Products of ozone oxidation of some saturated cyclic hydrocarbons

Article abstract of DOI:10.1134/S1070428015120076

Low-temperature ozone oxidation of a series of saturated carbocyclic hydrocarbons afforded the corresponding alcohols and/or ketones in high yield through intermediate trioxidanes. exo,endo-Tetracyclo-[6.2.1.0^3,5]undecane-2,7-dione and exo,endo,endo-hexacyclo[9.3.1.0^3,8.0^4,6.0^5,9.0^12,14]pentadecane-2,10-dione were isolated, and exo,endo,exo-pentacyclo[6.3.1.0^2,7.0^3,5.0^9,11]dodecyl-, exo,exo,exo-heptacyclo-[9.3.1.0^2,10.0^3,8.0^4,6.0^5,9.0^12,14]pentadecyl, and 1-methylcyclohexyltrioxidanes were identified and characterized for the first time.

Full text of DOI:10.1134/S1070428015120076

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2015, Vol. 51, No. 12, pp. 1710–1716. © Pleiades Publishing, Ltd., 2015.
Original Russian Text © L.R. Khalitova, S.A. Grabovskiy, A.V. Antipin, L.V. Spirikhin, N.N. Kabal’nova, 2015, published in Zhurnal Organicheskoi Khimii,
2015, Vol. 51, No. 12, pp. 1744–1750.
Products of Ozone Oxidation of Some Saturated
Cyclic Hydrocarbons
L. R. Khalitova, S. A. Grabovskiy, A. V. Antipin, L. V. Spirikhin, and N. N. Kabal’nova
Ufa Institute of Chemistry, Russian Academy of Sciences, pr. Oktyabrya 71, Ufa, 450054 Bashkortostan, Russia
e-mail: chemox@anrb.ru
Received July 21, 2015
Abstract—Low-temperature ozone oxidation of a series of saturated carbocyclic hydrocarbons afforded the
corresponding alcohols and/or ketones in high yield through intermediate trioxidanes. exo,endo-Tetracyclo-
[6.2.1.03,5]undecane-2,7-dione and exo,endo,endo-hexacyclo[9.3.1.03,8.04,6.05,9.012,14]pentadecane-2,10-dione
were isolated, and exo,endo,exo-pentacyclo[6.3.1.02,7.03,5.09,11]dodecyl-, exo,exo,exo-heptacyclo-
[9.3.1.02,10.03,8.04,6.05,9.012,14]pentadecyl, and 1-methylcyclohexyltrioxidanes were identified and characterized
for the first time.
DOI: 10.1134/S1070428015120076
Oxygen-containing derivatives of polycyclic hydro-
carbons attract much interest as potential biologically
active substances. Saturated polycyclic hydrocarbons
have found wide application in the manufacture of
multipurpose propellants [1] which undergo oxidation
on storage; therefore, studies of their oxidative trans-
formations by the action of various oxidants are also
topical. Ozone is a popular oxidant which is widely
used to obtain oxygen-containing organic compounds.
However, room temperature ozonolysis is insuffi-
ciently selective. The selectivity of ozonolysis both in
solution and on silica surface can be improved by
reducing the reaction temperature to –30°C and lower.
As a rule, low-temperature ozonation of cyclic hydro-
carbons and alkanes on silica gel is characterized by
high conversion, significant selectivity, and complete
retention of configuration [2–6].
was carried out on silica surface when the substrate
solubility was low or the reaction in solution was slow.
The oxidation of 1a with ozone was selective only on
silica surface, and the product was exo,endo-tetra-
cyclo[6.2.1.02,7.03,5]undecan-2-ol (1c); in addition,
exo,endo-tricyclo[6.2.1.03,5]undecane-2,7-dione (1d)
was formed as a result of cleavage of the C2–C7 bond.
Compound 2a was oxidized both in solution and on
silica surface. Unlike low-temperature ozonation in
methylene chloride, the oxidation on silica surface was
fast and selective with formation of exo,endo,exo-
pentacyclo[6.3.1.02,7.03,5.09,11]dodecan-2-ol (2c). The
ozonation of 3a both on silica surface and in solution
g a v e t h e C 2 – C 1 0 b o n d c l e a v a g e p r o d u c t,
exo,endo,endo-hexacyclo[9.3.1.03,8.04,6.05,9.012,14]-
pentadecane-2,10-dione (3c). The structures of 2c and
3c were determined by X-ray analysis (Figs. 1, 2).
