Kinetic Patterns of Condensation of Alkyl- and Cycloalkylcyclopentanones with Dihydric Alcohols in the Presence of Polyoxomolybdate Modified with Oxides of Rare-Earth Elements

Article abstract of DOI:10.1134/S1070427218110204

The results of condensation of C₅–C₇ alkyl- and cycloalkyl-substituted cyclopentanones with diatomic vicinal alcohols in the presence of polyoxomolybdate modified with gadolinium oxide are considered. Kinetic patterns are investigated and a kinetic model of the process is proposed. It was established that alkyl- and cycloalkyl derivatives of dioxaspironone are formed directly by two parallel-consecutive routes and through the stages of the preparation of the corresponding hemiacetal. The ratio of the rate constants of these routes depends on the composition and structure of the starting ketones and diols.

Full text of DOI:10.1134/S1070427218110204

ISSN 1070-4272, Russian Journal of Applied Chemistry, 2018, Vol. 91, No. 11, pp. 1882−1889. © Pleiades Publishing, Ltd., 2018.
Original Russian Text © Kh.M. Alimardanov, F.M. Veliev, Н.R. Dadashova, 2018, published in Zhurnal Prikladnoi Khimii, 2018, Vol. 91, No. 11, pp. 1658−1666.
CATALYSIS
Kinetic Patterns of Condensation of Alkyl-
and Cycloalkylcyclopentanones with Dihydric Alcohols
in the Presence of Polyoxomolybdate Modified
with Oxides of Rare-Earth Elements
Kh. M. Alimardanova, F. M. Velievaa,*, and Н. R. Dadashovaa
aMamedaliyev Institute of Petrochemical Processes, of the National Academy of Sciences of Azerbaijan,
Baku, AZ 1025 Azerbaijan
*e-mail: firuza1@aport2000.ru
Received May 7, 2018
Abstract—The results of condensation of C5–C7 alkyl- and cycloalkyl-substituted cyclopentanones with diatomic
vicinal alcohols in the presence of polyoxomolybdate modified with gadolinium oxide are considered. Kinetic pat-
terns are investigated and a kinetic model of the process is proposed. It was established that alkyl- and cycloalkyl
derivatives of dioxaspironone are formed directly by two parallel-consecutive routes and through the stages of
the preparation of the corresponding hemiacetal. The ratio of the rate constants of these routes depends on the
composition and structure of the starting ketones and diols.
Keywords: alkyl cyclopentanones, vicinal diols, kinetic model
DOI: 10.1134/S1070427218110204
The reaction of acetalization (or ketalization) of
aldehydes and ketones with dihydric alcohols is widely
used to protect carbonyl groups [1]. 1,3-Dioxalanes
and dioxaspiroalkanes with different functional groups
synthesized at the same time have independent significance
and are used as fragrant and flavoring compounds in the
perfume and food industry [2, 3], in the manufacture of
pharmaceutical preparations [4], solvents [5], biologically
active substances [6], insecticides with high biological
degradability [7], etc. In the literature there is enough
information about the production of 1,3-dioxolanes
with the participation of homogeneous acid-type
catalysts [8–11]. Recently, studies have emerged in
which complexes containing Rh, Pd, Pt, Ce [12, 13]
or heterogeneous catalytic systems [14, 15] have been
used as condensation catalysts. These works are mainly
devoted to the synthesis of 1,3-dioxolans from aromatic
or unsubstituted alicyclic aldehydes and ketones. On the
synthesis of dioxaspiroalkanes based on alkyl-substituted
alicyclic ketones, there are only a few works [3, 16].
The mechanism of these reactions is considered from
the generally accepted position and is not sufficiently
substantiated by step-by-step kinetic studies.
Thus, the synthesis of dioxaspiroalkanes based on
C5–C7 alkyl- and cycloalkyl-substituted cyclanones used
as aromatic compounds [2] and especially the study of the
step-by-step kinetic pattern of these reactions are relevant
both from theoretical and practical points of view.
The work is devoted to the preparation of the above
compounds using polyoxomolybdate modified with
neodymium or gadolinium cations, and the study of the
kinetic patterns by the multi-route mechanism of this
reaction.
