Oxidative dihydroxylation of alicyclic unsaturated hydrocarbons with vinyl- and norbornene fragments in pseudohomogenic system

Article abstract of DOI:10.1134/S1070363213010118

Oxidation of alicyclic unsaturated hydrocarbons (4-vinylcyclohexene, 5-vinylnorbornene, 5-cyclohexenylnorbornene, and 5-vinylbicyclooctene) with 30% hydrogen peroxide solutions and percarbamide is studied. Reaction was carried out at 40-70 C in the presence of heterogenized peroxocomplex compounds of molybdenum and tungsten formed "in situ" in the reaction of metal oxohalides with H₃PO₄, nano-dimensional particles of carbon material, and hydrogen peroxide. Main oxidation products of alicyclic diene hydro-carbons are the corresponding unsaturated epoxides and diols. Depending on the reaction condition their ratio varies in a wide range.

Full text of DOI:10.1134/S1070363213010118

ISSN 1070-3632, Russian Journal of General Chemistry, 2013, Vol. 83, No. 1, pp. 63–71. © Pleiades Publishing, Ltd., 2013.
Original Russian Text © Kh.M. Alimardanov, N.I. Garibov, M.Ya. Abdullaeva, O.A. Sadygov, A.D. Kuliev, E.G. Ismailov, 2013, published in Zhurnal
Obshchei Khimii, 2013, Vol. 83, No. 1, pp. 70–79.
Oxidative Dihydroxylation of Alicyclic Unsaturated
Hydrocarbons with Vinyl- and Norbornene Fragments
in Pseudohomogenic System
Kh. M. Alimardanov, N. I. Garibov, M. Ya. Abdullaeva,
O. A. Sadygov, A. D. Kuliev, and E. G. Ismailov
Mamedaliev Institute of Pertochemical Processes, National Academy of Sciences of Azerbaijan,
Khojaly avenue 30, Baku, 1025 Azerbaijan
e-mail: omar.sadiqov@gmail.com
Received November 22, 2011
Abstract—Oxidation of alicyclic unsaturated hydrocarbons (4-vinylcyclohexene, 5-vinylnorbornene, 5-cyclo-
hexenylnorbornene, and 5-vinylbicyclooctene) with 30% hydrogen peroxide solutions and percarbamide is
studied. Reaction was carried out at 40–70°C in the presence of heterogenized peroxocomplex compounds of
molybdenum and tungsten formed “in situ” in the reaction of metal oxohalides with H3PO4, nano-dimensional
particles of carbon material, and hydrogen peroxide. Main oxidation products of alicyclic diene hydro-carbons
are the corresponding unsaturated epoxides and diols. Depending on the reaction condition their ratio varies in
a wide range.
DOI: 10.1134/S1070363213010118
As known, many biologically active compounds of
natural and synthetic origin having oxirane or hydroxyl
fragments are formed by introduction of the cor-
responding oxygen-containing function in the un-
saturated compound [1, 2]. The synthesis and trans-
formations of epoxides of different structures is suf-
ficiently well described in a series of reviews [3–6].
dispersed carbon material modified with the
compounds of the VIb group metals in the presence of
aqueous or dioxane solution of hydrogen peroxide or
its adduct with carbamide. Among the problems under
study was the investigation of some rules of oxidation
of isolated structural fragments of diene hydrocarbons
with no more than one double bond in a single ring.
Main products of oxidation of the above-mentioned
hydrocarbons in the presence of pseudohomogenic
catalytic system under mild conditions were the
corresponding epoxides and diols formed according to
the scheme below.
One of the practically important directions of
transformation of these compounds is the synthesis of
alcohols with sterically hindered structure among
which a special place is occupied by mono- and poly-
hydroxy derivatives of di- and tricyclic hydrocarbons.
Catalytic epoxidation and dihydroxylation of un-
saturated hydrocarbons with hydroperoxides is the elec-
trophilic addition reaction. The rate of oxidation depends
on the structure of the substrate molecule as well as on
the electron density of the double bond. In particular,
cis-isomers of alkenes are usually oxidized faster than
their trans-analogs [10, 11]. This rule is observed also
in the reaction of 4-vinylcyclohexene and 5-vinylnor-
bornene with organic peroxides [11, 12]. The epoxida-
tion of the substrate at the ratio 4-vinylcyclohexane
(vinylnorbornene) : ROOH equal to 1:2 proceeds
strictly by the double bond of the ring having higher
No data was found on the liquid phase oxidation of
alicyclic dienes into saturated and unsaturated alcohols
with the participation of heterogenized compounds of
polyvalent metals and hydrogen peroxide.
Recently we have studied one-stage dihydro-
xylation of cyclohexene and its alkyl and vinyl deri-
vatives in the presence of soluble molybdenum
oxohalides and carboxylates [7–9]. In this paper there
have been presented results of the one-pot liquid phase
oxidation of cycloolefines with the vinyl and
norbornene substituents in the presence of finely
63

64
ALIMARDANOV et al.
