Epoxidation of tetracyclodecene hydrocarbons with the H2O2·CO(NH2)2 adduct in the presence of heteropoly compounds containing rare-earth metal cations

Article abstract of DOI:10.1134/S1070363217020098

Epoxidation of tetracyclododecene bridged hydrocarbons prepared via the [4+2]-condensation of bicyclo[2.2.1]hept-2-ene and its alkyl derivatives with cyclopentadiene in the presence of Н-form of synthetic mordenite has been studied. Phosphorus-molybdenum

Full text of DOI:10.1134/S1070363217020098

ISSN 1070-3632, Russian Journal of General Chemistry, 2017, Vol. 87, No. 2, pp. 208–214. © Pleiades Publishing, Ltd., 2017.
Original Russian Text © Kh.M. Alimardanov, O.A. Sadygov, N.I. Garibov, E.S. Musaeva, N.R. Dadashova, M.B. Almardanova, 2017, published in Zhurnal
Obshchei Khimii, 2017, Vol. 87, No. 2, pp. 230–237.
Epoxidation of Tetracyclodecene Hydrocarbons
with the H O ·CO(NH ) Adduct in the Presence
2
2
2 2
of Heteropoly Compounds Containing Rare-Earth Metal Cations
Kh. M. Alimardanov*, O. A. Sadygov, N. I. Garibov,
E. S. Musaeva, N. R. Dadashova, and M. B. Almardanova
Mamedaliev Institute of Petrochemical Processes, Azerbaijan National Academy of Sciences,
Khojaly ave. 30, Baku, 1025 Azerbaijan
*
e-mail: hafiz_alimardanov@yahoo.com
Received July 21, 2016
Abstract—Epoxidation of tetracyclododecene bridged hydrocarbons prepared via the [4+2]-condensation of
bicyclo[2.2.1]hept-2-ene and its alkyl derivatives with cyclopentadiene in the presence of Н-form of synthetic
mordenite has been studied. Phosphorus-molybdenum and phosphorus-tungsten heteropoly compounds doped
3
+
3+
3+
(4–x)+
with Co , Gd , Nd , Ce
material have exhibited high activity in epoxidation of the synthesized hydrocarbons under the action of the
·CO(NH adduct. Structures of the new bridged polycyclic epoxides have been elucidated by IR as well
(x = 0, 1) cations as well these compounds deposited on highly disperse carbon
H
2
O
2
2 2
)
1
13
as Н and С NMR spectroscopy.
Keywords: tetracyclododecene hydrocarbon, molybdenum heteropoly compound, tungsten heteropoly compound,
rare-earth metal cations pentacyclic epoxide, vicinal diol
DOI: 10.1134/S1070363217020098
Unsaturated hydrocarbons containing bicyclo-
heptene fragments are widely used in preparation of a
range of compounds applied in industry. Derivatives of
these hydrocarbons (especially these bearing oxygen-
or nitrogen-containing moieties) possess valuable
properties and, due to their unique structure, can be
used as biologically active and medical drugs [1–7],
synthetic fragrances [8], monomers for preparation of
polymeric materials for special applications, stabilizers,
etc. [9]. The availability of these hydrocarbons has
been improved due to the development of methods of
cyclic dienes with cyclopentadiene prepared by mono-
2
.6
merization of its dimer, tricyclo[5.2.1.0 ]deca-3.8-
diene, in the presence of decationated forms of mordenite
or NaY and hydrogenation of the formed compounds
in a flow-through system [10, 11].
2
.6
The dimer of cyclopentadiene, tricyclo[5.2.1.0 ]-
deca-3.8-diene, is completely monomerized at 160–
1
80°С in the presence of zeolite catalysts [9]. On the
contrary, co-dimer of cyclohexadiene-1.3 with cyclo-
2
.6
pentadiene, endo-bicyclo[5.2.2.0 ]undeca-3.8-diene,
is stable under these conditions.
[4+2], [3+2], and [4+1]-condensation of mono- and
diolefins involving homogeneous and heterogeneous
catalysts [10].
Extending the studies presented in Ref. [10], we
found that the reaction of bicyclo[2.2.1]hept-2-ene and
its 5-alkyl derivatives with cyclopentadiene dimer
under conditions of monomerization of the latter in the
presence of decationated forms of mordenite gave
In this work, we discuss the data on epoxidation of
tetracyclododecene hydrocarbons using the hydrogen
peroxide–urea adduct in the presence of phosphorus-
molybdenum and phosphorus-tungsten polyoxoperoxo
complexes.
3
.6 2.7
tetracyclo[6.2.1.1. .0 ]dodec-4-enes (1–5) in high
yield (Scheme 1).
We have earlier reported the selective synthesis of
The structure of products 1–5 was confirmed by the
data of IR as well as Н and С NMR spectroscopy.
The IR spectra contained the ν(С=С) absorption bands
1
13
С –С tricyclic unsaturated hydrocarbons of the pre-
1
1
13
defined structure via co-condensation of С –С ali-
6
8
2
08

EPOXIDATION OF TETRACYCLODECENE HYDROCARBONS
209
Scheme 1.
