Epoxidation and oxidative dihydroxylation of C10–C13 unsaturated bridged hydrocarbons involving hydrogen peroxide and modified forms of heteromolybdic compounds

Article abstract of DOI:10.1134/S0965544117050024

Induced oxidation of C₁₀–C₁₃ tricyclic bridged olefins synthesized from C₅–C₈ cyclodiene hydrocarbons using hydrogen peroxide has been studied. It has been shown that phosphomolybdic heteropoly compounds supported on a finely divided carbon material and additionally modified with HBr and CoCO₃ or Gd₂O₃ exhibit high activity in this reaction. Depending on the conditions of the experiments, the main reaction products are the corresponding oxiranes and diols that retain the structure of the reactant hydrocarbons.

Full text of DOI:10.1134/S0965544117050024

ISSN 0965-5441, Petroleum Chemistry, 2017, Vol. 57, No. 5, pp. 415–423. © Pleiades Publishing, Ltd., 2017.
Original Russian Text © Kh.M. Alimardanov, O.A. Sadygov, N.I. Garibov, N.R. Dadashova, M.B. Almardanova, A.D. Kuliev, 2017, published in Neftekhimiya, 2017, Vol. 57,
No. 3, pp. 304–312.
Epoxidation and Oxidative Dihydroxylation of C10–C13 Unsaturated
Bridged Hydrocarbons Involving Hydrogen Peroxide and Modified
Forms of Heteromolybdic Compounds
Kh. M. Alimardanov*, O. A. Sadygov, N. I. Garibov, N. R. Dadashova,
M. B. Almardanova, and A. D. Kuliev
Mamedaliev Institute of Petrochemical Processes, National Academy of Sciences of Azerbaijan, Baku, Azerbaijan
*e-mail: hafiz_alimardanov@yahoo.com
Received October 17, 2016
Abstract⎯Induced oxidation of C10–C13 tricyclic bridged olefins synthesized from C5–C8 cyclodiene hydro-
carbons using hydrogen peroxide has been studied. It has been shown that phosphomolybdic heteropoly com-
pounds supported on a finely divided carbon material and additionally modified with HBr and CoCO3 or
Gd2O3 exhibit high activity in this reaction. Depending on the conditions of the experiments, the main reac-
tion products are the corresponding oxiranes and diols that retain the structure of the reactant hydrocarbons.
Keywords: tricyclodecene, tricycloundecene, tricyclododecene, cyclohexenylnorbornane, phenylnor-
bornene, modified forms of heteromolybdic compounds, epoxidation, cyclic vicinal glycols
DOI: 10.1134/S0965544117050024
Oxidative functionalization of cyclic hydrocarbons
An increased amount of unsaturated alicyclic
(HCs) remains one of the priority areas of petrochem- hydrocarbons from industrial sources [11, 12] and
ical and organic synthesis. To introduce the oxygen improvements in their condensation methods [13–19]
function into substrates with different structures, liq- create real prerequisites for the synthesis of the afore-
uid-phase autooxidation using air oxygen as an oxi- mentioned oxygen-containing compounds.
dant or the insertion of oxygen-containing units by
means of various oxidants and polyvalent metal com-
pounds is currently preferred [1, 2]. Among the latter
oxidants and metal compounds, hydrogen peroxide as
a cheap and environmentally more appropriate oxi-
dant and heteropoly compounds in combination with
quaternary ammonium compounds as phase transfer
catalysts gain the most attention in application to cat-
alytic processes [3–6]. The selectivity of these pro-
cesses largely depends on the carrier of active oxygen
to the multiple bond of the substrate and also on the
catalytic system itself, which ensures the desired con-
version of the reactants and the yields of products with
a desired structure. However, the unresolved problem
in these processes is the isolation and reuse of the cat-
alyst systems.
In earlier studies on the synthesis of epoxides of
unsaturated hydrocarbons, peroxo acids [8, 20] and
peroxides or alkyl hydroperoxides [20, 21] were mainly
used. To date, procedures for the oxidation of organic
compounds with aqueous hydrogen peroxide solutions
under phase-transfer catalysis conditions using phase
transfer catalysts have been developed [22–25].
High selectivity for epoxides is achieved in the case
of hydroxyhalogenation of bridged unsaturated hydro-
carbons followed by dehydrohalogenation of the prod-
ucts with potassium hydroxide [26].
In this paper we present the results of epoxidation
and dihydroxylation of tricyclic bridged monoolefins
with hydrogen peroxide. The catalyst used was a phos-
phomolybdic heteropoly compound (PMHC) sup-
ported to a finely divided carbon material that was
additionally modified with hydrobromic acid and
cobalt(II) carbonate or gadolinium oxide.
It is known that mono- and diepoxy derivatives of
bridged bi- and tricyclic unsaturated hydrocarbons
can be used as binders and additives to create poly-
meric compositions for various purposes, such as
heat-resistant glass-reinforced plastics, coatings,
molded articles, and insulating materials [7, 8]. In
addition, these products have an independent value cycloolefins with hydrogen peroxide were synthesized
and are used to produce biologically active substances according to the procedure developed previously [28].
and pharmaceuticals [9], as well as fragrances [10].
EXPERIMENTAL
Samples of PMHC catalysts for the oxidation of
IR spectra of these samples in the form of white-oil
415

416
ALIMARDANOV et al.
nickel at T = 80–85°C, V = 0.5 h−1, and a diene : H2
molar ratio of 1 : 2 [28]. A mixture of exo- and endo-
mull or KBr tablets were taken on an Alpha FTIR
spectrometer in the region of 400–4000 cm−1 or a Ver-
tex (Bruker) instrument in the range of 100–700 cm−1. isomers of cycloolefins with a molar ratio of 90–95 :
5–10 is mainly formed in this case. After vacuum dis-
tillation of the catalyzate, corresponding cycloolefins
were obtained in a yield of 96–98.5%.