In this work we studied intermediates and products
of low-temperature ozonation of exo,endo-tetracyclo-
[6.2.1.02,7.03,5]undecane (1a), exo,endo,exo-pentacyclo-
[6.3.1.02,7.03,5.09,11]dodecane (2a), exo,endo,endo-
hexacyclo[9.3.1.02,10.03,8.04,6.05,9.012,14]pentadecane
( 3 a ) , e x o , e x o , e x o - h e p t a c y c l o-
[9.3.1.02,10.03,8.04,6.05,9.012,14]pentadecane (4a),
methylcyclohexane (5a), and bicyclo[4.1.0]heptane
(6a) in solution and on silica surface, the correspond-
ing alkyltrioxidanes (ROOOH) 1b–6b and alcohols
and/or ketones.
The oxidation of 4a occurred at an appreciable rate
only on silica surface at –35°C to afford exo,exo,exo-
heptacyclo[9.3.1.02,10.03,8.04,6.05,9.012,14]pentadecan-2-
ol (4c). As reported in [1], the oxidation of 3a and 4a
with dimethyl- and methyl(trifluoromethyl)dioxirane
(CCl4, 20°C) gave the corresponding alcohols in high
yields [1]. The ozonation of methylcyclohexane (5a)
on silica surface was described in [3]; therefore, we
examined its oxidation in solution. In both cases, the
final product was 1-methylcyclohexan-1-ol (5c).
A mixture of the corresponding alcohol and ketone,
bicyclo[4.1.0]heptan-2-ol (7a) and bicyclo[4.1.0]-
heptan-2-one (7c), was obtained in the oxidation of 6a
The oxidation of compounds 1a–6a with ozone was
characterized by high yields (Table 1). The oxidation
1710

PRODUCTS OF OZONE OXIDATION
Table 1. Ozonation of cyclic hydrocarbons 1a–6a at –78°C
1711
4
11
12
8
15
15
7
2
2
10
9
5
Me
4
4
5
1
1
1
1
11
13
3
4
3
3
3
13
9
3
1
8
8
9
3
1
14
8
4
14
5
5
1a
2a
3a
4a
5a
6a
Comp.
no.
Ozonation
time, min
Sorbent
or solvent
Conversion, %
ROOOH
Final product
Yield,a %
OOOH
OH
82
1b
1c
1a
050
SiO2
100
O
18
O
1d
OOOH
OH
2a
3a
120
090
120
CH2Cl2
SiO2
070
080
098
56
61
60
SiO2
2b
OOOH
2c
O
060
120
110
CH2Cl2
CH2Cl2
SiO2
050
098
098
70
82
80
O
3b
3c
4ab
5a
230
060
SiO2
040
060
98
OOOH
OH
4b
4c
Me
Me
OH
OOOH
t-BuOMe
98
5b
5c
H
OH
OOOH
05 [7]
92 [7]
6b
7a
6a
075
t-BuOMe
098
OH
OOOH
O
7b
7c
a
Based on the reacted substrate.
At –35°C.
b
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 51 No. 12 2015

KHALITOVA et al.
1712
C6
C1
C12
C5
C10
C7
C2
O1
C8
C9
C10A
C5
C2A
C2
C6
C3
C5A
C4
C8
C1
C6A
C3A
C4
C3
C9
C10
C7
C11
O1
O1A
Fig. 1. Structure of the molecule of exo,endo,exo-pentacyclo-
[6.3.1.02,7.03,5.09,11]dodecan-2-ol (2c) according to the X-ray
diffraction data.
Fig. 2. Structure of the molecule of exo,endo,endo-hexa-
cyclo[9.3.1.03,8.04,6.05,9.012,14]pentadecane-2,10-dione (3c)
according to the X-ray diffraction data.
with ozone in solution [7]. In all cases, the oxidation
involved the weakest tertiary C–H bond (Table 2),
which suggests a mechanism involving abstraction of
hydrogen. Among carbocycles 1a–6a, the reacting
C2–H bond in 4a is the strongest (ECH = 93.0 kcal×
mol–1), which is responsible for the low reactivity of
4a. Cleavage of the C2–C10 bond in 3a and retention of
the corresponding bond in exo,exo,exo isomer 4a may
be accounted for by the higher strength of that bond
in the latter [by 6.4 kcal/mol according to B3PW91/
6-31+G(d) calculations].