R
1
8
1
12
3
Δ, cat
H
2
1
2
R
10
4
Δ, cat
9
6
5
7
H
1_
5
R = H (1), CH
3
2
(2), C H
5
3
(3), C H
9
4 9
(4), C H (5).
Scheme 2.
H
H
_
t, cat
_
n 1)+
_
n+
2
_
Me(
(OH)
+
Me O
+
H
H
R
_
_
t, cat
Me(
n 1)+
(OH) +
H
H
+
H
H
R
R
H
+
+
H
H
R
_
R
R
+
_
–
1
at 1578–1553 cm [13], due to strain in the bicyclo-
density, is converted into nortricyclene cation. The
latter further gives a π-complex with cyclopentadienyl
anion, converted into the final tetracyclic product via
sigmatropic rearrangement of the C–C bonds.
heptene fragment of the molecule. The ν(СН) band
appeared at 3070–3035 cm .
–
1
1
In the Н NMR spectra, the olefinic protons of the
bicycloheptene fragment were observed as doublets at
In order to introduce the oxygen function into the
molecules of tetracyclododecenes 1–5, we oxidized
them at 60–70°С under the action of the hydrogen
peroxide–urea adduct or with a 30% solution of Н О
6
.08–6.11 ppm, whereas the methyl protons of the
alkyl groups appeared as triplets and doublets at
.98 ppm. Elongation of the side chain resulted in the
0
2
2
shift of the terminal methyl protons signal to 0.88–0.91
ppm [13–15]. The alkyl groups were predominantly in
the endo-position with respect to the bridge. The
endo : exo ratio ranged from 65 : 35 to 80 : 20.
in formic or acetic acid, at the substrate : oxidizer :
RCOOH molar ratio of 1 : (1–2) : (0.2–0.4), at 60–70°C
(Scheme 3). Under those conditions, the oxygen atom
transfer occurred via the in situ formation of a mixture
of polyoxo- and polyoxoperoxo phosphorus-molybdenum
or phosphorus-tungsten systems containing rare-earth
3.6 2.7
Tentative mechanism of tetracyclo[6.2.1.1. .0 ]dodec-
4-enes 1–5 formation is shown in Scheme 2.
metals [16]. The peracids RCO H formed at the initial
3
The molecule of cyclopentadiene is readily depro-
stage aided in accumulation of the active peroxo-
metallate intermediate, the latter acting as the oxygen
atom carrier to the double bond of the substrate.
tonated under the action of basic centers of the catalyst
2
–
(
О ) with the formation of aromatic cyclopentadienyl
anion. In contrast, the molecule of alkylbicyclo[2.2.1]-
hept-2-ene, due to high electron density at the multiple
bond, interacts with the acidic centers of the catalyst
Structure of the epoxy and dihydroxy derivatives
1
13
was confirmed by Н and С NMR spectroscopy data.
13
3.7 4.6 2.8
(
metal cation) and, after redistribution of the electron
С NMR spectra of 10-R-oxapentacyclo[6.2.1.1 .0 .0 ]-
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 87 No. 2 2017

2
10
ALIMARDANOV et al.
Scheme 3.
1
9
3
12
1
3
2
4
1
1
0
7
5
1
9
0
8
6
O
)
], Δ, сat
R
R
2
2
2 2
2
2
6_10
+
H O [or H O CO(NH
1_
5
1
1
12
OH
1
3
1
2
4
8
6
7
5
OH
1_15
4 9
(4, 9, 14), C H (5, 10, 15).
1
R = H (1, 6, 11), CH
3
(2, 7, 12), C
2
H
5
(3, 8, 13), C
3
H
9
dodecanes 6–10 contained the signals at 27.1–27.5 ppm,
evidencing the exo-configuration of the epoxide
fragment (the signals of the endo-isomer are found at a
weaker field, ≈40 ppm [5]).
The solvent nature is known to strongly affect the
solvation of the initial catalytic system, the in situ
formed peroxo complexes, and other components of
the reaction mixture [17–19]. Depending on the nature
of the solvent, the substrate conversion and the reac-
tion selectivity can vary widely. The largest yields of
Epoxidation of tetracycloolefins with 30% solution
of hydrogen peroxide in dioxane or with Gd(III) or
Ce(IV) polyoxo phosphorus-molybdenum complex
treated with 30% aqueous Н О was performed in the
3.6 2.7
the epoxide of 10-methyltetracyclo[6.2.1.1 .0 ]dodec-
-ene 7 were reached in dichloroethane, toluene, and
dioxane (Table 3). The use of aprotic dipolar solvents
acetonitrile and DMF) decreased the yield of the
4
2
2
absence of carboxylic acids. The obtained polyoxo-
peroxo phosphorus-molybdenum complex showed
high activity in the reaction of oxidation.