Reactant Preparation Procedure
Unsaturated bridged C10–C13 hydrocarbons were
exo-5-Cyclohexyl-
and
exo-5-phenylbicy-
obtained via the [4 + 2]-cycloaddition reaction of
cyclopentadiene with cyclohexadiene-1,3, 4-vinylcy-
clohexene, vinylcyclohexane, and styrene in the pres-
ence of the H-form of clinoptilolite (SiO2/Al2O3 = 5.4)
or mordenite (SiO2/Al2O3 = 10) at T = 180–200°C
over 2 to 3 h [28]. The addition reaction of cyclopen-
tadiene with styrene was carried out in the presence of
5 wt % hydroquinone [30]. The main products were
the corresponding endo-isomers (endo- to exo-isomer
molar ratio was 80–83 : 17–20).
clo[2.2.1]hept-2-enes used in the epoxidation reaction
were obtained from the respective endo-isomers
according to the procedure described in [29, 30].
Physicochemical and spectral parameters given below
for the compounds synthesized are consistent with rel-
evant published data [30–37].
13
1H and C NMR spectra were recorded in a deu-
terated chloroform solution at room temperature on a
Bruker Fourier-transform pulsed spectrometer oper-
ating on a frequency of 300.18 MHz. The relative
abundance of protons in different structural moieties
was determined by integrating the corresponding res-
onance absorption bands [32, 35].
General Procedure for Isomerization and Hydrogenation
of C10–C13 Bi- and Tricyclic Dienes
A predetermined amount of a synthesized diene
hydrocarbon (in an endo- to exo-isomer ratio of the
dimers or codimers of 4–5 : 1) and a 5% AlCl3 solution
in hexane (AlCl3 content of 10–15% of the total weight
of the isomer mixture) were charged to an autoclave
and heated at 150–160°C for 6–8 h [29]. The reactor
was then cooled to room temperature; the products
were washed with an aqueous KCl solution; and the
organic phase was separated from the aqueous phase,
diluted with toluene, and fed with a microdoser into a
flow reactor for hydrogenation to the corresponding
Mass chromatograms were recorded on an Agilent
Technologies GC 7890A-MSD 5975C instrument
using an HP5-MS column, temperature programming
within 40–280°C, and helium as the carrier gas. Ele-
mental analysis was performed with a Leco TruSpes
Micro analyzer. The molecular weights of some oxida-
tion products were determined cryoscopically. Cryo-
scopic benzene was used as the solvent. The relative
error was 1.0–1.5%.
Cycloolefins were synthesized according to the fol-
cycloolefins over a fixed bed of kieselguhr-supported lowing scheme:
x
x
x
x
+H2, Ni
150−160 C
isomerization
°
+
y
y
y
y
I, II, III
exo : endo = (17 −20) : (80−83)
V, VI, VII, (92−95%)
Va, VIa, VIIa, (92.6–96.5%)
exo : endo = (90 −95) : (5−10)
Vb, VIb, VIIb, (3.5−7.4%)
150−160oC
, Ni
+H
+
isomerization
IV
VIII, (93%)
VIIIa, (96%)
VIIIb, (4.0%)
vexo : endo = (20−80)
exo : endo = 93 : 7
x = у = 1 (I, V, mixture of Va and Vb); х = 2, y = 1 (II, VI, mixture of VIa and VIb);
х = 2, y = 2 (III, VII, mixture of VIIa and VIIb), exo : endo = (90–95) : (5–10), exo : endo = 93: 7
Scheme 1. Synthesis of cycloolefins.
exo-Tricyclo[5.2.1.02.6]dec-3(8)-ene (Va, Vb) was
prepared from 26.4 g (0.2 mol) of the cyclopentadiene
dimer (I). Yield 25.9 g (96.6 wt %, Va : Vb = 96.5 : 3.5).
lished data: bp 179–181°C, 101 kPa [31]). IR spec-
trum, ν, cm−1: 3060–3050 (СН=, νs), 2860–2850
(СН2, νs), 1670–1630 (С=С, ν), 1470–1465 (СН2,
20
20
1
Bp 71–72°C (2.13 kPa),
0.9986,
1.4988 (pub- δas), 1360, 1345 (CH, δ). H NMR, δ, ppm: 1.34–
d4
nD
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EPOXIDATION AND OXIDATIVE DIHYDROXYLATION
417
mixture of exo-2-(cyclohex-3l-en-ll-yl)bicy-
1.59 m (7H, H1, H6, H7, H8 , H8 , H9 , H9 ), 1.91–
A
B
A
A
B
2.40 m (5H, H2, H5 , H5 , H10A, H10B), 5.64 d.d. (1H,
clo[2.2.1]-heptane (VIIIa) and exo-5-cyclohexylbicy-
clo[2.2.1]hept-2-ene (VIIIb) was obtained by hydro-
genation of 34.8 g (0.2 mol) of exo-5-(cyclohex-3l-en-
A
B
2
3
2
H4, J4.3 11.1 Hz, J4.5 6.5Hz), 6.35 d.d. (1H, H3, J4.3
11.1 Hz, J3.2 6.5 Hz) [33]. 13C NMR, δ, ppm: 132.4
3
ll-yl)bicyclo[2.2.1]hept-2-ene (VIII). Yield: 31.8 g
(90.3 wt %, VIIIa : VIIIb = 96.0: 4.0). Bp 103–105°C
(C4), 132.2 (C3), 53.4 (C2), 43.2 (C6), 41.3 (C7), 40.0
(C1), 39 (C5), 32.6 (C10) , 28.8 (C8), 26.5 (C9). Mass
spectrum, m/z (abundance, %): 134[М]+• (8.6), 120
[C9H12]+• (6.7) 119 [C9H11]+ (4.4), 91 [C7H7]+ (12.4),
80 [C6H8]+• (100), 79 [C6H7]+ (60.1), 78 [C6H6]+•
(8.9), 77 [C6H5]+ (21.4), 68 [C5H8]+• (14.2), 67
[C5H7]+ (4.4), 66 [C5H6]+• (25.6), 65[C5H5]+ (15.4).