Table 2. Energies of dissociation of C–H bonds in mole-
cules 1a–6a, calculated by the DFT/(U)B3PW91/6-31+G(d)
method
Comp.
no.
EC–H, kcal/mol (atom number)
As a rule, ozonation of saturated organic com-
pounds involves intermediate formation of trioxidanes.
We were the first to identify by NMR spectroscopy
three new trioxidanes 2b, 4b, and 5b. The low-tem-
1a
2a
3a
4a
101.1 (1), 88.4 (2), 101.8 (3), 102.9 (4), 102.7
(5), 89.5 (6), 91.8 (7), 100.9 (8), 91.9 (9), 92.5
(10), 99.2 (11)
1
perature H NMR spectra (–40°C, CFCl3–acetone-d6)
100.1 (1), 88.4 (2), 101.9 (3), 102.9 (4), 102.6
(5), 90.2 (6), 92.7 (7), 100.0 (8), 102.4 (9),
102.3 (10), 103.4(11), 97.6 (12)
of the reaction mixtures displayed a multiplet in the
region δ 11.5–14 ppm, which was assigned to the
OOOH proton. The signal disappeared when the tem-
perature rose to ambient (Table 3). Broadening of that
signal in the spectra of 2b and 4b is likely to be related
to specific solvation of trioxidanes with acetone to
form stronger solvate shells which stabilize different
trioxidane associates [8]. In the ozonation of 1a and
3a, diketones 1d and 3c may be formed via decom-
position of bis-trioxidanes (Scheme 1).
99.9 (1), 89.7 (2), 99.2 (3), 105.1 (4), 107.5 (5),
104.6 (8), 95.0 (9), 102.1 (13), 103.8 (14), 96.6
(15)
100.6 (1), 93.0 (2), 99.4 (3), 106.4 (4), 107.5 (5),
103.2 (8), 95.1 (9), 101.9 (13), 103.7 (14), 94.0
(15)
5a
6a
90.1 (1), 93.3 (2), 93.0 (3), 93.1 (4), 96.8 (Me)
98.8 (1) 88.7 (2) 91.5 (3) 102.7 (7)
It is known that many oxidation processes are
accompanied by chemiluminescence which provides
information on both emission source and reaction
kinetics. We determined kinetic parameters of thermal
decomposition of trioxidanes 5b and 6b in tert-butyl
methyl ether by the IR chemiluminescence (IR-CL)
method. Here, singlet oxygen acts as emitter. Com-
pounds 1b–4b showed no chemiluminescence in the
IR region. The IR-CL decay curves for 5b and 6b are
well described by first-order equations. The effective
rates of decomposition (kd) were calculated from the
Table 3. Chemical shifts of the OOOH proton in alkyltri-
oxidanes 2b, 4b, and 5b
Comp. no.
Solvent
δOOOH, ppm
2b
4b
5b
Acetone-d6–CFCl3, 1:1
Acetone-d6–CFCl3, 1:1
Toluene-d8–CFCl3, 1:1
11.7–13.7 m
12.6–13.0 m
13.60 br.s
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 51 No. 12 2015

PRODUCTS OF OZONE OXIDATION
1713
Scheme 1.
H
OOOH
OOOH
OOOH
O3
O3
H
H
·
O
O
O
·
HOO
OOOH
OOOH
O
+
·
–HOO
·
≠
OH
O
O
O
O
H
O
O
+ O2 + H2O2
O
Scheme 2.
OH
H
O
O
OH
O3, –78°C
O3, –78°C
O
+
6a
H
O
OH
endo-6b
exo-6b
7a
OH
OH
O
O
O
O3
O
+
+
HOOOH
OH
O
OH
endo-7b
exo-7b
7c
semilog CL decay plots (Table 4), and the obtained
data were used to calculate the activation parameters.
singlet oxygen in the decomposition of 5b does not
exceed 1%, which is consistent with the data obtained
previously for other alkyltrioxidanes. For example, the
1
logk5b = (3.5±0.3) – (26.8±0.7)/2.3RT;
yield of O2 from adamantyltrioxidane is 7.2%
logk7b = (11.9±0.9) – (81.7±1.9)/2.3RT (kJ/mol).