(
oxidation products. When oxidizing with aqueous
Н О the reaction proceeded either in organic phase or
2
2
The oxidation reaction selectivity, rate and the
products yield were affected by temperature, duration
of the reaction, and nature of the solvent and the
oxidant. The increase in temperature from 40 to 70°С
resulted in the increase in the total yield of epoxides
and glycols from 28 to 86%. The highest yields (78–
at the interphase. From the available data [16], one
could assume that the transfer of the active oxygen
atom to the multiple bond of tetracyclododecene and
its alkylderivatives 1–5 occurred in organic phase, the
carrier being the peroxo complex formed in situ in the
aqueous phase rather than hydrogen peroxide itself.
After the transfer of active oxygen to the substrate, the
catalytic complex regenerated its activity via the
contact with hydrogen peroxide. Hence, the content of
active oxygen (the peroxo complex) in the organic
phase remained practically throughout the reaction
course. In view of that, we attempted to increase the
target products yield performing the reaction at
vigorous stirring (600–700 rpm; in the case of the
reaction in dioxane solution of Н О or in solution of
8
6%) were attained at 50–70°С and the reaction dura-
tion of 2.5–3.0 h. Further increase in the temperature
to 80–90°С) and the reaction duration led to the
(
formation of high-boiling products and the reduced
yield of the target products, due to the reaction of the
oxirane ring and the hydroxyl groups of the vicinal
diols with the unreacted molecules of С –С
1
2
carboxylic acids and the substrate. The major product
of the reaction at 68–85% conversion was the vicinal
diol when using aqueous solution of Н О (Table 1),
2
2
2
2
H O ·CO(NH ) in acetic acid the stirring rate did not
2
2
2 2
whereas the corresponding epoxides were formed when
exceed 150–200 rpm). Under those conditions, the
using the dioxane solution of Н О or Н О ·СО(NH)
fraction of Н О decomposed in the side process was
2
2
2
2
2
2
2
adduct (Table 2).
reduced, and the main products of the reaction were
the corresponding epoxides.
The alkyl radical in the molecules of alkyl
derivatives of tetracyclododecene 2–5 was located far
from the multiple bond and practically did not affect
their reactivity, as confirmed by the data given in
Tables 1–4.
The structure of the synthesized compounds was
1
13
confirmed by IR as well as Н and С NMR spec-
troscopy, elemental analysis, and determination of the
content of epoxide groups. The epoxide number [20]
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 87 No. 2 2017

EPOXIDATION OF TETRACYCLODECENE HYDROCARBONS
211
3
.6 2.7
Table 1. Oxidation of 5-R-tetracyclo[6.2.1.1 .0 ]dodec-4-ene with 30% aqueous H
2
O
2
in the presence of modified forms of
a
phosphorus-molybdenum heteropoly compound (PMHC)
Yield, %
Yield, %
Olefin
Conversion, %
Olefin
Conversion, %
epoxide
diol
epoxide
diol
b
РMYC–HBr–CoCO
3
(1 : 0.8 : 3.5)
10.5
PMHC–HBr–Gd
86/84
2 3 2 3
O /Nd O
1
2
3
4
5
90
82
78
73
68
67.6
65.4
61.0
56.0
42.0
1
2
3
4
5
16.4/15.5
18.6/18.5
23.5/22.6
19.3/18.4
13.7/12.5
74.6/75.5
70.4/72.5
66.6/68.8
58.4/60.5
54.5/57.8
12.0
83/81.6
22.4
80/81.5
16.8
76/75.4
11.6
71/70
а
b
Molar ratio olefin : Н
2
О
2
= 1 : 2, 50 mmol of olefin, 10 mL of С
2
Н
4
Сl
2
, 70°C, 6.5 h. Both catalysts were used without preliminary
treatment with hydrogen peroxide.
3
.6 2.7
Table 2. Oxidation of 5-R-tetracyclo[6.2.1.1 .0 ]dodec-4-ene with 30% dioxane solution of H
2
O
2
aand H
2 2 2 2
O ·СO(NH )
adduct in the presence of phosphorus-molybdenum heteropoly compound modified with HBr and Nd
2 3
O
Yield, %
Yield, %
epoxide
Olefin
Conversion, %
Olefin
Conversion, %
СO(NH
epoxide
diol
diol
H
2
O
2
H
2
O
2
)
2 2
1
2
3
4
5
82
78
70
65
63
65.0
10.8
9.5
1
2
3
4
87
72.5
16.0
12.0
9.0
60.0
64.0
62.0
56.0
89
86
83
69
76.5
76.0
69.0
64.0
9.3
11.6
12.5
7.0
5
6.7
а
Molar ratio olefin : Н
2
О
2
= 1 : 2, 50 mmol of olefin, 10 mL of С
2
Н
4
Сl
2
, 70°C, 6.5 h.