20
d4
nD20
1.4887. IR spectrum, ν,
(0.53 kPa),
0.9878,
cm−1: 3050–3040 (СН=, νs), 2860–2855 (СН2, νs),
1655–1628 (С=С, ν), 1470–1465 (СН2, δas), 1360,
1
1345 (CH, δ). H NMR, δ (ppm) in bicycloheptane:
1.26–1.62 m (8H, H2, H3A, B, H4, H5A, B, H6A, B), 1.91–
2.15 m (2H, H7A, B); in cyclohexene: 1.52–2.07 m (7H,
exo-Tricyclo[5,2.2.02.6]undec-3(8)-ene (VIa, VIb) H1, H2A, B, H5A, B, H6A, B), 5.61 dd (1H, H3, J4.3 11.2
2
Hz, J3.2 6.5 Hz), 6.63 dd (1H, H4, J4.3 11.2Hz, J5.4
6.5Hz): 13C NMR, δ (ppm) in bicycloheptane: 44.3
(C2), 40.5 (C7), 38.1 (C4) , 35.9 (C1), 29.5 (C5), 29.1
(C6), 26.7 (C3); in cyclohexene: 126.3 (C3), 126 (C4),
33.1 (C1), 32.2 (C2), 29.0 (C6), 23.6 (C5). Mass spec-
trum, m/z (abundance, %): 176[М]+• (8.5), 148
[C11H16]+• (2.3), 134 [C10H14]+• (4.7), 91 [C7H7]+•
(6.8), 81 [C6H9]+ (10.7), 80 [C6H8]+• (100), 79
[C6H7]+• (50.6), 66 [C5H6]+• (2.8).
3
2
3
was obtained by hydrogenation of 29.2 g (0.2 mol) of
exo-tricyclo[5.2.2.02.6]undeca-3,8-diene (VI). Yield
27.4 g (92.6 wt %, VIa : VIb = 94.0 : 6.0). Bp 76–78°C
20
(1.73 kPa),
0.9983,
d4
nD20
1.4963. IR spectrum, ν,
cm−1: 3050–3030 (СН=, νs), 2860–2855 (СН2, νs),
1640–1635 (С=С, ν), 1470–1465(СН2, δas), 1365,
1
1345 (CH, δ). H NMR, δ, ppm: 1.29–1.54 m [12H,
H1, H5 , H6, H7, H(8–11)A, B], 2.13–2.39 m (2H, H2,
A
H5 ), 5.62 d.d. (1H, H4, 2J4.3 11.1Hz, 3J4.5 6.4 Hz), 6.28
B
d.d. (1H, H3, 2J4.3 11.1 Hz, 3J3.2, 6.4 Hz). 13C NMR, δ,
ppm: 132.2 (C4), 132 (C3), 39.4 (C5), 38.2 (C2), 31.2
(C1), 31.0 (C7), 29.2 (C6), 24.2 (C10, 11), 22.9 (C9).
Mass spectrum, m/z (abundance, %):148 [М]+•
(4.8), 120 [C9H12]+• (6.8), 92 [C7H8]+• (11.4),
82 [C6H10]+• (10), 81 [C6H9]+ (9.2), 80 [C6H8]+•
(100), 79 [C6H7]+ (59.6), 78[C6H6]+• (9.9),
77[C6H5]+ (23.6), 68 [C5H8]+• (13.7). 66 [C5H6]+•
(29.3), 65 [C5H5]+(19.0).
exo-5-Cyclohexylbicyclo[2.2.1]hept-2-ene (VIIIb)
was prepared by condensation of 22.0 g (0.2 mol) of
vinylcyclohexane and 33.0 g of the dimer fraction of
cyclopentadiene (dimer content, 80% or 0.2 mol) fol-
lowed by isomerization of the endo-addition product
according to a procedure reported in [29]. Yield 21.9 g
d420
nD20
(62.3%). Bp 100–101°C (0.53 kPa)
1.5123 (published data [30] 100–101°C [0.53 kPa],
0.9693,
20
d4
20
0.9695,
1.5120). IR spectrum, ν, cm−13045–3040
nD
(СН=, νs), 2920–2890 (СН2, νs), 1635–1625 (С=С,
exo-Tricyclo[6,2.2.02.7]dodec-3(9)-ene
(VIIa,
ν), 1470–1465 (СН2, δas), 1360, 1345 (CH, δ). H
1
VIIb) was prepared by hydrogenation of 32.0 g
(0.2 mol of exo-tricyclo[6.2.2.02.7]dodeca-3,9-diene
(VII). Yield 29.1 g (89.3 wt %, VIIa : VIIb = 92.6 : 7.4).