CHn
R
R
H2O2
(CH2)x
O
20_40oC
CHn
(CH2)x
CHn
R
CHn
Iа_Ie
kt
CHn
OH
OH
H2O2
(CH2)x
60_80oC
CHn
IIа_IIe
n = 2, x = 0, R = CH=CH2 (a); n = x =1, R = CH=CH2 (b); n = x = 1, R = cyclo-С6Н9 (c); n = 1, х = 2, R = CH=CH2 (d);
n = 1, x = 2, R = cyclo-С6Н9 (e).
electron density than the side vinyl group. Under the
analogous conditions the epoxidation of cyclo-
pentadiene dimer leads to the mixture of isomers of
monoepoxide in the ratio close to equimolar [13].
of molybdenyl groups MoO3+ and MoO4+ respectively.
While treated with 30% H2O2, the blue color of the
starting sample changes to golden yellow, and the
intensity of the band at 985 cm–1 strongly decreases.
Simultaneously intense bands at 920 and 952 cm–1
corresponding to MoO4+ fragment appear, and also
intense bands at 889, 680, 592, 562, 531, and 515 cm–1
related to the vibrations of peroxide bond –O–O–, to
the symmetric and asymmetric vibrations of MoO2
fragment [15]. In the IR spectrum of peroxophosphate
complex of molybdenum the absorption bands of the
PO42– group vibration at 1090 and 1024 cm–1 were
observed. The results obtained by us permit a sugges-
tion that in the reaction of ethanol solution of molyb-
denum blue with H2O2 and H3PO4 peroxophosphate
complexes of the dimeric or oligomeric forms of
molybdenyl groups are formed according to the
following scheme.
Use of the hydrogen peroxide instead of organic
hydroperoxides does not affect significantly the direc-
tion of the oxidation. As known, the oxidation of
alicyclic unsaturated hydrocarbons C6–C12 with peroxo-
complex compounds of molybdenum and tungsten at
65°C gives 1,2-epoxycyclanes in 70–90% yield. But
vinylcyclohexane is not oxidized under these condi-
tions [14]. It is interesting to note that 4-vinyl-
cyclohexane in the presence of Mo(V) oxobromide and
acetic acid is oxidized at a high rate mainly with the
formation of 1,2-dihydroxy-4-vinylcyclohexane [7].
Preliminary experiments carried out with the par-
ticipation of alicyclic dienes having different location
of double bonds showed that while using 30% hydro-
gen peroxide or percarbamide in pseudohomogenic
catalytic systems the oxidation of substrates proceeded
strictly at the more strained double bond with the forma-
tion of the corresponding epoxides and vicinal diols.
.
MoOBr3 2HBr + 2C2H5OH
.
MoOBr3 2C2H5Br + 2H2O,
.
MoOBr3 2C2H5Br + 3H2O
Br
O
O
Mo
O
+ 2C2H5OH + 2H2O + 2/3Br2.
For the investigation of state of catalysts highly
dispersed on the carbon carrier we used Fourier-IR,
EPR, and UV spectral methods. IR spectra of hetero-
genized catalysts were compared with the spectra of
ethanol solution of molybdenum blue, of the solid
residue obtained after evaporation of solvent, and also
of the batches treated with hydrogen peroxide and 85%
phosphoric acid.
Br
IR spectra of heterogenized samples contain all the
above-mentioned bands. But some of these bands, in
particular, those characteristic of PO42– group, are
shifted to the long-wave range which is caused by their
interaction with some fragments of the carbon
material.
Electron absorption spectra of ethanol solution of
MoOBr3·2HBr have characteristic maxima at
14200 cm–1 (20), 21100 cm–1 (400), 24100 cm–1
In the IR spectrum of ethanol solution and of the
solid residue of molybdenum blue (Fig. 1) strong
bands are observed at 985 and 940 cm–1 characteristic
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OXIDATIVE DIHYDROXYLATION OF ALICYCLIC UNSATURATED HYDROCARBONS
Т, % Т, %
65
ν, cm–1
ν, cm–1
Fig. 1. Fourier IR spectra (1) of solid MoOBr3·2HBr isolated from ethanol solution, (2) after treating with 30% H2O2, (3) a mixture
of H3PO4 and H2O2, and (4) after four times application.
(2400), 26500 cm–1 (2000) which indicate the presence
of MoO3+ ion in the complex (Fig. 2).
with ethoxy and ethyl bromide ligands. Under these
conditions Mo(V)=O group is retained.
ESR spectra of MoOBr3·2HBr contain the signals
with g11 2.094, g1 1.943, A11(Mo) 82 Gs, A1(Mo) 31 Gs.
The dependence of the intensity of ESR signal on the
concentration of MoOBr3·2HBr in acetone and ethanol
solutions (Fig. 3) show that the main part of MoO3+ ion
is in the dimeric state.