for compounds 6–10 was 8.5 (6), 8.3 (7), 8.2 (8), 8.3
trometer. NMR spectra were registered using a Bruker
1
(
9), 8.1 (10). Н NMR spectra of compounds 6–10
spectrometer (300.18 MHz) in CDCl with HMDS as
3
contained doublets of the oxirane fragment (2.87 ppm)
and a doublet of the terminal methyl group protons
internal reference. The composition and purity of the
reagents and products of epoxidation were monitored
by GC using a Tsvet 500 chromatograph with flame-
ionization detector, column 200×3 mm, polyethylene
glycol succinate on chromosorb (5 wt %), nitrogen as
gas carrier, column temperature 160°С, injector tem-
1
3
(
0.97 ppm) [14, 15]. С NMR spectra contained the
signals at 53.5 ppm assigned to the epoxide ring
carbons, and the signals at 18.5–14.1 ppm corres-
ponded to the carbon atom of the terminal methyl
group of alkyl chain.
perature 280°С. Concentration of Н
О was determined
2
2
by titration with permanganate.
The product obtained via oxidation of tetracyclo-
6.2.1.1 .0 ]dodec-4-ene and its methyl derivative
was tested as film-forming material without fractiona-
tion. Preliminary results showed that the produced
coatings exhibited excellent protective properties and
can be applied as thermoreactive film-forming agents.
3
.6 2.7
[
Alkylbicyclo[2.2.1]hept-2-enes were prepared as
described elsewhere [21], their physico-chemical
constants coincided with the reference data [21–23].
С –С hydrocarbons of the bridged structure were
1
2
17
synthesized via the reaction of 5-alkylbicyclo[2.2.1]-
hept-2-ene with dicyclopentadiene. The latter, in the
presence of synthetic mordenite (SiO /Al O 10, 200°C,
EXPERIMENTAL
2
2
3
IR spectra of the suspensions in Vaseline oil or KBr
pellets were recorded using an Alpha Fourier (400–
3 h), was decomposed to yield two molecules of cyclo-
pentadiene with further transformation of the mixture
of the endo- and exo-isomers (4 : 1) into individual exo-
–
1
–1
4
000 cm ) or a Vertex (Bruker) (100–700 cm ) spec-
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 87 No. 2 2017

2
12
ALIMARDANOV et al.
system at 40°С with 30% aqueous solution of Н О
Table 3. Solvent effect on the reaction of oxidation of 5-
methyltetracyclo[6.2.1.1 .0 ]dodec-4-ene in the presence
of phosphorus-molybdenum heteropoly compound modified
with HBr and Gd
2
2
3
.6 2.7
(
0.923 mol) during 24 h. The prepared complex was
introduced into the system without using of carboxylic
acids.
a
2 3
O
Selectivity, %
epoxide diol
3.6 2.7
Conversion,
%
Tetracyclo[6.2.1.1 .0 ]dodec-4-ene (1) was prepared
Solvent
ε [18]
from 13.4 g (0.1 mol) of dicycloheptadiene dimer and
9
.4 g (0.1 mol) of bicyclo[2.2.1]hept-2-ene. Yield 13.8 g
СCl
4
2.3
1.5
85
92
90
65
88
61
89
88
79
94
92
86
93
76
68
63
21
2
0
(86%), bp 215–217°С [80–82°С (0.5 kPa)], d 0.9856,
4
2
0
–1
2
С H
4
Cl
Dioxane-1,4
НСОN(CH
СН
CN
CN+H
Dioxane+H
2
6.0
n 1.4951. IR spectrum, ν, cm : 1630–1670, 3050–
D
1
4,5
3
1
7
060. Н NMR spectrum, δ, ppm: 6.1 d.d (2Н , J =
1.1, 6.4 Hz), 2.59 m (2Н ), 2.14 t (1Н, Н , J =
.2 Hz), 1.90 t (1Н, Н , J = 6.8 Hz), 1.60 m (2Н,
2.2
8.0
3
,6
12y
3
)
2
37.6
14.0
7.0
12x
1
,8
2,7
1,8
6
С Н
5
3
2.38
Н ), 1.46 m (2Н, Н ), 1.44 m (2Н, Н ), 1.35 m (2Н,
Н
J = 6.7 Hz. С NMR spectrum, δ , ppm: 136 (С ),
5
(С ), 24.9 (С ) [12–15]. Found, %: С 89.93; Н 10.08.
С Н . Calculated, %: С 89.93; Н 10.06.
9
х,10х
11у
11х
), 0.97 t (1Н, Н , J = 7.0 Hz), 0.7 t (1Н, Н ,
CH
CH
3
38.0
–
24.0
32.0
37.0
1
3
4,5
C
12
11
2,7
3,6
3
2
O (1 : 1)
3.5 (С ), 48.8 (С ), 46.7 (С ), 44.9 (С ), 40.4
1
,8
9,10
2
O (1 : 1)
–
а
Molar ratio olefin : Н
Taken as 30% solution in dioxane.
2
О
2
= 1 : 2, 15 mL of solvent, 70°С, 6 h.