EXPERIMENTAL
The procedures of preparation of the catalyst and
the experiment performing are similar to that described
earlier in [16, 17]. In the experiments, Nd- and Gd-
containing samples of polyoxomolybdate were used,
prepared by mixing aqueous solutions of (NH4)6Mo7O24,
(СH3COO)2Nd, Gd(NO)3 of chemically pure grade, 85%
1882

KINETIC PATTERNS OF CONDENSATION
1883
Scheme 1.
where R1 = R3 = H, R2 = n-C3H7 (1); R1 = R3 = H, R2 = n-C4H9 (2); R1 = R3 = H, R2 = n-C5H11 (3); R1 + R2 = C4H8, R3 =
H (4); R1 + R2 = C5H8, R3 = H (5); R1 = H, R2 = C5H11, R3 = CH3 (6); R1 + R2 = C4H8, R3 = CH3 (7); R1 + R2 = C5H8, R3 =
CH3 (8).
H3PO4 and carbon material obtained by the interaction of
CCl4 (chemically pure grade) and metallic Al according
to the method of [17]. Stirring was continued for 8 h at
a temperature of 85–90°С, followed by evaporation of
the suspension and heat treatment of the dry residue at
150–180°С.
(15 wt %). IR spectra were recorded on anAlpha Fourier
transform spectrometer in the range 400–4000 cm–1.
RESULTS AND DISCUSSION
It is known that some spiroacetals, in particular
7-tert-butyl-1,4-dioxaspiro[4,5]decane (Kiprenal) and
2-butyl-1,4-dioxaspiro[4,4]nonane (jasmonan), are used
in the composition of various perfume compositions [2].
The starting compounds were ethane-1,2- and propane-
1,2-diols of the chemically pure grade, cyclopentanone
(Alfa Aesar Co.). Alkyl- and cycloalkylcyclopentanones
were obtained according to the previously developed
method [18]. A preset amount of cyclopentanone, C5–
C7 α-olefins (or C6–C7 cycloolefins), and di-tert-butyl
peroxide were loaded into a 2 L autoclave with a molar
ratio of of 4 : 1 : 0.15 and kept at 140–160°C for 4–6 h.
Alkyl- and cycloalkylcyclopentanones were isolated from
the reaction mixture by atmospheric vacuum distillation.
The latter is characterized by the scent of jasmine
note. The synthesized alkyl and cycloalkyl-substituted
dioxaspiroalkanes according to Scheme 1 are analogues
of jasmonan. Physicochemical and spectral data of these
compounds are given in Table 1 and Fig. 2. The kinetic
patterns of the reaction were investigated using the
example of the condensation of 2-n-pentylcyclopentanone
and ethane-1,2-diol.
Ketones and glycols were condensed in a thermostated
glass reactor; the kinetic studies were performed in
a 25 mL microreactor equipped with a thermometer,
magnetic stirrer, reflux condenser, Dean–Stark nozzle,
and sampling device. Ketone (0.0025 mol), glycol
(0.03 mol), catalyst (0.05 mol Mon+), and toluene (10 mL)
as a solvent were simultaneously charged to the reactor.
After reaching the set temperature, the catalyzate was
analyzed every 30 min. The reaction was monitored
by gas-liquid chromatography (GLC) and infrared
spectroscopy (IR). In the IR spectrophotometric analysis
a change in the absorption band of the carbonyl group at
1730 cm–1 was taken as a criterion (Fig. 1).
Effective separation of ketones and synthesized
spirodioxolanes was achieved on a Tsvet-100m
chromatograph with a thermal conductivity detector,
helium carrier gas, 1 m × 2 mm column with a stationary
phaseApiezon Ldeposited on Chromaton N-AW-HMDS
Wavenumber, cm‒1
Fig. 1. Comparative description of the IR spectra corresponding
to each hour of the condensation reaction of ethanediol-1,2 with
2-n-pentylcyclopentanone. τ (min): (1) 60, (2) 120, (3) 180,
(4) 240.