ESR spectra of acetone solution of MoOBr3·2HBr
show that it contains at least two complexes of MoO3+
with close values of magnet resonance parameters. At
the increase in concentration of MoOBr3·2HBr in the
solution the intensity of signals of paramagnetic
complexes of the second type increases as compared to
that of the first type. In the ethanol solution bromide
ligands of MoOBr3·2HBr are gradually substituted
In the course of the reaction of the above-men-
tioned solutions with H3PO4 these ligands are partially
substituted with the phosphate ones, but the valence
state of MoO3+ practically does not change. The
addition of H2O2 to this solution leads to formation of
a mixture of at least two peroxocomplexes with the
participation of MoO4+ which is also confirmed by
their IR spectra (absorption bands at 985, 952, 920,
889, 680, 592, 561, 531, 515 cm–1). The obtained
peroxocomplexes exhibit high activity in oxidation of
unsaturated compounds.
The selection of the effective catalyst and oxidant
was carried out by an example of oxidation of 4-vinyl-
cyclohexene and 5-vinylnorbornene chosen as model
O
O
Br
O
O
O
O
O
Mo
2
+ 2H2O2
+ H2O + 2Br2
Mo
O
Mo
Br
O
OH
O
OH
O
O
O
O
O
O
O
O
O
O
O
O
Mo
O
+ H3PO4
+ H2O
Mo
OH
O
Mo
OH
Mo
O
O
P
O
OH
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 83 No. 1 2013

66
ε×10–3
ALIMARDANOV et al.
DPPH
DPPH
DPPH
H0
10 mT
20 mT
H0
H0
Fig. 3. ESR spectra at 77 K of frozen solutions of
MoOBr3·2HBr (1%) (1, 1') in acetone and (2, 2')ethanol;
ESR spectra at 300 K of MoOBr3·2HBr on carbon carrier
treated with H3PO4 and H2O2 (3) before and (4) after the
reaches 50–60 min. The oxidation is accelerated only
after the formation in the system of peroxocomplexes
of Mo(VI) and W(VI), and it is accompanied by the
change of the solution color to the golden yellow. But
after the complete consumption of H2O2 the color
again becomes blue green. In this case the use of acetic
or oxalic acid (pH 1.8–3.7) favors the transformation
of low active diolate complex to the active peroxide
form. The catalysts I and II exhibit high activity in
oxidation of substrates, and the reactions proceed
practically without the inductive period. In contrast to
the oxidation in the presence of homogenic catalysts,
the peroxophosphate complexes of Mo and W
heterogenized on the carbon material (catalysts IIIk–
VIk) in the process 6 h long at 70°C provide mainly
trans-glycols (ratio of cis- and trans-isomers from 5–
25 to 75–85 at the conversion of the starting
substances 72–78%. Some decrease in the activity of
complexes IIIk–VIk as compared to homogenic
catalysts Ik and IIk may be connected with the
complications by diffusion. It is confirmed indirectly
by the relatively high activity of the samples Vk and
VIk prepared on the basis of highly dispersed
nanocarbon material as compared to the samples IIIk
and IVk prepared on the basis of the AG-3 carbon.
Catalysts Vk and VIk after four times use retain their
high activity.
λ×10–3, cm–1
Fig. 2. Electron absorption spectra of ethanol solutions of
MoOBr3·2HBr (Mo = 6×10-3 g-at/l) (1) before and (2) after
the oxidation of 4-vinylcyclohexane (T = 70°C, t = 2 h).
substances. For comparison of the results ethanol
solutions of molybdenum and tungsten blue and spe-
cially prepared diolate complex of molybdenum were
used. The activity of catalysts and the effectiveness of
oxidant were evaluated from the conversion of
cycloolefin and the selectivity of the reaction by the
overall amount of the formed epoxide and isomers of
dihydric alcohol (see Tables 1–3).