12 16
b
3.6 2.7
9
-Methyltetracyclo[6.2.1.1 .0 ]dodec-4-ene (2)
was prepared from 13.4 g (0.1 mol) of dicyclo-
pentadiene and 17.4 g (0.1 mol) of 5-methylbicyclo-
isomers [24]. The dimer of cyclo-pentadiene was
isolated by vacuum distillation from the industrial
fraction (the purity of the dimer was 99.0%, GC)
[
8
2.2.1]hept-2-ene. Yield 15.5 g (89%), bp 236°С [85–
20
20
6°С (0.53 kPa)], d 0.9851, n 1.4948. IR spectrum,
4 D
–
1
1
ν, cm : 1625–1675, 3050–3060. Н NMR spectrum, δ,
ppm: 6.09 d.d (2Н , J = 11.1, 6.3 Hz), 2.60 m (2Н ),
2
6
6
Н-forms of synthetic mordenite (SiO /Al O 10)
4,5
3,6
2
2
3
were used as the condensation catalysts, after four
12y
12x
.15 t (1Н, Н , J = 7.1 Hz), 1.91 t (1Н, Н , J =
times treatment with 10% solution of NH Cl [25]. The
4
.8 Hz), 1.41–1.45 m (4Н, СН), 0.98 t (3Н, СН , J =
3
degree of decationation was 75 wt %.
11у
11х
.7 Hz), 0.93 t (1Н, Н , J = 6.8 Hz), 0.71 t (1Н, Н ,
1
3
4,5
Catalysts for epoxidation were prepared via
refluxing of aqueous solutions of (NH ) Mo O or
J = 6.6 Hz). С NMR spectrum, δ , ppm: 136 (С ),
53.5 (С ), 48.8 (С ), 46.7 (С ), 45.0 (С ), 40.5
C
1
2
11
2,7
3,6
4
6
7
24
1,8
9,10
13
(
NH ) W O (1.98 mmol), М(NO ) (М = Co, Gd,
(С ), 24.9 (С ), 18.8 (С ). Found, %: С 89.6; Н 10.56.
4
10 12 41
3 3
Nd, or Ce) (1.155 mmol), and H PO (1.155 mmol)
С Н . Calculated, %: С 89.66; Н 10.35.
3
4
13 18
during 5–6 h [26]. The solution was cooled to room
temperature, filtered, evaporated at 110–120°С, and
kept during 2–3 h at 220–250°С. The same catalyst
deposited on highly dispersed carbon material (AG-3)
was prepared similarly [27].
3.6 2.7
9
-Ethyltetracyclo[6.2.1.1 .0 ]dodec-4-ene (3)
was prepared from 13.4 g (0.1 mol) of dicyclo-
pentadiene and 18.8 g (0.1 mol) of 5-ethylbicyclo-
[2.2.1]hept-2-ene. Yield 16.2 g (86%), bp 259°С [93.6–
–1
9
5.8°C (0.26 kPa)], mp 33–35°С. IR spectrum, ν, cm :
1
Peroxometallate complexes were prepared via
stirring of the abovementioned amount of the catalytic
1623–1670, 3050–3060. Н NMR spectrum, δ, ppm:
6.1 d.d (2Н, Н , J = 11.1, J5,6 = 6.4 Hz), 2.61 m
4
,5
4
,3
3.6 2.7
2 2
Table 4. Oxidant effect on the oxidation of 9-methyltetracyclo[6.2.1.1 .0 ]dodec-4-ene with different olefin : H O molar
a
2 3
ratios in the presence of phosphorus-molybdenum heteropoly compound modified with HBr and Nd O
–
3
–1 –1
b
Initial rate of active oxygen consumption, ×10 mol L s
Selectivity, %
epoxide diol
Conversion
Oxidant
of olefin, %
1
: 0.5
1 : 1
1.28
2.14
4.23
1 : 1.5
2.13
1 : 2
3.46
4.12
6.26
Н
Н
2
2
О
О
2
2
(30% aqueous solution)
(30% dioxane solution)
0.93
1.48
2.56
42.5
85
22.5
65.0
78.4
68.4
13.5
8.3
3.86
Urea peroxide [Н
2
О
2
·СО(NH
2
)
2
]
5.76
88
а
b
Solvent – С
2
4
H Cl
2
, 70°С, 6 h. With molar ratio olefin : Н
2
О
2
= 1 : 2.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 87 No. 2 2017

EPOXIDATION OF TETRACYCLODECENE HYDROCARBONS
213
3
,6
12y
(
2Н, Н ), 2.15 t (1Н, Н , J = 7.0 Hz), 1.86 t (1Н,
in vacuum. Yield of epoxide 6 12.8 g (72.5%). mp
239°С, mp 62–64°С. IR spectrum, ν, cm : 865, 873,
1
2x
1,2,7–10,13
–1
Н , J = 6.8 Hz), 1.25–1.56 m (9Н, Н
), 0.96 t
1
1х
1
4,5
(
0
1Н, Н , J = 6.8 Hz), 0.92 t (3Н, СН , J = 7.8 Hz),
880. Н NMR spectrum, δ, ppm: 2.87 d (2Н, Н , J =
3
1
1у
13
12х,13х
12y,13y
.71 t (1Н, Н , J = 6.6 Hz). С NMR spectrum, δ ,
ppm: 136 (С ), 53.1 (С ), 46.7 (С ), 41.7 (С ), 40.2
С ), 33.8 (С ), 29.3 (С ), 12.2 (С ). Found, %: С
9.3; Н 10.5. С Н . Calculated, %: С 89.08; Н 10.61.
