (10), 45
The successive treatment of the ozonolysis product
of castor oil (IIa) in dichloromethane with hydroxylamine
hydrochloride (boiling, 10 h) and methanol in the
presence of p-toluenesulfonic acid (boiling, 6 h) resulted
in a single product of low molecular weight, hydroxy-
2
n
rel
(
[
7), 59 (8), 87 (8), 101 (4), 115 (2)], and a peak
.
+
CH C(OH)OMe] m/z (I , %): 74 (33) typical of
2
rel
aliphatic acids methyl esters. The position of the hydroxy
group is established from the known fact [13] that the
Scheme 2.
Scheme 3.
OH
.
COOMe
_
COOMe
(
CH ) OH
2
n
n = 1 7
_
H O
2
VIII, [M]+ 188 (0.3)
170 (1)
_
_
C6H13
CO Me
2
OH
_
OMe
OH
O
CO Me
2
1
11 (0.6)
1
03 (100)
O
7
4 (33)
1
39 (8)
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 43 No. 8 2007

OZONOLYSIS OF ALKENES: LXVIII.
1117
Scheme 4.
MeOH at 0°C was bubbled a mixture of ozone with oxy-
gen till amount of consumed O was 1 mol per 1 mol of
double bonds. The reaction mixture was flushed with
argon, then at stirring at 0°C was added within 0.5 h
3
OH
а, b
IIa
СH (СH )
3 2 5
O
2
.4 g (35 mmol) of NH OH·HCl per 1 mol of double
2
bonds. The reaction mixture was boiled till disappearance
of peroxides (10 h), MeOH was distilled off, the residue
was diluted with CH Cl , washed with H O, the organic
OH
OMe
OMe
c
2
2
2
СH (СH )
3
2 5
layer was dried over Na SO , and evaporated.
XV
2
4
Ozonolysis of cyclooctene (I). We obtained 1.0 g of
reaction product containing according to GLC dimethyl
octandioate (VI) and methyl 7-cyanoheptanoate (VII)
in a ratio 1:1.
Reagents: (a) O /CH Cl ; (b) NH OH·HCl/CH Cl ; (c)
MeOH/TsOH.
3
2
2
2
2
2
acetal XV. These findings show, that the hydroxylamine
hydrochloride acts just as a reducer of the ozonides most
probably formed under the conditions producing the
precursor of compound XV, (3R)-3-hydroxynonanal.
Methyl 7-cyanoheptanoate (VII). Mass spectrum,
+
m/z (I , %): 169 (0.4) [M] , 138 (57), 110 (31), 109
rel
(
24), 97 (18), 96 (57), 83 (58), 82 (24), 74 (100), 69
Thus it follows from the previous data [6–9] and the
findings reported here that the hydroxylamine hydro-
chloride is an efficient reducer of peroxide products of
olefins ozonolysis to carbonyl compounds. Depending
on the substrate, solvent [15], and the treatment condi-
tions the arising aldehydes undergo further transforma-
tions along the route aldehyde → aldoxime → nitrile →
ester, or form the corresponding acetal.
951), 68 (13), 55 (48), 54 (19), 41 (48), 40 (7). NMR
and IR spectra of compounds VI and VII are identical to
published data [16].
Ozonolysis of castor oil (IIa). We obtained 10.1 g of
reaction product containing according to GLC methyl
(
(
3R)-3-hydroxynonanoate (VIII), dimethyl nonanedioate
IX), and methyl 8-cyanooctanoate (X) in a ratio 1.6 :
4
.9:1.