Data of Tables 1–3 show that the conversion of
starting hydrocarbons and the composition of the
reaction products depend significantly on the nature of
the catalyst and the oxidant used. In the presence of
molybdenum and tungsten blue and also of the diolate
complex VIIk in acetic acid the oxidation proceeds
non-specifically. At the conversion of hydrocarbons
26.4–91.5% the product contains mainly mono-
epoxides (9.3–27.4 wt %) and a mixture of isomers of
glycols (47.3–72.7 wt %). Using the molybdenum and
tungsten blue and especially complexes VIIk without
the addition of carboxylic acids (formic, acetic, and
oxalic) blue green color of solution conserves for 30–
40 min. Under these conditions non-productive
transformation of H2O2 prevails over the oxidation of
substrates. The induction period of accumulation of
oxidation products in the presence of complex VIIk
According to the reported data [14, 15] the acidic
groups in the peroxocomplexes MoO4+ and WO4+ (in
this case PO43– ions) under the conditions of
epoxidation and dihydroxylation of unsaturated
compound successfully compete with the oxidation
products, in particular with diols, for the occupation of
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OXIDATIVE DIHYDROXYLATION OF ALICYCLIC UNSATURATED HYDROCARBONS
67
Table 1. Activity and selectivity with respect to diol (S, %) of Mo- and W-containing catalysts in the oxidative
dihydroxylation of 4-vinylcyclohexene with 30% aqueous H2O2 (T = 70oC, t = 6 h, vinylcyclohexene : H2O2 : CH3COOH =
1:2:0.2)
Composition of product, wt %
Conversion,
Catalyst
S, %
diol+
%
epoxide
α-oxyketone
unknown compounds
monoacetate
Molybdenum blue
81.7
82.4
89.5
88.1
69.2
65.7
77.0
72.3
31.0
51.7
46.3
14.8
4.8
8.1
6.2
6.0
4.0
8.2
5.0
17.3
3.8
3.0
68.6
72.7
75.4
81.3
58.0
61.6
76.5
72.0
57.0
74.5
69.4
6.2
6.5
10.4
16.0
12.0
8.5
25.6
22.6
10.7
14.6
14.3
14.7
18.4
66.3
62.6
73.1
79.0
55.5
58.0
74.4
69.0
54.1
72.7
67.1
Tungsten blue
4.5
Ik
IIk
IIIk
IVk
Vk
VIk
VIIk
Vkа
VIkа
4.0
10.4
11.8
4.6
8.4
11.4
7.0
9.2
a Results obtained after 4-time use of catalyst.
Table 2. Activity and selectivity with respect to diol (S, %)of Mo- and W-containing catalysts in the reaction of oxidative
dihydroxylation of 5-vinylnorbornene with 30% aqueous H2O2 (T = 70°C, t = 6 h, vinylnorbornene : H2O2 : CH3COOH = 1:2:0.2)
Composition of product, wt %
Conversion,
Catalyst
S, %
diol+
%
epoxide
α-oxyketone
unknown compounds
monoacetate
Molybdenum blue
87.0
91.5
92.7
93.0
73.4
70.0
76.2
78.0
26.4
54.7
58.1
9.3
5.0
6.2
4.8
5.9
4.2
7.8
4.5
27.4
5.1
3.6
73.5
74.8
80.1
80.5
64.0
62.2
73.0
74.6
47.3
70.9
66.5
3.8
4.7
5.0
6.0
8.3
10.7
4.8
6.7
3.2
8.0
9.6
13.4
15.5
8.7
71.4
72.1
78.3
78.6
60.8
58.8
70.2
71.7
44.7
69.2
64.3
Tungsten blue
Ik
IIk
IIIk
IVk
Vk
VIk
VIIk
Vka
VIkа
8.7
21.8
22.9
14.4
14.2
22.1
16.0
20.3
a Results obtained after 4-time use of catalyst.
coordination centers on the MeO4+ ion. It prevents
washing out of peroxocomplexes and the products of
its transformation from the surface of carbon material.
The epoxidation proceeds exclusively at the double
bond of the ring. The formation of bis-epoxide was
observed only at a high ratio of H2O2 to 5-vinyl-
norbornene (4–6 : 1). But the epoxide yield does not
exceed 8–12% because the reaction is accompanied by
the opening of the oxirane fragments of the ring and
the formation of carboxylic acids in the system [16–18].
From the data of table 4 it is seen that in going from
aqueous H2O2 solution to dioxane and then to per-
carbamide both the rate of oxidation of 5-vinyl-
norbornene and the composition of reaction products
considerably change. Whereas at the use of 30%
aqueous hydrogen peroxide the main reaction products
are isomers of 5-vinylbicyclo[2.2.1]norbornandiol, in
the case of percarbamide under the same conditions
monoepoxide becomes the main component of the
product. Probably at the use of percarbamide this
compound forms a complex with acetic acid and with
the liberated water preventing the hydrolysis of
epoxide, the primary reaction product.
The direction of transformation of active oxygen
and the selectivity of the reaction significantly depend
on the temperature of the experiment (see Fig. 4).
In the temperature range 30–50°C the oxidation of
4-vinylcyclohexene in the presence of complex Vk
proceeds with the expressed induction period, and at
low conversion of cycloolefin (8–15%) the main
reaction product is 1,2-epoxy-4-vinylcyclohexane.
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68
ALIMARDANOV et al.