Table 4. Effective rate constants (kd) for the decomposition
of trioxidanes 5b–7b (t-BuOMe; c5b = 3.1×10–2, c6b = c7b
=
The IR-CL decay curve for the low-temperature
ozonation of 6a consists of two parts, which may be
rationalized assuming the presence of two trioxidanes,
6b (endo,exo) and 7b (endo,exo), since the rate of
ozonation of alcohols is much higher than the rate of
ozonation of hydrocarbons [9] (Scheme 2). Compar-
ison of the rate constants for the decomposition of 6b,
calculated from the IR-CL decay curve by the first-
order equation (Table 4), with published data [7] led us
to conclude that the first (fast) part of the IR-CL decay
curve corresponds to the decomposition of alkyltriox-
idane 6b, and the second (slow), to the decomposition
of trioxidanyl alcohol 7b.
3.36×10–2 M)
Comp.
no.
Temperature,
°C
kd ×102, s–1 kd ×102, s–1 [7]
0–9.0–
00.0
10.0
20.0
00.0
10.0
20.0
00.0
10.0
20.0
1.8±0.2
3.2±0.3
–
5b
–
4.7±0.4
–
6.3±0.6
–
6b
7b
1.5±0.2
0.5±0.05
1.5±0.10
2.9±0.20
0.05±0.005
0.19±0.020
0.75±0.070
2.1±0.2
3.5±0.3
00.03±0.003
00.08±0.008
0.24±0.02
The observed chemiluminescence in the IR region
suggests formation of singlet oxygen (1O2) in the
decomposition of trioxidanes 5b and 6b. The yield of
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 51 No. 12 2015

KHALITOVA et al.
1714
(–3.0°C, CH2Cl2), and from decahydronaphthalen-4a-
yltrioxidane, 1.2% (6.0°C, CH2Cl2) [8]. The overall
yield of singlet oxygen in the decomposition of mix-
ture 6b/7b is 15.2% (20°C, t-BuOMe), and the major
contribution is that of 7b.
1.4 mmol) or 3a (0.13 g, 0.6 mmol) in 3 mL of
methylene chloride or of 5a (0.2 mL, 1.6 mmol) or 6a
(0.2 mL, 2 mmol) in 10 mL of tert-butyl methyl ether,
maintained at –78°C.
b. Ozonation on silica surface. Compound 1a
(0.15 mL, 1.1 mmol), 2a (0.2 mL, 1.4 mmol), 3a
(0.26 g, 1.3 mmol), or 4a (0.12 g, 0.6 mmol), was dis-
solved in 15 mL of pentane, the solution was added to
3 g of freshly calcined silica gel under vigorous stir-
ring, and the solvent was evaporated [16]. The sorbent
was placed into a reactor, the reactor was cooled to
a required temperature, and a cold ozone/oxygen mix-
ture was supplied thereto.
In summary, we have found conditions for efficient
ozonation of cyclic hydrocarbons 1a–6a. The reaction
involves the weakest C–H bond with intermediate
formation of the corresponding trioxidanes. The oxida-
tion of 1a and 3a with ozone is accompanied by
decomposition of the carbon skeleton and formation of
previously unknown diketones 1d and 3c.
EXPERIMENTAL
Excess ozone was removed from the solution or
silica surface by purging with oxygen. In both cases,
the amount of absorbed ozone was determined by
spectrophotometry [17]. The products were eluted
from silica with cold acetone, and the concentration of
trioxidanes 1b–6b was determined as described in
[18]. The solution was then allowed to warm up to
room temperature to obtain final products.
The spectral and analytical data were obtained at
the Khimiya Joint Center, Ufa Institute of Chemistry,
1
Russian Academy of Sciences. The H and 13C NMR
spectra were recorded on a Bruker AM-300 spectrom-
eter at 300 and 75.47 MHz, respectively, using tetra-
methylsilane as internal standard. Chromatographic
analysis was performed on a Chrom-5 gas chromato-
graph (5 m×3-mm column, stationary phase SE-30,
oven temperature 50–270°C, carrier gas helium). The
mass spectra were recorded on a Finnigan MAT GCQ
GC/MS System (DB-5MS column, 30 m×0.25 m, film
thickness 0.25 μm; carrier gas helium). The elemental
compositions were determined on an EA-300 CHNS-
analyzer (HEKA-Tech).