2
0
Methyl (3R)-3-hydroxynonanoate (VIII). [α]
D
EXPERIMENTAL
–1
–
(
(
1
2
198.7° (c 0.08, CH Cl ). IR spectrum, ν, cm : 1140
C–O), 1740 (C=O), 3420 (OH). H NMR spectrum
2
2
1
NMR spectra were registered on a spectrometer
Bruker AMX-300 [at operating frequencies 300.13 ( H)
3
acetone-d ), δ, ppm (J, Hz): 0.93 t (3H, CH , J 7.0),
1
6
3
4
2A
.35 m (8H, 4CH ), 1.52 m (2H, H ), 2.41 d.d (1H, H ,
2
13
and 75.47 MHz ( C)], TMS reference. IR spectra were
recorded on a spectrophotometer Specord M-82 from thin
films. Chromatographic analysis was carried out on
a chromatograph GC-9A Shimadzu (quartz capillary
column 25 m long, stationary phase OV-101, oven
temperature 80–260°C). Mass spectra were measured on
a system with coupled chromatograph, mass spec-
trometer, and computer (chromatograph HP 5890 with
a mass-selective detector HP 5972A, chromatographic
column HP 5MS 25 m × 0.25 mm, column temperature
conition: 40°C, isotherm 5 min, heating rate 8 deg/min
3
2B
2
3
J 15.1, J 8.1), 2.50 d.d (1H, H , J 15.1, J 4.8),
.67 s (3H, CH ), 3.98–4.03 m (1H, H ). C NMR
3
13
3
3
9
8
spectrum, δ, ppm: 13.32 q (C ), 22.24 t (C ), 25.21 t
5
6
7
4
2
(
5
C ), 28.97 t (C ), 31.56 t (C ), 36.90 t (C ), 41.96 t (C ),
3
1
0.50 q (CH ), 67.54 d (C ), 171.89 s (C ). Mass
spectrum, m/z (I , %): 188 (0.3) [M] , 170 (1), 139 (8),
38 (8), 111 (0.6), 115 (1), 113 (8), 103 (100), 97 (8), 96
3
+
rel
1
(
10), 87 (8), 74 (100), 59 (8), 45 (7), 31 (10).
Methyl 8-cyanooctanoate (X). IR spectrum, ν,
–
1
1
cm : 1745 (C=O), 2220 (C≡N). H NMR spectrum
O
O
(acetone-d ), δ, ppm (J, Hz): 1.35 m (6H, 3CH ), 1.40–
tillO 250 C, injector temperature 260 C, mass spectrum
scanning: 1 s per spectrum from 28 to 300 a.m.u.). The
optical rotation was measured on a polarimeter Perkin-
Elmer 241-MC. TLC control was carried out on SiO2
Sorbfil grade (Russia). For column chromatography was
6
2
7
3
2
1.50 m (2H, H ), 1.55–1.65 m (2H, H ), 2.30 t (2H, H ,
3
8 3
J 7.2), 2.46 t (2H, H , J 7.0), 3.61 s (3H, CH ).
3
13
8
3
C NMR spectrum, δ, ppm: 16.04 t (C ), 24.47 t (C ),
7
4
6
2
25.08 t (C ), 28.57 t (C –C ), 34.85 t (C ), 50.42 q (CH ),
3
9
1
used SiO (70–230) Lancaster (GB). Ozonizer capacity
0 mmol of O per hour.
120.00 (C ), 173.03 s (C ). Mass spectrum, m/z (I , %):
183 (0.2) [M] , 152 (39), 124 (21), 123 (20), 110 (19),
2
rel
+
4
3
111 (7), 98 (9), 97 (32), 96 (9), 83 (32), 82 (25), 74 (100),
Ozonolysis of olefins I, IIa, IIb, III–V. Through
a solution of 10 mmol of olefin in 50 ml of anhydrous
69 (11), 68 (7), 59 (39), 54 (8), 41 (25), 40 (8).
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 43 No. 8 2007

1118
ISHMURATOV et al.
Ozonolysis of castor oil acetate (IIb). We obtained
.2 g of reaction product containing according to GLC
methyl (3R)-3-hydroxynonanoate (VIII), dimethyl
nonanedioate (IX), and methyl 8-cyanooctanoate (X) in
a ratio 1:4.6:2.4.
(98%) of (3R)-1,1-dimethoxy-3-nonanol (XV). IR and
NMR spectra of compound XV were virtually identical
to those published before [18].
9
The study was based on a complex program of
the RussianAcademy of Sciences “Directional Synthesis
of Substances with Desired Properties and Prepara-
tion of Functional Materials Therefrom” (State Contract
no. 36).