Table 3. Conversion and selectivity of oxidation of cycloolefins with 30% water solution of H2O2 in the presence of the
catalyst Vk at different temperatures (molar ratio cycloolefin : H2O2 : CH3COOH 1 : 2 : 0.2, t = 4 h)
Temperature, °C
50°С
Unsaturated
hydrocarbon
30°С
40°С
60°С
70°С
conversion,
conversion,
conversion,
conversion,
conversion,
I:II
I:II
I:II
I:II
I:II
%
%
%
%
%
4-Vinylcyclohexene 57.3:11.5
8.0
68.4:14.2
75.0:14.2
10.3
14.0
65.8:17.6
60.6:27.4
12.8
19.5
53.7:32.0
42.1:45.4
21.7
32.3
47.0:50.5
19.4:68.3
30.5
45.6
5-Vinylbicyclo[2.2.1]- 72.4:12.6
hept-2-ene
11.7
5-Vinylbicyclo[2.2.1]- 64.4:8.4
oct-2-ene
9.4
65.0:13.5
74.2:18.3
11.0
14.5
59.7:23.2
57.0:31.4
13.1
18.0
44.2:42.5
40.8:49.2
20.4
28.8
30.7:52.5
24.2:62.6
32.2
47.0
5-(Cyclohexen-3-yl)- 70.7:13.0
bicyclo[2.2.1]pent-2-
ene
12.3
5-(Cyclohexen-3-yl)- 64.0:10.5
bicyclo[2.2.2]oct-2-
ene
11.0
68.7:14.0
13.0
53.3:29.8
17.0
49.0:34.5
28.0
32.0:53.2
37.4
Table 4. Dependence of the conversion of 5-vinylnorbornene and the selectivity of the reaction on the nature of oxidant used
(catalyst complex Vk, T = 70°C, t = 6 h, [CH3COOH] 0.2 M )
Starting rate of consumption of
Selectivityа, %
active oxygen, (mol l–1 s–1)×10–3
Conversionа,
Oxidant
5-vinylnorbornene:Н2О2 ratio
%
by
epoxide
by
diol
1:0.5
0.71
1.22
2.34
1:1
1:1.5
1.84
2.42
4.43
1:2
Н2О2 (30% water solution)
1.13
1.89
3.51
2.53
2.82
5.54
76.2
92.6
90.0
6.6
52.3
73.7
70.2
37.5
14.7
Н2О2 (30% dioxane solution)
Percarbamide [adduct Н2О2 and СО(NH2)2]
a Amount of oxidant is 2 mol.
After 7 h of the process the summary yield of
epoxyvinylcyclohexane is only 25.7–32.0% though the
degree of transformation of active oxygen reaches
75.0–82.5%. Probably the formation of intermediate
with the participation of oxoperoxocomplex compound
MoO4+ and the transfer of active oxygen to substrate
under these conditions is connected with energy
hindrances, therefore its oxidation is accompanied by
non-productive transformation of H2O2. At the
increase in temperature from 50 to 70°C the rate of
oxidation and the degree of dihydroxylation of 4-
vinylcyclohexene sharply increase, and the yield of
glycol reaches 67.5–73.0%. Further increase in
temperature to the range 70–90°C causes the decrease
in selectivity of the reaction with respect to diol,
though conversion of 4-vinylcyclohexene reaches 95–
97%. Under these conditions dihydroxylation of 4-
vinylcyclohexene is accompanied by intensifying of
oxidation of glycol to the isomers of α-oxyketones and
further to carboxylic acids.
Note that in the presence of complexes Vk and VIk
dihydroxylation of 4-vinylcyclohexane in the tempe-
rature range 40–60°C proceeds with the forma-tion of
a mixture of trans-(75–85%) and cis-isomers (15–25%).
At the increase in temperature the content of trans-
isomer in product increases and above 70°C cis-1,2-
dioxy-4-vinylcyclohexane practically does not form.
The investigation of dynamics of accumulation of
the oxidation products of 4-vinylcyclohexene by
means of GLC and IR spectroscopy shows that in the
temperature range 30–50°C mainly the epoxidation of
cycloolefine takes place, and the accumulation of
epoxide passes through the maximum. In this case the
oxirane ring forms only in the cyclohexene fragment,
and the vinyl group remains untouched. The formation
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(a) (b)
69
Q, %
С, %
τ, h
τ, h
Fig. 4. Dynamics of transformation of (a) starting substances and (b) accumulation of main reaction products of dihydroxylation of
4-vinylcyclohexene at various temperatures. Catalyst: H3{PO4[MoO(O2)2]4}/C (catalyst A), 4-vinylcyclohexene : H2O2 :CH3COOH =
1:2:0.1. Temperature: (1, 1', 1'', 1''') 30oC; (2, 2', 2'', 2''') 50oC; (3, 3', 3'', 3''') 70oC; (4, 4', 4'', 4''') 90oC; (1–4) is the degree of
transformation of hydrogen peroxide; (1'–4') is the conversion of vinylcyclohexene; (1''–4'') is the yield of 4-vinyl-1,2-
epoxycyclohexane; (1'''–4''') is the yield of 4-vinylcyclohexane-1,2-diol.
of some amount of diepoxide, the product of oxidation
of 4-vinylcyclohexene at both double bonds is
observed in more rigid reaction conditions (tem-
perature range 70–90°C, 4-vinylcyclohexene-H2O2
molar ratio 1 : 4–6). Its content in the product
according to GLC data does not exceed 5–8% from the
amount of 4-vinyl-1,2-epoxycyclohexane. Under such
conditions the epoxidation of vinyl group competes
with the hydrolysis of oxirane cycle and further with
the oxidation of glycol.
octane fragments (for compounds Ib–Id, IIb–IId at
131 ppm) in the 13C NMR spectra of epoxides Ia–Id
and diols IIa–IId were also absent. Signals at 57-60
ppm (for Ia) and at 63–68 ppm (for compounds Ib–Ie)
are attributed to the carbon atoms of oxirane fragment.