The kinetics of decomposition of trioxidanes 1b–6b
were studied by the IR-CL method [17] in the tempera-
ture range from –9 to 20°C. A 10-mL reactor main-
tained at a constant temperature was charged with 1–
2 mL of tert-butyl methyl ether, and 0.5–1.5 mL of
a solution of ROOOH (0.012–0.049 M) was quickly
added. After thermal equilibration, the kinetics of
chemiluminescence decay were measured. The chemi-
luminescence setup was calibrated against triphenyl
phosphite ozonide with a known yield of singlet
oxygen (F = 1.0) [19]. The yield of singlet oxygen in
the thermolysis of trioxidanes was calculated as de-
scribed in [20].
exo,endo-Tetracyclo[6.2.1.02,7.03,5]undecan-2-ol
(1c). Yield 82%. 13C NMR spectrum (CDCl3), δC, ppm:
10.89 (C5), 21.38 (C6), 21.84 (C4), 22.87 (C9), 26.60
(C10), 28.73 (C3), 40.61 (C11), 41.73 (C8), 49.00 (C1),
55.80 (C7), 92.00 (C2). Found, %: C 80.42; H 9.88.
C11H16O. Calculated, %: C 80.44; H 9.82.
Quantum-chemical calculations were performed
using a combination of the Becke three-parameter
hybrid exchange functional (B3) [10, 11] and PW91
correlation functional [12] (B3PW91) and standard
6-31+G(d) basis set [13]. All geometric parameters of
molecules and radical species were optimized at the
B3PW91/6-31+G(d) level of theory without symmetry
restrictions. The optimized structures were localized
on the potential energy surface by analysis of the
corresponding Hessian eigenvalues. The energies were
corrected for zero-point vibration energy calculated by
the DFT/B3PW91/6-31+G(d) method. The thermody-
namic parameters were calculated for 298 K and 1 atm.
All calculations were performed at the Khimiya Joint
Center using NW Chem Ver. 5 software package [14].
exo,endo-Tetracyclo[6.2.1.03,5]undecane-2,7-di-
13
one (1d). Yield 18%. C NMR spectrum (CDCl3), δC,
ppm: 9.87 (C5), 17.10 (C4), 26.91 (C10), 28.05 (C9),
30.81 (C6), 36.66 (C3), 41.00 (C11), 51.34 (C1), 53.16
(C8), 212.4 (C7), 213.4 (C2). Found, %: C 74.15;
H 7.93. C11H14O2. Calculated, %: C 74.13; H 7.91.
General procedure for low-temperature ozona-
tion. Ozone was generated in a conventional ozonizer
[15]. Silica gel (Lancaster, 0.06–0.2 mm) was calcined
at 300–350°C. All solvents were dried by standard
procedures and distilled before use.
exo,endo,exo-Pentacyclo[6.3.1.02,7.03,5.09,11]do-
decan-2-ol (2c). 13C NMR spectrum (CDCl3), δC, ppm:
3.32 (C10), 9.38 (C9), 10.36 (C11), 10.41 (C4), 22.91
a. Ozonation in solution. A cold ozone/oxygen mix-
ture was passed through a solution of 2a (0.2 mL,
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 51 No. 12 2015

PRODUCTS OF OZONE OXIDATION
1715
(C3), 25.92 (C5), 27.65 (C6), 28.28 (C12), 39.98 (C8),
47.85 (C1), 57.08 (C7), 93.21 (C2). Mass spectrum, m/z
(Irel, %): 176 (0.3) [M]+, 158 (0.6), 147 (0.8), 133 (1.6),
121 (1.8), 117 (2.2), 115 (3.2), 107 (2.2), 97 (10.3), 96
(100), 95 (52.4), 91 (10.5), 81 (23.5), 80 (9.3), 79
(20.7), 78 (7.3), 77 (20.3), 67 (17.8), 55 (12.6), 53
(9.7). Found, %: C 81.76; H 9.17. C12H16O. Calculat-
ed, %: C 81.77; H 9.15. M 176.26.
Final divergence factors: wR2 = 0.1913 (all indepen-
dent reflections), R1 = 0.0983 [4653 reflections with
I > 2σ(I)]; goodness of fit 0.902.
Compound 3c. C15H16O2; M 228.28; orthorhombic
crystal system, space group P21/mn; unit cell param-
eters [293(2) K]: a = 9.218(5), b = 6.148(3), c =
9.907(5) Å; V = 561.4(5) Å3; Z = 2; dcalc = 1.350 g×
cm–3. Total of 4017 reflection intensities were mea-
sured from a 0.4×0.3×0.2-mm colorless single crystal.