Ozonolysis of (Z, 7R)-octadec-9-en-7-ol (III). We
obtained 2.6 g of product containing according to GLC
nonanenitrile (XI), methyl nonanoate (XII), and methyl
(
3R)-3-hydroxynonanoate (VIII) in a ratio 1:1.6:1.
REFERENCES
–
1
Nonanenitrile (XI). IR spectrum, ν, cm : 2230
1
(
0
(
C≡N). H NMR spectrum (acetone-d ), δ, ppm (J, Hz):
6
1
2
3
4
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Kharisov, R.Ya., Lozhkina, E.A., Mustafin, A.G.,
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p. 3446.
9
3
.94 t (3H, H , J 7.0), 1.3–1.5 m (10H, 5CH ), 1.68 q
2
3
3
2
3
13
2H, H , J 7.0), 2.50 t (2H, H , J 7.0). C NMR
9
2
spectrum, δ, ppm: 13.39 q (C ), 16.09 t (C ), 22.32 t
(
(
8
3
4
6
7
C ), 25.17 t (C ), 29.06 q (C –C ), 31.46 q (C ), 92.41 s
C1).
Ozonolysis of (1R)-menth-3-ene (IV). From
compound IV prepared as described in [11] we obtained
after chromatographic isolation (SiO , petroleum ether–
2
methyl tert-butyl ether, 50:1, R 0.34) 1.30 g (65%) of
f
methyl (3R)-3,7-dimethyl-6-oxooctanoate (XIII), [α]2
3
D
+
9.50 (c 5.27, CHCl ). IR and NMR spectra of compound
3
XIII were identical to those published before [17].
Ozonolysis of (1R)-3-methylmenth-3-ene (V). From
compound V prepared as described in [12] we obtained
1
.59 g (86%) of (4R)-4,8-dimethyl-2,7-nonanedione
2
0
(
XIV), [α] +8.88° (c 2.5, CHCl ). IR and NMR spectra
D
3
of compound XIV were virtually identical to those
published before [12].
(
3R)-1,1-Dimethoxy-3-nonanol (XV). Through a
8
solution of 1.0 g (1.1 mmol) of castor oil in 10 ml of
CH Cl at 0°C was bubbled a mixture of ozone with
oxygen till amount of consumed O was 3 mol per 1 mol
of castor oil. The reaction mixture was flushed with
argon, then diluted with 6 ml of CH Cl , and at stirring
was added thereto at 0°C within 0.5 h 0.8 g (11.55 mmol)
of NH OH·HCl. The reaction mixture was boiled till
disappearance of peroxides (10 h), then it was diluted
with 100 ml of CH Cl , washed with H O, the organic
layer was dried with Na SO and evaporated. The residue
(
in the presence of a catalytic quantity of p-TsOH and
evaporated. Then 100 ml of methyl tert-butyl ether was
added, the solution was washed with H O, the organic
layer was dried with Na SO and evaporated. We
obtained 0.86 g of reaction product that yielded after
2
2
3
1
9
2
2
2
1
2
2
2
2
1
1
2
4
0.94 g was boiled for 6 h in 5 ml (112 mmol) of MeOH
2. Ishmuratov, G.Yu., Yakovleva, M.P., Zaripova, G.V.,
Botsman, L.P., Muslukhov, R.R., and Tolstikov, G.A.,
Khim. Polim. Soed., 2004, vol. 6, p. 451.
13. Lebedev,A.T., Mass-spektrometriya v organicheskoi khimii
(Mass Spectrometry in Organic Chemistry), Moscow:
BINOM, 2003, 493 p.
2
2
4
column chromatography (SiO , CH Cl , R 0.45) 0.42 g
14. Terent’ev, P.B. and Stankyavichyus, A.P., Mass-
2
2
2
f
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 43 No. 8 2007

OZONOLYSIS OF ALKENES: LXVIII.
1119
spektrometricheskii analiz biologicheski aktivnykh
osnovanii (Mass Spectrometry of Biologically Active
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Akad. Nauk, Ser. Khim., 1993, p. 1301.
1
1
18. Kula, J., Quang, T. B., and Sikora, M., Tetrahedron:
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RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 43 No. 8 2007