NMR, δ (ppm) in bicycloheptene: 1.37–1.63 m (4H,
H5, H6A, B, H7 ), 1.77–2.60 m (3H, H1, H4, H7 ), 6.27
B
A
d (1H, H2, 2J3.2 11.3 Hz, 2J2.1 6.5 Hz), 6.29 d (1H, H3,
20
20
Bp. 78–80°C (0.53 kPa),
0.9852,
1.4946. IR
nD
d4
2J3.2 11.3 Hz, J4.3 6.5 Hz); in cyclohexane: 1.29–1.48
3
spectrum, ν, cm−1: 3050–3040 (СН=, νs), 2860–
2855 (СН2, νs), 1640–1630 (С=С, ν), 1460–1470
m (6H, H1, H2 , H3 , H4 , H5 , H6 ), 1.50–1.56 m
B
B
B
B
B
(5H, H2 , H3 , H4 , H5 , H6 ). 13C NMR, δ (ppm) in
A
A
A
A
A
(СН2, δas), 1360, 1345 (CH, δ). H NMR, δ, ppm:
1
bicycloheptene: 136.2 (C2, C3), 49.0 (C5), 47.8 (C7),
43.8 (C1), 37.3 (C4), 31.6 (C6); in cyclohexane: 37.6
(C1), 33.3 (C2 and C6), 26.4 (C3 and C5), 26.2 (C4).
Mfound = 174.3, Mcalc. = 176.
1.30–1.77 m [13H, H1, H6A, B, H7, H8, H(9-12)A, B],
1.94–2.14 m (3H, H2, H5A, B), (1H, 5.62 dd (1H, H4,
2J4.3 11.1 Hz, J5.4 6.5 Hz), 5.93 dd (1H, H3, J4.3 11.2
Hz, 3J3.2 6.5 Hz ) . 13C NMR, δ, ppm: 129.2 (C3), 128
(C4), 34.1 (C7), 31.6 (C1), 31.1 (C2), 28.6 (C8), 24.5
(C9, 12), 23.8 (C5), 22.8 (C10, 11), 19.2 (C6). Mass spec-
trum, m/z (abundance, %): 162 [М]+• (4.8), 134
[C10H14]+• (4.9), 119 [C9H11]+ (4.7), 91 [C7H7]+
(11.3), 82 [C6H10]+• (10), 81 [C6H9]+ (10.3),
80 [C6H8]+• (100), 79 [C6H7]+ (57.4), 78[C6H6]+•
(10.3), 77 [C6H5]+ (23.6), 68 [C5H8]+• (13.7). 65
[C5H5]+• (9.3).
3
2
exo-5-Phenylbicyclo[2.2.1]hept-2-ene (IX) was
prepared by condensation of 104 g of freshly distilled
styrene (1 mol), 165 g of the dimer fraction of cyclo-
pentadiene (dimer content of 80% or 1 mol), and 5 wt
% hydroquinone in an autoclave at a temperature of
200°C followed by isomerization of the endo-addition
product according to the procedure reported in [29].
20
Yield 111.4 g (65.5%). Bp. 135–136°C (1.2 kPa),
d4
20
1.0272, 20 1.5481 (published data [30]: 20 1.0270,
nD
d4
nD
PETROLEUM CHEMISTRY Vol. 57 No. 5 2017

418
ALIMARDANOV et al.
1.5480). IR spectrum, ν, cm−1: 785–680 (C6H5, δ),
1650–1640 (С=C, ν), 3050–3040 (СН=, νs), 1470–
ously charged with cycloolefin (0.1 mol), catalyst, and
toluene (or dichloroethane) as a solvent (15 mL). A
measured amount of the oxidant (0.2 mol) was intro-
duced into the reactor at 50°C within 1 h, with the
temperature being raised to 70–75°C. The reaction
mixture was stirred for 3 h. The H2O2 consumption
was monitored using permanganatometric titration,
and the composition of the oxidation products was
1
1465 (СН2 δas), 1360, 1345 (CH, δ). H NMR, δ
(ppm) in bicycloheptene: 1.52–1.96 m (4H, H6
,
A, B
H7A, B), 2.30–2.85 m (3H, H1, H4, H5), 6.25 (2H, H2,
H3, 2J3.2 6.5 Hz), 7.28–7.39 m (5H, Ar). 13C NMR, δ,
ppm: 132.4 (C2), 131.3 (C3), 53 (C4), 50.8 (C7), 43
(C1), 35.8 (C5), 31.7 (C6); in the C6H5 moiety: 144.7 determined by GLC on a Tsvet-500 chromatograph
(C1), 128.5 (C3 and C5), 127 (C2 and C6), 126 (C4).
Mass spectrum, m/z (abundance, %): 170 [М]+•, 141
[C11H9]+ (3.2), 115[C9H7]+ (3.1), 10 [C8H7]+ (55.6),
102 [C8H6]+• (5.6), 91 [C7H7]+ (7.8), 79 [C6H7]+
(45.3), 78 [C6H6]+• (100), 77 [C6H5]+ (10.2), 66
[C5H6]+• (4.7).
with a flame ionization detector, using a 2000 × 3 mm
column packed with polyethylene glycol succinate-
coated (5 wt %) Chromosorb, nitrogen as a carrier gas,
a column temperature of 160°C, and an evaporator
temperature of 280°C. The reactivity of the substrates
was determined as the time dependence of the yield of
corresponding epoxides and diols. The IR spectra of
the epoxides and diols were recorded on an Alpha
spectrometer in the region of 400–4000 cm−1. The
assignment of their absorption bands was made on the
basis of published data [32].