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KINETIC PATTERNS OF CONDENSATION
1885
Table 2. The observed rate of accumulation of key substances in the reaction of 2-pentylcyclopentanone and ethylene glycol
at different temperatures. Catalyst GdPO4·(MoO2)0.5·PMo12O40, 0.1 g
с0 × 10–1, M
ω, M min–1 10–3
Experience
time, min
Conversion,
%
ketone diol
–W1
–W2
W3
W4
W5
W6
Solvent–isooctane, Т = 99°С
7.0
7.0
7.0
7.0
7.0
7.0
7.0
7.0
7.0
7.0
60
120
180
240
300
16.4
28.0
43.1
54.9
63.4
1.92
1.64
1.675
1.60
1.48
2.26
1.84
1.88
1.78
1.64
0.203
0.110
0.111
0.088
0.068
1.71
1.53
1.485
1.47
1.38
–
0.17
0.10
0.10
0.08
0.08
–
0.08
0.05
0.03
Solvent—toluene, Т = 110°С
7.0
7.0
7.0
7.0
7.0
7.0
7.0
7.0
7.0
7.0
60
120
180
240
300
18.7
40.8
55.1
56.9
63.3
2.18
2.38
2.14
1.66
1.48
2.53
2.73
2.47
1.96
1.78
0.14
0.15
0.15
0.08
0.08
1.95
2.11
1.95
1.55
1.38
0.092
0.117
0.045
0.025
0.015
0.18
0.174
0.164
0.153
0.153
7.0
7.0
7.0
7.0
7.0
14.0
14.0
14.0
14.0
14.0
60
120
180
240
300
44.3
45.8
51.3
53.7
60.9
5.17
2.67
2.00
1.57
1.42
5.58
2.98
2.33
1.895
1.74
0.41
4.34
2.36
1.74
1.43
1.31
0.425
0.139
0.110
0.025
0.002
0.205
0.155
0.166
0.165
0.161
0.175
0.14
0.11
0.095
7.0
7.0
7.0
7.0
28.0
28.0
28.0
28.0
60
120
180
240
55.4
63.3
82.0
91.8
6.47
3.69
3.19
2.68
7.08
4.09
3.59
3.09
0.683
0.058
0.340
0.228
5.46
3.18
2.14
2.35
0.327
0.150
0.149
0.068
0.307
0.201
0.196
0.207
14.0
14.0
14.0
14.0
7.0
7.0
7.0
7.0
60
120
180
240
11.4
25.4
30.6
36.7
1.326
1.480
1.191
1.363
1.767
1.737
1.424
1.363
0.067
0.105
0.075
0.083
1.25
0.01
0.175
0.128
0.117
0.146
1.295
1.079
0.956
0.08
0.037
0.032
Solvent–benzene, Т = 80°С
7.0
7.0
7.0
7.0
7.0
7.0
7.0
7.0
7.0
7.0
60
120
180
240
300
12.7
17.6
21.9
38.3
45.7
1.483
1.025
1.086
1.118
1.067
2.26
0.203
0.108
0.111
0.088
0.068
1.713
1.529
1.485
1.467
1.379
–
0.173
0.100
0.100
0.088
0.082
1.837
1.877
1.776
1.645
–
0.079
0.046
0.033
Solvent–m-xylene, Т = 130°С
7.0
7.0
7.0
7.0
7.0
7.0
7.0
7.0
7.0
7.0
60
120
180
240
300
41.6
51.4
64.3
74.6
82.7
4.85
3.00
2.50
2.175
1.93
5.27
3.32
2.82
2.48
2.26
0.478
0.250
0.183
0.114
0.087
4.14
2.64
2.25
1.95
1.69
0.232
0.115
0.093
0.111
0.154
0.212
0.160
0.158
0.152
0.164
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ALIMARDANOV et al.
Scheme 2.
The main products of the reaction in the presence
experiments were carried out with binary mixtures. In
particular, the condensation of ketone with ethylene glycol
was carried out by introducing the above compounds
into the system. The results of the studies indicate that
no inhibition by the reaction products occurs at least to
the degree of conversion of the initial ketone 30–40%
(Fig. 3). According to the reported data and taking into
account the results obtained, conversion curves of the
process selectivity vs. the conversion of the initial ketone
were constructed at various temperatures.
of a catalytic system (polyoxomolybdate modified with
gadolinium oxide) are spiroacetal, hemiacetal, and
1,4-dioxane, product of ethane-1,2-diol self-condensation.
In order to study the possible effect of the above
compounds on the condensation process, special
The selectivity of the reaction for the corresponding
spiroacetal in the reaction conditions remains high, but at
a conversion close to zero, determined by differentiating
the corresponding curves, it differs from 100%, which
indicates a parallel-sequential scheme of the ketone
transformation.
Wavenumber, cm‒1
Based on the experimental data in Table 2, the
following independent routes can be proposed for the
transformation of ketone and ethanediol-1,2 (Scheme 2).
Fig. 2. IR spectrum of 5-pentyl-1,4-dioxaspiro[4.4]nonane.