For diols IIa-e these signals appear at 72–82 ppm
respectively. The obtained data are also confirmed by
the H NMR spectra [20,21]. Besides, in the IR, H,
and 13C NMR spectra of starting substances and the
products Ia–Ie, IIa–IIe the absorption bands and
signals characteristic of the vinyl and cyclohexenyl
residues practically do not change.
Hence, it was established that heterogenized per-
oxocomplexes prepared on the basis of molybdenum
and tungsten oxohalides with the participation of
orthophosphoric (or oxalic and acetic) acid and
nanoparticles of carbon exhibit high efficiency in the
oxidation of cyclic diene hydrocarbons to the
corresponding unsaturated epoxides and diols which
may be used as starting substances for preparing or-
ganic compounds for different applications.
1
1
The substitution of vinyl group with cyclohexenyl
one in the molecule of 5-vinylnorbornene practically
does not affect the direction of the attack of the active
oxygen from the peroxocomplexes (Table 3). The
epoxidation and dihydroxylation of substrate proceeds
mainly at the norbornene fragment. The reactivity of 5-
cyclohexenylbicyclo[2.2.1]-octen-2 to some extent
differs. The part of its epoxidation by cyclohexene
fragment reaches 20–25 wt %.
The composition and structure of synthesized
monoepoxides Ia-e and diols IIa-e were established by
the IR and 1H and 13C NMR spectroscopy.
EXPERIMENTAL
In the IR spectra of monoepoxides synthesized Ia–
Id the absorption bands characteristic of the multiple
bond of cyclohexene (680 and 1649 cm–1, Ia),
bicycloheptene, and bicyclooctene (720 and 1670 cm–1,
Ib–Id) fragments are absent. Strong absorption bands
at 910, 990, and 3040 cm–1 belong to vinyl group (in
the compounds Ia, Ib), and in the range 800, 858, and
1260 cm–1, to the oxirane ring [22]. Characteristic
signals of carbon atoms at the double bond of
cyclohexene (for compounds Ia and IIa in the range
126 ppm), of bicyclo[2.2.1]heptene and bicyclo[2.2.2]-
Fourier IR spectra were recorded on a Perkin-Elmer
FT-IR Spectrum BX spectrometer in KBr pellets in the
range 450-4400 cm–1. ESR spectra were measured on a
JEOL JES-PL 3x radiospectrometer (9300 MHz) at 77
and 300 K. Diphenylpicrylhydrazyl was used as a
standard while measuring g factor values (g = 2.0036).
Electron absorption spectra were measured on a
Specord M 40 UV/Vis spectrophotometer. IR spectra
1
were obtained on an UR-20 spectrometer. H NMR
spectra were taken on a Varian T-60 (60 MHz) and
Jeol FX 90Q (90 MHz) spectrometers in CCl4 and
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 83 No. 1 2013

70
ALIMARDANOV et al.
acetone-d6. 13C NMR spectra were recorded on a Varian
T-60 (20 MHz) and Bruker AM-300 (75.432 MHz)
spectrometers.
75–78°C in the presence of the metallic aluminum
activator. Subsequent treating of obtained batches
according to the above-reported procedure gave highly
dispersed molybdenum- and tungsten-containing
catalysts Vk and VIk on nanocarbon material.
The composition and purity of starting hyd-
rocarbons and products of their oxidation were
evaluated by GLC on a Tsvet-500 chromatograph with
flame ionization detector, 2000×2 mm column filled
with polyethyleneglycol succinate on Chromosorb
(5 wt %), and helium carrier gas. Column temperature
160°C, evaporator temperature 280°C.
For comparison of the activity of catalyst the
diolate complex of
molybdenum VIIk was used. It was prepared by
heating of a mixture of isomers of norbornandiol and
molybdenum blue at 50–60°C for 1.5–2 h. The
oxidation of unsaturated hydrocarbons was carried out
in glass 100 cm3 microreactor equipped with tem-
perature-controlled jacket, dropping funnel, and
condenser under the intense stirring by means of
magnetic stirrer. The reactor was loaded with the given
amount of unsaturated hydrocarbon, of the catalyst,
and of acetic acid and heated to the temperature 40–
70°C. After that 30% water or dioxane solution of hyd-
rogen peroxide was added dropwise. For comparison
of the results a solution of percarbamide in acetic acid
was used.
The composition of obtained catalysts was con-
firmed by IR, ESR, and UV spectroscopy.
4-Vinylcyclohexene, 5-vinylnorbornene, and the
adducts of 4-vinylcyclohexene to cyclopentadiene and
1,3-cyclohexadiene were used as starting substances.