General Procedure for Oxidation
of Bridged Unsaturated Hydrocarbons
The reaction was carried out in the liquid phase at
atmospheric pressure in a laboratory unit with a glass
reactor equipped with an oxidant (hydrogen peroxide
Scheme 2 shows the oxidation products of the main
isomers of cycloolefins contained in the mixture (Va,
solution) supply system. The reactor was simultane- VIa, VIIa, VIIIa).
x
OH
x
+
O
OH
X (75%), XI (72%)
XII (69.3%)
Xa (24%), XIa (27%)
XIIa (30%)
Va, VIa, VIIa +H2O2, cat.
VIIIa
4'
HO
3'
O
5'
6'
4'
5'
2'
1'
3'
7'
2'
1'
7
7
6'
OH
1
1
6
6
2
2
4
+
4
5
5
3
3
XIII (54%)
XIIIa (46%)
x = у = 1(X, Xа); х = 2, у = 1(XI, XIа); х = у = 2(XII, XIIа)
Scheme 2. Oxidation of isomeric cycloolefins.
endo-4-Oxa-exo-tetracyclo[6.2.1.03.502.7]undec-
ane (X) was prepared from 13.4 g (0.1 mol) of Va; oxi-
dant: H2O2 ⋅ CO(NH2)2. Yield 11.3 g (75.3 wt %). Bp
20
1.91–2.57 m (4H, H3, H5, H11A, B). 13C NMR, δ
(ppm): 61.9 (C5), 53.4 (C3), 52.2 (C2), 37.6 (C8), 36.7
(C1), 34.8 (C11), 34.0 (C6), 32.6 (C7), 28.9 (C9), 28.7
(C10). Mass spectrum, m/z (abundance, %): 150
[М]+• (3.8), 132 [C11H14]+• (6.6), 120 [C9H12]+• (4.4),
119 [C9H11]+ (4.3), 118[C9H10]+• (6.0), 92 [C7H8]+•
(10.7), 91 [C7H7]+ (4.5), 81[C6H9]+ (51.8), 80
[C6H8]+• (100), 78 [C6H6]+• (9.1), 68 [C5H6]+• (14.0),
66 [C5H6]+• (29.4).
44–45°C (0.24 kPa),
1.0235, 201.4876. IR spec-
nD
d4
trum, ν, cm−1: 3040 (HC, νs, oxirane), 2890 (СН, ν),
2860 (СН2, νs), 1458 (СН2, δas), 1340 (СН, δ), 1260
(HC
CH,
νs),
975,
910,
860,
O
1
845(HC
CH, νаs). H NMR, δ (ppm): 1.36–
endo-4-Oxa-exo-tetracyclo[6.2.2.03.502.7]dodec-
ane (XI) was obtained from 14.8 g (0.1 mol) of VIa;
O
1.76 m (10H, H1, H2, H6A, B, H7, H8, H9A, B, H10A, B),
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EPOXIDATION AND OXIDATIVE DIHYDROXYLATION
oxidant: H2O2 ⋅ CO(NH2)2. Yield 11.8 g (72.0 wt %).
419
1440 (СН2, δаs), 1345 (CH, δ), 1260 (HC
νs), 990, 903, 870, 850 (HC
CH,
Bp. 75–77°C (0.66 kPa) 1.0426, 1.4906. IR spectrum,
ν, cm−1: 3035 (HC, νs, oxirane), 2892 (СН, ν), 2855
(СН2, νs), 1450 (CH2, δas), 1350 (CH, δ), (1245
O
CH, νas). 1H NMR,
O
CH, νs), 985, 910, 870, 845
δ (ppm) in tricyclooctane: 1.23–1.78 m (6H, H1, H5, H6,
(HC
H7A, B, H8 ), 1.91–2.90 m (3H, H2, H4, H8 ) 2.29 m; in
O
B
A
1
cyclohexane: 1.29 m (2H, H2 , H6 ), 1.44 m (1H, H1),
(HC
CH,ν аs). H NMR, δ (ppm): 1.29–1.56
B
B
1.46 m (2H, H3 , H5 ); 1.48 m (1H, H4 ), 1.51 m (1H,
O
B
B
B
(12H, H1, H6 , H8, H7, H(9–12)A, B), 1.67–2.73 m (4H,
H4 ), 1.56 m (4H, H2 , H3 , H5 ). 13C NMR, δ (ppm) in
B
A
A
A
A
H2, H3, H5, H6 ). 13C NMR, δ (ppm): 62.3 (C5), 53.8
bicyclooctane: 53.9 (C2), 53.4 (C4), 43.0 (C6), 37.8 (C1),
32.0 (C5), 26.0 (C7), 24.5 (C8); in cyclohexane: 40.8 (C1),
33.2 (C2, C6), 26.3 (C3, C5), 26.1 (C4). Found: C, 81.54;
H 10.28. Calculated for C13H 20O: C, 81.25; H 10.42,
Mfound = 190.2, Mcalc = 192.
A
(C3), 52.9 (C2), 34.3 (C7) , 32.6 (C6), 31.0 (C8), 24.4
(C(9-12)), 24.0 (C1). Found: C, 80.15; H, 9.97. Calcu-
lated for C11H16O: C, 80.49; H, 9.76; Mfound = 162.0,
Mcalc = 164.