Final divergence factors wR2 = 0.0962 (all independent
reflections), R1 = 0.0477 [1226 reflections with I >
2σ(I)]; goodness of fit 0.960.
exo,endo,endo-Hexacyclo[9.3.1.03,8.04,6.05,9.012,14]-
1
pentadecane-2,10-dione (3c). H NMR spectrum
(acetone-d6), δ, ppm: 0.20 d.t (1H, 13-H, J = 3.81,
3.77 Hz), 0.70 d.t (1H, 13-H, J = 8.22, 8.20 Hz),
1.30 d.t (1H, 6-H, J = 1.04, 5.54 Hz), 1.38 m (2H,
7-H), 1.42–1.50 m (1H, 15-H), 1.85–1.93 m (4H, 4-H,
5-H, 12-H, 14-H), 2.02–2.10 m (2H, 8-H, 15-H), 2.50–
2.55 m (2H, 3-H, 9-H), 2.90–3.00 m (2H, 1-H, 11-H).
13C NMR spectrum (acetone-d6), δC, ppm: 7.13 (C13),
10.63 (C6), 15.18 (C4, C5), 21.63 (C12, C14), 31.15
(C15), 36.80 (C7), 42.26 (C8), 54.39 (C1, C11), 58.92
(C3, C9), 213.18 (C2, C10). Found, %: C 78.91; H 7.08.
C15H16O2. Calculated, %: C 78.92; H 7.06.
The authors thank Prof. V.A. Dokichev (Head of
Organometallic Synthesis and Catalysis Laboratory,
Ufa Institute of Chemistry, Russian Academy of
Sciences) for providing compounds 1a–4a and
Dr. I.V. Fedyanin (Institute of Organoelement Com-
pounds, Russian Academy of Sciences) for his help in
performing the X-ray analysis.
REFERENCES
The spectral parameters of exo,exo,exo-heptacyclo-
[9.3.1.02,10.03,8.04,6.05,9.012,14]pentadecan-2-ol (4c),
1-methylcyclohexan-1-ol (5c), bicyclo[4.1.0]heptan-2-
ol (7a), and bicyclo[4.1.0]heptan-2-one (7c) were con-
sistent with published data [1, 7, 21–29].
1. Grabovskiy, S.A., Antipin, A.V., Ivanova, E.V.,
Dokichev, V.A., Tomilov, Y.V., and Kabal’nova, N.N.,
Org. Biomol. Chem., 2007, vol. 5, p. 2302.
2. Tal, D., Keinan, E., and Mazur, Y., J. Am. Chem. Soc.,
1979, vol. 101, p. 502.
3. Cohen, Z., Keinan, E., Mazur, Y., and Varkony, T.,
J. Org. Chem., 1975, vol. 40, p. 2141.
4. Sosnowski, J.J., Danaher, E.B., and Murray, R.K.,
J. Org. Chem., 1985, vol. 50, p. 2759.
5. Proksch, E. and De Meijere, A., Angew. Chem., 1976,
vol. 88, p. 802.
6. Proksch, E. and De Meijere, A., Angew. Chem., Int. Ed.
Engl., 1976, vol. 15, p. 761.
The X-ray diffraction data for compounds 2c and 3c
were obtained at the Institute of Organoelement Com-
pounds, Russian Academy of Sciences, on a Bruker
SMART diffractometer with a CCD detector (MoKα
radiation, λ 0.71073 Å, ω-scanning, 2θmax = 58.24°).
A correction for absorption was applied using
SADABS program [30] (Tmax = 0.923, Tmin. = 0.056).
The structures were solved by the direct method and
were refined against F2hkl by the full-matrix least-
squares procedure in anisotropic approximation for all
non-hydrogen atoms and isotropic approximation for
all localized hydrogen atoms. The positions of hydro-
gen atoms were calculated on the basis of geometry
considerations and were refined according to the riding
model: U(H) = 1.5 Ueq(C), where Ueq(C) is the equiv-
alent temperature factor of the corresponding carbon
atom. All calculations were performed using
SHELXTL-Plus 5 software package [31].
7. Erzen, E., Cerkovnik, J., and Plesničar, B., J. Org.
Chem., 2003, vol. 68, p. 9129.