The latter were prepared by (4+2) addition of
hydrocarbons in a pressure reactor in the presence of
5.0 wt % of synthetic mordenite or natural clino-
ptilolyte transformed to H-form. The reaction was
carried out under nitrogen at 200–220°C and molar
ratio vinylcyclohexene–cyclopentadiene (or cyclohexa-
diene) 1:1.5 in the course of 2–4 h. After the reaction
was complete, the reactor was quickly cooled, and the
Hydrogen peroxide concentration was evaluated by
permanganatometric method.
reaction mixture was distilled in
a
vacuum.
6-Vinyl-exo-3-oxatricyclo[3.2.1.02,4]octane (Ib)was
prepared from 12.0 g of 5-vinylnorbornene, yield 9.0 g
(66%), bp 83–86oC (3.5 mm Hg), d420 1.0235, nD20
1.4876. IR spectrum, ν, cm–1: 3060, 3040, 1620, 890,
930–900 (–CH=CH2); 1250, 866, 858 (–C–O–C–)
Physicochemical properties of the dienes synthesized
coincide with the reported data [22, 23].
The catalysts heterogenized on carbon material
were synthesized according to the following procedure.
1
[21]. H NMR spectrum, δ, ppm: 3.47 (2H, H2, H4),
(a) A powder of metallic molybdenum or tungsten
was heated to 80–100°C in a porcelain cup and treated
with an excess of bromine under moist air atmosphere.
After that reaction mixture was dissolved in anhydrous
ethanol or acetone and filtered. The filtrate obtained
was evaporated to dryness. Yield of the molybdenum
or tungsten blue was 45-48%. The solid obtained was
2.13 t (1H, H5), 5.79 q (H9), 4.89–4.96 m (2H10,
J
9,10''16.4 Hz, J9,10 9.0 Hz, J10',10'' 2.0 Hz), 1.25–1.75 m
(6H, cycle, J7a,7s 11.4 Hz, J6,7exo 3.9 Hz, J6,7endo 9.2 Hz)
[20, 21].
exo-6-(Cyclohex-3-enyl)-exo-3-oxatricyclo-
[3.2.1.02.4]-octane (Ic) was prepared from 17.4 g of 5-
vinylnorbornene, yield 9.8 g (51.6 %), bp 108–110°C
(2 mm Hg), mp 46–48°C. IR spectrum, ν, cm–1: 3068,
1640–1650 (–CH=CH–), 840, 920, 1250–1260 (–C–
treated in succession with the required amount (Mon+
:
PO43– = 4:1) of 85% H3PO4 and 30% hydrogen
peroxide (catalysts Ik and IIk). Heterogenized
catalysts (IIIk and IVk) were prepared by impregna-
tion of the powder-like AG-3 carbon with the ethanol
solutions of the molybdenum or tungsten blue. The
obtained mass was treated with water solutions of
phosphoric acid and hydrogen peroxide and heated for
2 h at 50–60°C and 2 h at 120–150°C. The content of
molybdenum in the catalyst IIIk or tungsten in the
catalyst IVk was 15 wt %.
1
O–C–). H NMR spectrum, δ, ppm: 5.59 m (2H, H3',
H4', J3',4' 11.2 Hz ), 1.48–2.03 m (6H, 3CH2 of
cyclohexene, J5',6' 4.4 Hz), 2.89 q (2H, H2, H4), 1.25–
1.76 m (7H of tricyclooctane, J6endo,7endo 9.2 Hz, J6endo,5
4.5 Hz, J6endo,1' 4.5 Hz).
exo-6-(Cyclohex-3-enyl)-exo-3-oxatricyclo-
[3.2.2.02.4]nonane (Id) was prepared from 18.8 g of 5-
cyclohexenylbicyclo[2.2.2]octane. Yield 8.6 g (42.3%),
mp 58–60°C. IR spectrum, ν, cm–1: 3060, 1620–1640
(–CH=CH–), 835, 842, 860, 910, 1260 (epoxy group).
(b) A powder of metallic molybdenum and tungsten
was reacted with carbon tetrachloride or bromoform at
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OXIDATIVE DIHYDROXYLATION OF ALICYCLIC UNSATURATED HYDROCARBONS
71
1H NMR spectrum, δ, ppm: 5.58 d (2H, H3', H4', J3',4'
11.4 Hz) 1.49–2.04 m (6H, 3H2 of cyclohexene, J5',6'
4.4 Hz), 2.86 q (2H, H2, H4), 1.27–1.78 m (9H,
tricycloninane, J6endo,7endo 9.2 Hz, J6endo,5 4.3 Hz), 1.26 t
(2H, H8a, H9a, J8a,9a 2.6 Hz), 1.51 t (2H, H8b, H9b, J8b,9b
3.5 Hz).
nost’ (Oxiranes. Synthesis and Biological Activity),
Moscow: Bogorodskiy Pechatnik, 1999.
7. Alimardanov, Kh.M., Suleimanova, E.T., Ismailov, E.G.,
and Akhundova, A.A., Neftekhimiya, 1994, vol. 34,
no. 4, p. 344.