5-exo-Cyclohexyl-exo,endo-2,3-dihydroxybicy-
clo[2.2.1]heptane (5-cyclohexylnorbornane-2,3-diol)
(XIVa) was obtained from 17.6 g (0.1 mol, VIIIb); oxi-
dant: 30% H2O2 aqueous solution. Yield 12.2 g
endo-4-Oxa-exo-tetracyclo[7.2.2.03.502.8]tridec-
ane (XII) was prepared from 16.2 g (0.1 mole) of VIIa,
oxidant: H2O2 ⋅ CO(NH2)2, yield 12.3 g (69.3%). Bp
92–93°C (0.5 kPa) 1.0745, 1.4914. IR spectrum, ν,
cm−1: 3030 (CH, νs, oxirane), 2890 (CH, ν), 2855
(СН2, νs), 1455 (CH2, δas), 1340 (CH, δ), (1250
(58.6 wt %). Mp 108–110°C. IR spectrum ν, cm−1:
3620 (OH, ν), 3580 (OH, ν), 2905 (CH, ν), 2860
(CH2, νs), 1440 (СН2, δаs), 1355 (СН, δ), 1125 (ОН,
(HC
CH, νs), 900, 870, 850 (HC
CH,
δ). 1H NMR, δ (ppm): 1.26–2.16 m (1H, H1, H4, H5,
H6A, B, H7A, B), 3.27 d (2H, H2 and H3, J3.2, 7.2 Hz) 3.61
br.s (2H, 2OH); in cyclohexane: 1.44–1.55m (11H).
13C NMR, δ (ppm) in bicycloheptane: 82 (C2), 79.6
(C3), 45.8 (C4), 41 (C5), 39.4 (C1), 28 (C7), 24.3 (C6);
in cyclohexane: 41.3 (C1), 33.2 (C2 and C6), 26.3 (C3
and C5), 26.1 (C4). Found: C, 74.54; H 10.36. Calcu-
lated for C13H22O2: C, 74.29; N 10. 48, Mfound = 207.2,
Mcalc = 210.
O
O
1
νаs). H NMR, δ, ppm: 1.29–1.56 m [14H, H1, H2,
H6 , H7 , H8, H9, H(10–13)A, B], 1.67–2.89 m (H3, H5,
B
B
H6 , H7 ). 13C NMR, δ, ppm: 54.5 (C5), 51.2 (C3),
A
A
42.3 (C8), 32.8 (C2) 29.3 (C7), 28.4 (C9), 24.5 (C1, C10,
C13), 24.2 (C11, C12), 24.0 (C6). Found: C 81.11, H
10.28. Calculated for C12H18O: C, 80.90; Н 10.11,
Mfound = 176.2, Mcalc = 178.
endo-3-Oxa-exo-6-phenyltricyclo[3.2.1.02.4]octane
(XV) was obtained from 17.0 g (0.1 mol) of IX; oxidant:
H2O2 ⋅ CO(NH2)2. Yield 10.1 g (54.2 wt %). Mp 63–
exo-2-(4l-Oxabicyclo[4.1.0]heptyl)bicyclo[2.2.1]hep-
tane (XIII) was obtained from 17.6 g (0.1 mol) of VIIIa;
oxidant: H2O2 ⋅ CO(NH2)2. Yield: 10.4 g (54.0 wt %). Bp
65°C. IR spectrum, ν, cm−1: 3040 (HC, νs, oxirane),
90–92°C (0.2 kPa), mp 46–48°C. IR spectrum, ν, cm−1:
3030–3040 (HC, νs, oxirane), 2890 (CH, ν), 2850 (СН2,
2890 (CH, ν), 2855 (СН2, νs), 1660 (C6H5, ν), 1430
(СН2,
δas),
1265
(HC
CH,
νs),
νs), 1430 (СН2, δаs), 1348 (СН, δ), 1265 (HC
CH,
O
O
845(HC
CH, νas), 975, 910, 778–685 (C6H5, δ).
1
νs), 990, 910, 870(HC
CH, νas). H NMR, δ
O
O
1H NMR, δ (ppm): 1.58 m (1H, H7 ), 1.83 m (1H,
B
(ppm) in bicycloheptane: 1.27–2.16 m [11H, H1, H2,
H3A, B, H4, H5A, B, H6A, B, H7A, B], in epoxycyclohexane:
1.29–2.89 m (9H, H1, H2A, B, H3, H5A, H6A, B, H7A, B). 13C
H7 ), 1.91 m (1H, H8 ), 2.15 m (2H, H5, H8 ), 2.30 m
A
B
A
(1H, H1), 2.88 d (1H, H2, H4, J4.2 7.2 Hz), 7.28–7.39 m
(5H, Ar). 13C NMR, δ (ppm): 67.2 (C4), 54 (C2), 43
(C6), 39.8 (C7), 39.4 (C5), 37 (C1), 23.8 (C8), in C6H5:
NMR, δ (ppm) in norbornane: 42.4 (C2), 40.6 (C7), 38.0
(C4), 36.0 (C1), 29.5 (C5), 29.1 (C6), 26.5 (C3) Epoxycy-
clohexane: 62.3 (C5), 52.5 (C3), 34.2 (C2), 33.3 (C1),
30.8 (C7), 21.8 (C6). Found: C, 81.44; H 10.63. Calculated
for C13H20O: C, 81.95; H, 10.42.