7.2 Hz), 2.15 q (2Н, Н
1.25–1.77 m (10Н, Н
δ , ppm: 53.4 (С ), 48.1 (С ), 41.3 (С ), 41.4 (С ),
), 1.89 q (2Н, Н
),
С
4,5
12
2,7
9
1,2,3,8,9,10,11
2,8
13
). С NMR spectrum,
1
,8
10
11,13
14
4,6
3,7
12
(
8
C
1,9
10,11
39.9 (С ), 25.5 (С ). Found, %: С 81.86; Н 9.12.
С Н О. Calculated, %: С 81.82, Н 9.09.
1
4
20
3
.6 2.7
1
2
16
9
-Propyltetracyclo[6.2.1.1 .0 ]dodec-4-ene (4)
was prepared from 13.4 g (0.1 mol) of dicyclo-
pentadiene and 13.6 g (0.1 mol) of 5-propylbicyclo-
2.2.1]hept-2-ene. Yield 16.4 g (81%), bp 281°С
112.5–114.3°С (0.27 kPa)], mp 44–46°С. Н NMR spec-
trum, δ, ppm: 6.08 d.d (2Н, Н , J = 11.1, J =
.4 Hz), 2.60 m (2Н, Н ), 2.15 t (1Н, Н , J =
.1 Hz), 1.87 t (1Н, Н , J = 6.7 Hz), 1.25–1.51 m
11Н, Н
3
.7 4.6 2.8
10-Methyl-5-oxapentacyclo[6.2.1.1 .0 .0 ]tri-
decane (7) was prepared similarly from 17.4 g of com-
pound 2. Yield 14.5 g (76.5%). mp 257°С, mp 68–71°С.
[
[
1
–1
1
IR spectrum, ν, cm : 865, 873, 880. Н NMR spec-
4
,5
4,6
trum, δ, ppm: 2.89 d.d (2Н, Н , J = 7.2 Hz), 2.15 q
4,3
5,6
3
,6
12y
12х,13х
12y,13y
13
6
7
(
(2Н, Н
Н
), 1.89 q (2Н, Н
), 0.97 d (3Н, СН ). С NMR spectrum, δ ,
3 C
); 1.25–1.76 m (9Н,
1
2x
1–3,7–11
1,2,7–10, 13,14
11х
4 6
8
2
1
), 0.97 t (1Н, Н , J = 6.8 Hz), 0.93
ppm: 53.4 (С , ), 50.8 (С ), 48.2 (С ), 45.1 (С ), 42.3
(С ), 41.6 (С ), 41.4 (С ), 38.8 (С ), 28.9 (С ), 27.1
(С ), 18.5 (С ). Found, %: С 82.16; Н 9.51. С13
Calculated, %: С 82.15; Н 9.47.
1
1у
9
7
3
11
12
t (3Н, СН , J = 7.8 Hz), 0.71 t (1Н, Н , J = 6.6 Hz).
3
1
3
4,5
12
11
14
С NMR spectrum, δ , ppm: 135.8 (С ), 53.2 (С ),
Н18О.
С
7
2
6
8
1
4
3
1
8.2 (С ), 46.8 (С ), 45.1 (С ), 40.5 (С ), 38.1 (С ),
9
10
11
13
14
3
.7 4.6 2.8
5.0 (С ), 34.1 (С ), 29.3 (С ), 23.9 (С ), 23.3 (С ),
1
0-Ethyl-5-oxapentacyclo[6.2.1.1 .0 .0 ]tri-
1
5
4.4 (С ). Found, %: С 89.11; Н 10.93. С Н . Cal-
15 22
decane (8) was prepared similarly from 18.9 g of
compound 3. Yield 15.6 g (76%), bp 280°С [109.5–
culated, %: С 89.91; Н 10.9.