8. Alimardanov, Kh.M., Akhundova, A.A., Velieva, F.M.,
and Aliev, F.T., Neftekhimiya, 1996, vol. 36, no. 5,
p. 444.
9. Alimardanov, Kh.M., Sadygov, O.A., Gajiev, T.A.,
Abdullaeva, M.Ya., Asirova, R.B., and Babaev, N.R.,
Protsessy Neftekhim. i Neftepererab., 2007, no. 5(32),
p. 66.
5-Vinylbicyclo[2.2.1]heptan-exo,endo-2,3-diol
(IIb) was prepared from 12.0 g of 5-vinylnorbornene,
yield 8.2 g (53.5%), mp 57–59°C. IR spectrum, ν, cm–1:
3050, 1650 (–CH=CH2), 3600–3200, 1150, 1120,
1
1100, 1080, 1050 (OH). H NMR spectrum, δ, ppm:
3.25 d (2H, H1, H4), 3.12 d.d (1H, H5), 2.91 d.d (1H,
10. Voronenkov, V.V. and Osokin, Yu.G., Usp., Khim.,
H6, J5endo,6endo 9.1 Hz, J1,6 5.2 Hz), 3.87–4.93 m (2H,
1972, vol. 41, no. 8, p. 1366.
H9a, H9b,
J9a,9b 2.8 Hz, J8,9a 12.4 Hz), 4.95 d (1H,
11. Yur’ev, V.P., Gailyunas, G.A., Tolstikov, G.A., and
Volyanova, F.G., Neftekhimiya, 1972, vol. 12, no. 3,
p. 354.
OHendo), 4.89 d (1H, OHexo).
exo-5-(Cycloxex-3-enyl)-bicyclo[2.2.1]heptan-
exo,endo-2,3-diol (IIc) was prepared from 17.4 g of 5-
vinylnorbornene. Yield 10.3 g (48.7%), mp 112–114°C.
IR spectrum, ν, cm–1: 3020–3050, 1620–1650
(–CH=CH–), 3600–3200, 1150, 1100, 1180 (OH). 1H
NMR spectrum, δ, ppm: 5.61 t (2H, H3',H4', J3',4' 12.4 Hz),
1.51–1.99 m (6H, 2CH2 of cyclohexene), 3.25 d (2H,
H2, H3, J1',2 6.8 Hz), 3.08 d.d (1H, H5, J4,5 5.2 Hz, J5,6
10.2 Hz) 1.25–1.56 m (6H, bicycloheptane, J5endo,6endo
9.2 Hz, J6,6 12.1 Hz), 4.93 d (1H, OHendo),4.93 d (1H,
OHexo).
12. Osokin, M.Yu., Neftekhimiya, 2000, vol. 40, no. 6,
p. 449.
13. Zefirov, N.S. and Sokolov, V.N., Usp., Khim., 1972,
vol. 36, no. 2, p. 243.
14. Timofeeva, M.N., Pay, Z.P., Tolstikov, A.G., Kustova, G.N.,
Selivanova, N.V., Berdnikova, P.V., Brylyakov, K.P.,
Shangina, A.B., and Utkin, V.L., Izv. Ross. Akad. Nauk,
Ser. Khim., 2003, no. 2, p. 458.
15 .Konishevskaya, G.A., Filippov, A.P., Sobchak, Yu.,
Zyulkovskii, Yu.Yu., Yatsimirskii, K.B., and Belouso-
va, V.M., Kinetika i Kataliz, 1980, vol. 21, no. 4, p. 933.
16. Alimardanov, Kh.M., Sadygov, O.A., Abdullaeva, M.Ya.,
and Jafarova, N.A., Azerb. Khim. Zh., 2010, no. 2,
p. 130.
17. Alimardanov, Kh.M., Sadygov, O.A., Garibov, N.I.,
Abbasov, M.F., Abdullaeva, M.Ya., and Jafarova, N.A.,
Zh. Prikl., Khim., 2011, vol. 84, no. 2, p. 240.
exo-5-(Cyclohex-3-enyl)bicyclo[2.2.2]octan-
exo,endo-2,3-diol (IId) was prepared from 18.8 g of
exo-5-(cyclohex-3-enyl)bicyclo[2.2.2]oct-2-ene. Yield
10.75 g (48.4%), mp 120–122°C. IR spectrum, ν, cm–1:
3020–3050, 1650 (–CH=CH–), 3200–3600, 1150,
1
1120, 1180, 1050 (OH). H NMR spectrum, δ, ppm:
18. Dryuk, V.G. and Kartsev, V.G., Usp., Khim., 1999, vol. 68,
3.24 d (H2, H3), 5.61 t (H3', H4' of cyclohexene), 4.81
br.s (2OH).
no. 3, p. 206.
19. Nakanishi, K., Infrakrasnye spektry
i
stroenie
organicheskikh molekul (IR Spectra and Structure of
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