146.5 (C1), 1(8.6 (C3 and C5), 126.7 (C2 and C6), 126
(C4). Found: C, 83.51; H, 7.38. Calculated for
C13H14O: C, 83.87; H, 7.53; Mfound = 184.4, Mcalc = 186.
exo-5-Phenyl-exo,endo-2,3-dihydroxybicyclo [[2,
2, 1]heptane (5-phenylnorbornane-2,3-diol) (XVa) was
obtained from 17.0 g (0.1 mol) of IX; oxidant: 30%
H2O2 aqueous solution. Yield 8.9 g (44.0 wt %). Mp
endo-3-Oxa-exo-6-cyclohexyltricyclo[3.2.1.02.4]octane
(XIV) was obtained from 17.6 g (0.1 mol) of VIIIb; oxi-
dant H2O2•CO(NH2)2. Yield 14.7 g (76.4 wt %). Bp 94–
95°C (0.2 kPa), 1.0683, 1.4926. IR spectrum, ν, cm−1:
228–230°C. IR spectrum ν, cm−1: 3580 (OH, ν), 3550
3050 (HC, νs, oxirane), 2890 (CH, ν), 2850 (CH2, νs), (OH, ν), 2890 (CH, ν), 2850 (CH, νs), 1640 (C6H5,
PETROLEUM CHEMISTRY Vol. 57 No. 5 2017

420
ALIMARDANOV et al.
Table 1. Results of experiments on the oxidation of cycloolefins with a 30% H2O2 aqueous solution in the presence of mod-
ified forms of the phosphomolybdic heteropoly compound (PMHC)* (olefin : H2O2 molar ratio = 1 : 2, 50 mmol of olefin,
15 mL of C2H4Cl2, T = 70°C, τ = 6 h)
Yield, wt % **
Cycloolefin
Conversion, %
epoxide
diol
10
3
1
9
91
90
21.3
20.5
60
65.3
2
Vа
VIа
X −
Xa −
4
7
8
5
6
10
11
3
89
82
23
25.4
60
50.6
2
1
9
XI –
XIa –
4
7
8
5
6
11
12
3
10
82
80
18.6
22.0
55
52
1
VIIа
VIIIа
XII –
XIIa –
4
2
8
6
9
5
7
4'
7
3'
2'
1'
5'
61
59
7.4
10.3
74.2
74.5
6'
6
XIII –
XIIIa –
1
2
4
5
3
4'
5'
3'
6'
2'
7
4
75
91
29
30.4
58.5
58.6
***VIIIb
XIV –
XIVа –
XVа –
1
2
1'
6
5
3
7
1
52
63
11
43
78
44
6
2
IX
XV –
4
3
5
In Tables 1 and 2:
* PMHC : HBr : CoCO molar ratio is 1 : 0.8 : 3.5, the support is a carbon material.
3
** The value in the numerator refers to the yield of the product of the reaction in the presence of a sample modified with HBr and
CoCO and that in the denominator, over PMHC modified with HBr and Gd O .
3
2 3
*** The catalyst was used without pretreatment with hydrogen peroxide.
δ), 1460 (CН2, δas), 1360 (CН, δ), 778–685 (C6H5, δ). [C11H14]+ (6.3), 144 [C11H12]+• (11.2), 121 [C9H13]+
(3.2), 120 [C9H12]+• (5.8), 106 [C7H10]+• (56.8), 92
[C7H8]+• (11.6), 79 [C6H7]+ (51.0), 78 [C6H6]+• (100),
77 [C6H5]+ (10.3), 66 [C5H6]+• (21.4), 65 [C5H5]+•
(5.0), 66 [C5H6]+•. Found: C, 76.24; H 7.97. Calcu-
lated for C13H16O2: C, 76.47; H, 7.84.
1H NMR, δ ppm: 1.58 m (1H, H6 ), 1.83 m (1H, H6 ),
B
A
1.89 m (1H, H7 ), 1.91 m (1H, H4), 2.05 m (1H, H7 ),
B
A
2.73 m (1H, H5), 3.26 d (2H, H2 and H3, J3.2 7.2 Hz),
3.60 br.s (2H, 2OH), 7.28–7.39 m (5H C6H5). 13C
NMR, δ (ppm) in bicycloheptane: 81.8 (C2), 78.9
(C3), 41.2 (C5), 39.8 (C4), 38.0 (C6), 37.3 (C1); in the
C6H5 moiety: 146.5 (C1), 128.6 (C3 and C5), 126.7 (C2
The reactivity of the cycloolefins was determined
by comparing their conversion and the yield of the
corresponding epoxides or diols under the conditions
and C6). m/z (abundance, %):186 [C13H14]+•(3.4), 145 adopted as standard (T = 70°C; τ = 6 h; olefin : H2O2
PETROLEUM CHEMISTRY
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2017

EPOXIDATION AND OXIDATIVE DIHYDROXYLATION
421
Table 2. Results of experiments on the oxidation of cyclo-
olefins with 30% H2O2 solution in dioxane or with the
adduct H2O2 ⋅ СO(NH2)2 in the presence of PMHC (I)
modified with HBr and CoCO3 (II) or HBr and Gd2O3
(III)* (olefin : H2O2 molar ratio= 1 : 2, 50 mmol of olefin,
15 mL of С2Н4Сl2, T = 70°C, τ = 6 h)
molar ratio = 1: 2; olefin amount, 50 mmol; solvent
C2H4Cl2, 15 mL) (Tables 1, 2).
RESULTS AND DISCUSSION
Epoxidation (or dihydroxylation) of tricyclic
unsaturated hydrocarbons with hydrogen peroxide in
the two-phase water–organic solvent system selec-
tively proceeds at 65–85°C according to Scheme 2.
Yield, wt %**
Cycloolefin Conversion, %
epoxide
diol
In contrast to the norbornene epoxidation reac-
tion, the Wagner–Meerwein rearrangement in tricy-
clic hydrocarbons does not occur under these condi-
tions,.