–
1
3
.6 2.7
1
8
11.7°С (0.26 kPa)], mp 80–82°С. IR spectrum, ν, cm :
9
-Butyltetracyclo[6.2.1.1 .0 ]dodec-4-ene (5)
1
65, 873, 880. Н NMR spectrum, δ, ppm: 2.89 d (2Н,
was prepared from 13.4 g (0.1 mol) of dicyclo-
pentadiene and 15 g (0.1 mol) of 5-butylbicyclo[2.2.1]-
hept-2-ene. Yield 16.9 g (78.6%), bp 305°С [125.2–
26.8°С (0.27 kPa)], mp 56–58°С. IR spectrum, ν, cm :
635–1675, 3045–3070. Н NMR spectrum, δ, ppm:
4
,6
12х,13х
Н , J = 7.2 Hz), 2.15 q (Н
, J = 7.1 Hz), 1.89 q
6,7
2y,13y
1
1–3,7–11,14,15
(
Н
, J = 6.9 Hz), 1.23–1.76 m (13Н, Н
),
1
3
–1
0
.97 t (3Н, СН , J = 7.0 Hz). С NMR spectrum, δ ,
1
1
6
3
С
4
,6
8
2
1
1
ppm: 53.4 (С ), 51.1 (С ), 48.4 (С ), 45.4 (С ), 41.6
), 41.4 (С ), 39.8 (С ), 33.7 (С ), 29.3 (С ), 29.3
С ), 27.1 (С ), 12.2 (С ). Found, %: С 82.38; Н
7
1
,10
4
3
9
11
12
4
,5
(
(
С
.09 d (2Н, Н , J = 11.1, J5,6 = 6.4 Hz), 2.56 m (2Н,
Н ), 2.11 t (1Н, Н , J = 6.8 Hz), 1.86 t (1Н, Н ,
4
,3
13
15
3
,6
12х
12у
1
,2,7–10,13–15
9
.85. С Н О. Calculated, %: С 82.36; Н 9.81.
J = 7.0 Hz), 1.23–1.52 m (13Н, Н
), 0.96 t
14 20
1
1х
3.7 4.6 2.8
(
0
1Н, Н , J = 6.8 Hz), 0.92 t (3Н, СН , J = 7.8 Hz),
10-Propyl-5-oxapentacyclo[6.2.1.1 .0 .0 ]tri-
3
1
1у
13
.70 t (1Н, Н , J = 6.6 Hz). С NMR spectrum, δ ,
ppm: 136.0 (С ), 53.2 (С ), 48.2 (С ), 46.8 (С ), 45.1
С ), 44.8 (C ), 40.5 (С ), 38.1 (С ), 35.4 (С ), 34.2
decane (9) was prepared similarly from 20.2 g (0.1 mol)
of compound 4. Yield 15.0 g (69%), bp 303°С [123.5–
С
4
,5
12
7
2
6
3
8
1
9
–1
(
(
1
125.6°С (0.21 kPa)], mp 89–91°С. IR spectrum, ν, cm :
1
0
14
11
13
14
1
С ), 30.0 (C ), 29.3 (С ), 28.2 (C ), 23.0 (С ),
865, 873, 880. Н NMR spectrum, δ, ppm: 2.89 d (2Н,
1
5
4,6
12х,13х
4.2 (С ). Found, %: С 89.91; Н11.09. С Н . Cal-
Н , J = 7.3 Hz), 2.15 q (2Н, Н
, J = 7.1 Hz),
1
6
24
4,3
1
2y,13y
culated, %: С 88.89; Н 11.12.
1.89 q (2Н, Н
, J = 6.9 Hz), 1.23–1.76 m (15Н,
), 0.97 t (3Н, СН , J = 7.0 Hz). С NMR,
1
–3,7–11,14,15
13
3
.7 4.6 2.8
Н
3
5
-Oxapentacyclo[6.2.1.1 .0 .0 ]tridecane (6).
.05 mol of acetic acid was added to a mixture of 16.0 g
0.1 mol) of compound 1 and 8 g of H O ·CO(NH )
2 2
adduct (active oxygen content 30%) in 50 mL of
toluene or dichloroethane with 0.102 g of the catalyst.
The mixture was stirred of 70°C, during 6 h. The
completion of the reaction was determined by GC. The
reaction mixture was treated with saturated solution of
4
,6
8
2
1
δ , ppm: 53.4 (С ), 51.1 (С ), 48.4 (С ), 45.4 (С ),
С
0
(
3
9
10
11
12
4
2
1.4 (С ), 40.1 (С ), 34.9 (С ), 34.0 (С ), 29.3 (С ),
7.1 (С ), 23.9 (С ), 23.3 (С ), 14.4 (С ). Found, %:
2
2
13
14
15
16
С 82.51; Н 10.16. С Н О. Calculated, %: С 82.87; Н 10.1.
15 22
3
.7 4.6 2.8
10-Butyl-5-oxapentacyclo[6.2.1.1 .0 .0 ]tri-
decane (10) was prepared similarly from 21.6 g
(0.1 mol) of compound 5. Yield 14.0 g (69%), bp 326°С
[137.6–139.3°С (0.21 kPa)], mp 101–103°С. IR
NaHCO , the organic layer was separated, and the
3
–
1
1
aqueous layer was extracted with toluene or dichloro-
ethane. The organic extracts were dried with MgSO4,
the solvent was removed, and the residue was distilled
spectrum, ν, cm : 865, 873, 880. Н NMR spectrum,
4,6
δ, ppm: 2.89 d (2Н, Н , J6,7 = 7.3 Hz), 2.15 q (2Н,
1
2х,13х
12y,13y
Н
, J = 7.0 Hz), 1.89 q (2Н, Н
, J = 6.9 Hz),
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 87 No. 2 2017

2
14
.23–1.77 m (17Н, Н
ALIMARDANOV et al.