8. Avzyanova, E.V., Cand. Sci. (Chem.) Dissertation, Ufa,
1998.
9. Shereshovets, V.V., Khursan, S.L., Komissarov, V.D.,
and Tolstikov, G.A., Russ. Chem. Rev., 2001, vol. 70,
p. 105.
10. Becke, A.D., Phys. Rev. A, 1988, vol. 38, p. 3098.
11. Becke, A.D., J. Chem. Phys., 1993, vol. 98, p. 5648.
12. Perdew, J.P., Chevray, J.A., Vosko, S.H., Jackson, K.A.,
Pederson, M.R., Singh, D.J., and Fiolhais, C., Phys.
Rev. B, 1992, vol. 46, p. 6671.
Compound 2c. C12H15O; M 175.24; monoclinic
crystal system, space group P21/c; unit cell parameters
[173(2) K]: a = 13.333(3), b = 17.160(3), c =
12.218(2) Å; V = 2793.7(10) Å3; Z = 4; dcalc = 1.257 g×
cm–3. Total of 4898 reflection intensities were mea-
sured from a 0.2×0.1×0.1-mm colorless single crystal.
13. McLean, A.D. and Chandler, G.S., J. Chem. Phys., 1980,
vol. 72, p. 5639.
14. Bylaska, E.J., De Jong, W.A., and Kowalski, K., NW
Chem. A Computational Chemistry Package for Parallel
Computers, Version 5.0, Washington, 2006.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 51 No. 12 2015

KHALITOVA et al.
1716
15. Vendillo, V.P., Emel’yanov, Yu.M., and Filippov, Yu.V.,
23. Newcomb, M., Lansacara-P., D.S.P., Kim, H.-Y.,
Chandrasena, R.E.P., Lippard, S.J., Beauvais, L.G.,
Murray, L.J., Izzo, V., Hollenberg, P.F., and Coon, M.J.,
J. Org. Chem., 2007, vol. 72, p. 1128.
Prib. Tekh. Lab. Rab., 1959, vol. 25, p. 1401.
16. Haines, A.H., Methods for the Oxidation of Organic
Compounds: Alkanes, Alkenes, Alkynes, and Arenes,
London: Academic, 1985.
24. Coleman, M.G., Brown, A.N., Bolton, B.A., and
17. Abdrakhmanova, A.R., Khalitova, L.R., Spirikhin, L.V.,
Dokichev, V.A., Grabovskiy, S.A., and Kabal’no-
va, N.N., Russ. Chem. Bull., Int. Ed., 2007, vol. 56,
p. 271.
18. Shereshovets, V.V., Galieva, F.A., Shafikov, N.Ya., Sady-
kov, R.A., Panasenko, R.A., and Komissarov, V.D., Bull.
Acad. Sci. USSR, Div. Chem. Sci., 1982, vol. 31, p. 1050.
Guan, H., Adv. Synth. Catal., 2010, vol. 352, p. 967.
25. Gonzalez-Nunez, M.E., Mello, R., Olmos, A.B.A., and
Accrete, R., J. Org. Chem., 2006, vol. 71, p. 1039.
26. Gamble, D.L., Hems, W.P., and Ridge, B., J. Chem.
Soc., Perkin Trans. 1, 2001, p. 248.
27. Kim, Do-H., Kim, Soon-I., Chang, K.-S., and Ahn, Y.-J.,
J. Agric. Food Chem., 2002, vol. 50, p. 6993.
19. Caminade, A.M., El Khatib, F., and Koenig, M., Can. J.
Chem., 1985, vol. 63, p. 3203.
28. Fringuelli, F., Gazz. Chim. Ital., 1975, vol. 105, p. 1215.
29. Hodgson, D.M., J. Am. Chem. Soc., 2004, vol. 126,
20. Bagdasar’yan, Kh.S., Russ. Chem. Rev., 1984, vol. 53,
p. 8664.
p. 623.
30. Görbitz, C.H., Acta Crystallogr., Sect. C, 2000, vol. 56,
21. Preuss, T., Proksch, E., and De Meijere, A., Tetrahedron
Lett., 1978, vol. 19, p. 833.
p. 500.
22. Molander, G.A. and Harring, L.S., J. Org. Chem., 1989,
31. SHELXTL-Plus, Madison, WI: Bruker Analytical X-Ray
vol. 54, p. 3525.
Systems.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 51 No. 12 2015