The results of the study are presented in Tables 1
and 2.
According to published data [36, 37], acid groups
preliminarily introduced into the composition of per-
oxo complexes under the conditions of oxidation of
unsaturated compounds successfully compete with
substrate conversion products (diols in this case) for
coordination sites at the MeO4+ ion, thereby prevent-
ing the peroxo complexes from washing out of the sur-
face of the carbon material.
81.0
86.0
60
75.3
12.5
4.4
Va
VIa
84
85.0
67.2
72.0
12
7.4
80
79.0
64.5
69.3
9.7
8.7
VIIa
VIIIa
VIIIb
IX
58
62
43.3
54.0
10.5
5.9
79
83.0
51.6
76.4
20.4
6.8
The activation of H2O2 and the product composi-
tion in the oxidation of mono- and polycyclic olefins
in a pseudohomogeneous system largely depend on
the nature of the solvent used, the oxidizing agent, and
the reaction-mixture stirring speed. In particular, it is
known that solvents actively participate in the solva-
tion of the initial catalytic system, the forming peroxo
complexes, and other components of the reaction
mixture [38, 39]. Depending on the solvent nature, the
substrate conversion and selectivity for the products
can vary over a wide range. The results of experiments
on the oxidation of exo-tricyclo[5.2.1.02,6]dec-3(8)-
ene with a 30% H2O2 solution in dioxane show that
there is no distinct dependence of the initial oxidation
rate of this cycloolefin on the dielectric constant (ε) of
the solvent. The highest epoxide yields were obtained
using dioxane (93%), toluene (92%), and dichlo-
roethane (85%) with a cycloolefin conversion of 90–
97%. In the case of basic polar solvents (dimethylfor-
mamide, acetonitrile), the yields of the oxidation
products were significantly lower to be as small as
72.8–82%. On passing from the dioxane solution of
H2O2 to an aqueous or alcohol solution of the H2O2
adduct with urea, both the active-oxygen consump-
tion rate, calculated by graphical differentiation of the
curves in the product yield–reaction time coordi-
nates, and the product composition are changed. In
the case of the dioxane solution of H2O2 or the [H2O2 ·
CO(NH2)2] adduct in ethanol, the main product of
the reaction is a mixture of endo-4-oxa-exo-tetracy-
64
67.0
52.0
54.2
8.4
6.1
mation of a hardly separable mixture of tricyclodec-
anediol isomers. Probably, in the case of the H2O2
adduct with urea or its dioxane solution, the isomers
bind the released water molecules to form hydrates,
thereby precluding the hydrolysis of the primary oxi-
dation products, namely, the epoxides.
The temperature and time of the reaction have a
significant effect on the yields and the epoxide to diol
molar ratio; in the case of aqueous solution, the speed
of stirring of the reaction mixture has an effect as well.
Since cycloolefins are practically insoluble in the
aqueous medium, the reaction proceeds in the hetero-
geneous system. Oxidation of the reduced forms of
PMHC occurs in the aqueous phase, and the oxida-
tion of the substrate occurs either in the organic phase
or at the interface. Therefore, in the case of an aqueous
H2O2 solution, a high conversion of cycloolefins is
achieved using intense stirring of the reaction mixture
at a rate of 600–700 rpm. In the case of dioxane or
alcoholic solutions of the oxidant, the stirring speed
does not exceed 150–200 rpm. With an increase in
temperature from 40 to 70°C, the total yield of epox-
ides and glycols (depending on the oxidant used)
increases from 26.5 to 95.4%. A further increase in
temperature leads to an increase in the amount of
oligomerization products and a decrease in the
amount of epoxides and glycols in the oxidate.
clo[6.2.1.03.502.7]-
and
exo-3-oxa-exo-tetracy-
clo[5.3.1.02.4.06.10]undecanes (yield 69.5–82.8%).
However, the oxidation of this hydrocarbon with the
30% H2O2 aqueous solution leads mainly to the for-
PETROLEUM CHEMISTRY Vol. 57 No. 5 2017

422
ALIMARDANOV et al.
The yield of epoxides and diols also depends on the
Higher selectivity for epoxides and diols is observed
structure of the substrates, the reactivity of which var- in the case of oxidation of compounds with a multiple
ies in the order: VIIIb > Va ~ VIa ~ VIIa > VIIIa > IX. bond in the bicycloheptene moiety (Scheme 3):
4'
4'
3'
6'
3'
7
2'
2'
5'
5' HO
8
1
6'
3
O
6
1
2
7
2
3
1'
1'
+H2O2, cat.
1)
2) isomerization
+
4
5
1
5
6
4
HO
VIIIb
XIV
XIVa
7
8
1
HO
1)
3
+H2O2, cat.
2
2
6
5
O
+
7
2) isomerization
3
4
5
4
6
HO
IX
XV
XVa
Scheme 3. Oxidation of compounds with a multiple bond.
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Russian].
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Note that after completing the oxidation experi-
ments, the catalysts are easily separated from the liq-
uid phase by filtration. Fivefold reuse of these systems
has shown that their activity in the oxidation reaction
remains almost unchanged.
12. A. D. Berents, A. B. Vol’-Enshtein, T. N. Mukhina,
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In summary, the study of the oxidation of C10–C13
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with HBr and CoCO3 (or Gd2O3) and supported on a
carbon material has shown that in the case of a 30%
H2O2 aqueous solution or the H2O2–carbamide
adduct as an oxidant, the main products of the reac-
tion are respectively corresponding vicinal glycols or
epoxides.
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