1
–3,7–11,14–16
17
1
), 0.92 t (3Н , СН ,
for the Perfume and Household Chemicals), Moscow:
Pishchevaya Pro–st’, 1994.
9. Kashkovskii, V.I. and Grigor’ev, A.A., Katal.
Neftekhim., 2006, no. 14, p. 1.
3
1
3
4,6
J = 7.8 Hz). С NMR spectrum, δ , ppm: 53.4 (С ),
5
3
С
8
2
1
3
9
1.1 (С ), 48.4 (С ), 45.4 (С ), 41.4 (С ), 40.1 (С ),
1
0
11
15
12
5.2 (С ), 34.0 (С ), 29.9 (С ), 29.3 (С ), 28.3
1
4
13
16
17
1
0. Garibov, N.I., Alimardanov, Kh.M., Dadashova, N.R.,
Sadigov, O.A., Almardanova, M.B., and Kuliev, A.D.,
Russ. J. Gen. Chem., 2015, vol. 85, no. 5, p. 1025. doi
(
С ), 27.1 (С ), 23.0 (С ), 14.1 (С ). Found, %: С
8
1
2.73; Н 10.37. С Н О. Calculated, %: С 82.76; Н
16 24
0.35.
Tetracyclo[6.2.1.1 .0 ]dodeca-4.5-diol (11) was
prepared from 16.0 g of compound 1. Yield 14.6 g
1
0.1134/S1070363215050035
3
.6 2.7
1
1. Alimardanov, Kh.M., Sadygov, O.A., Dzhalilova, A.A.,
and Almardanova, M.B., Az. Khim. Zh., 2015, no. 3,
p. 67.
–
1
(
75%), mp 126–128°С. IR spectrum, ν, cm : 818, 974,
1
1
100, 3615, 3625. Н NMR spectrum, δ, ppm: 3.60 br.s
12. Nakanishi, K., Infrared Absorption Spectroscopy, San
4
,5
11х,12х
(
2Н, ОН); 3.25 t (2Н, Н ), 2.15 q (2Н, Н
), 1.90
Francisco: Practical-HoldenDay, 1964.
1
1у,12у
1–3,6–10 13
q (2Н, Н
), 1.25–1.61 m (9Н, Н
). С NMR
13. Kas’yan, L.I., Okovityi, S.I., Bambushkar, M.F., and
Dryuk, V.G., Russ. J. Org. Chem., 2000, vol. 36, no. 2,
p. 195.
4
,5
2,7
spectrum, δ ppm: 79.7 (С ), 46.2 (С ), 41.8
C,
3
,6,12
1,8
9,10
(
С
), 40.5 (С ), 25.6 (С ). Found, %: С 74.26; Н
9
.31. С Н О . Calculated, %: С 74.23; Н 9.28.
14. Gordon, A.J. and Ford, R.A., The Chemist’s Com-
panion. A Handbook of Practical Data, Techniques and
References, New York: Wiley, 1972.
1
2
18
2
3
.6 2.7
9
-Methyltetracyclo[6.2.1.1 .0 ]dodeca-4.5-diol
(
12) was prepared from 17.4 g compound 2. Yield 15.1 g
1
5. Ionin, B.I. and Ershov, B.A., NMR Spectroscopy in
Organic Chemistry, Leningrad: Khimia, 1967.
–
1
(
72.5%), mp 131–133°С. IR spectrum, ν, cm : 820,
1
8
3
q (Н
74, 1100, 3615, 3625. Н NMR spectrum, δ, ppm:
1
6. Timofeev, M.N., Pai, Z.P., Tolstikov, A.G., Kustova, G.N.,
Selivanova, N.V., Berdnikova, P.V., Brylyakov, K.P.,
Shangina, A.B., and Utkin, V.A., Russ. Chem. Вull.,
2003, no. 2, p. 480. doi 10.1023/A:1023495824378
4
,5
11х,12х
.60 br. s (2Н, ОН), 3.25 t (Н ), 2.16 q (Н
), 1.90
1
1у,12у
1–3,6,7,9,10
), 1.25–1.61 m (9Н, Н
), 0.97 t (3Н,
1
3
4,5
СН ). С NMR spectrum, δ , ppm: 79.7 (С ), 46.2
3
,7
C
1,8
2
3,6,12
9,10
13
(
С ), 41.8 (С
), 40.5 (С ), 25.6 (С ), 18.6 (С ).
17. Moelwyn Hughes, E.A., The Chemical Statics and
Kinetics of Solutions, London: Academic Press, 1971.
18. Reinhardt, C., Solvent Effects in Organic Chemistry,
Wienheim: Verlag Chemie, 1979.
Found, %: С 74.95; Н 9.66. С Н О . Calculated, %:
С 75.0; Н 9.62.
1
3
20
2
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1
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2
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8
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 87 No. 2 2017