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KINETIC PATTERNS OF CONDENSATION
1887
In the study area (Table 2) with an increase in the initial
concentration of the initial ketone, ethylene glycol, and
catalyst at a constant value of the concentrations of other
components of the reaction mixture, the accumulation
of spiroacetal proceeds linearly, which indicates the first
order of reaction for these components:
W = k[с1][с2 × cat],
Conversion, %
where W is the formal rate of accumulation of spiroacetal
(M–1 min–1), c1 and c2 are the concentrations of ketone and
ethylene glycol, respectively.
Fig. 3. Selectivity S of reaction for spiro acetal vs. conversion
of 2-n-pentylcyclopentanone at different temperatures. Т (°С):
(1) 100, (2) 120, (3) 130.
Theoretically, the first product of the interaction of
2-pentylcyclopentanone and ethanediol-1,2 is hemiac-
etal : 1-hydroxy-1-(2-hydroxyethoxy)-2-pentylcyclo-
pentane. The formation of ketal and hemiacetal was
also indirectly proved by the reaction of cyclopentanone
and ethanol in the presence of strong mineral acids
(HCl, H2SO4). Consequently, the condensation of these
compounds must proceed in a sequential pattern [9].
However, the type of graphical dependence of selectivity
for hemi- and spiroacetals on ketone conversion (Fig. 3)
shows that in this case the reaction proceeds according
to a parallel-sequential scheme of their transformation.
In addition to spiroacetal and hemiacetal, GLC analysis
showed that the catalysate contained 1,4-dioxane and
two products, presumably hydroxyesters, indicated in
the reaction scheme.
The parallel-sequential scheme of the reaction is
likely due to the bifunctional properties of the catalyst.
According to the results of kinetic studies (Table 2), the
closest convergence of the calculated and experimental
data was achieved using the kinetic equations of the
power type:
Table 3. Staged condensation scheme of 2-alkylcyclopentanone and ethylene glycol in the presence of a complex
GdPO4·(MoO2)0.5PMo12O40
Number of stages along stoichiometric
routes
Stage no.
Routea
I
II
III
IV
V
VI
1
2
C2H4(OH)2 + ZO → HOC2H4OZOH
1
1
1
0
0
0
0
0
0
0
0
0
1
1
0
1
0
0
0
0
0
0
0
0
0
0
0
1
1
1
0
0
0
0
0
0
0
0
0
0
1
0
1
1
0
0
0
0
0
0
0
0
1
0
0
0
1
1
0
0
1
0
0
0
0
0
0
0
0
0
1
1
R = O + HOC2H4OZOH → HOC2H4OROZOH
3
HOC2H4OROZOH → R(O)2C2H4 + ZO + H2O
4
HOC2H4OROZOH → HOROC2H4OH + ZO
5
HOROC2H4OH + ZO → HOROC2H4OZOH
6
HOROC2H4OZOH → R(O)2C2H4 + ZO + H2O
7
HOROC2H4OZOH + R(O)2C2H4 → HOC2H4OROC2H4OZOH
HOC2H4OROC2H4OZOH → HOC2H4OROC2H4OH + ZO
HOROC2H4OZOH + C2H4(OH)2 → HOROC2H4OC2H4OZOH + H2O
HOROC2H4OC2H4OZOH → HOROC2H4OC2H4OH + ZO
HOC2H4OZOH + C2H4(OH)2 → HOC2H4OC2H4OZOH + H2O
HOC2H4OC2H4OZOH → C4H8O2 + ZO + H2O
8
9
10
11
12
a R = O—2-pentylcyclopentanone, ZO—GdPO4·(MoO2)0.5PMo12O40.
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ALIMARDANOV et al.
r1 = k1[c1][c2],
r2 = k2[с1][с2],
r3 = k3[с3],
(1)
(2)
(3)
(4)
Taking into account the results obtained, the process
of condensation of ketone and glycol in spiroacetal can be
described by the step-by-step scheme (Table 3). The stage
responsible for the interaction of alkylcyclopentanone
with the Gd-polyoxomolybdate diolate complex
according to Scheme 2 was chosen as the limiting one.
r4 = k4[с2][с3],
r5 = k5[с2][с3],
r6 = k6[с2]2,
(5)
(6)
where k1–k6 are reaction rate constants along routes I–VI;
r1–r6 are the rates of accumulation of reaction products
using the corresponding stoichiometric equations; c1–c3
are the concentrations of the starting ketone, diol, and
hemiacetal.
CONCLUSIONS
(1) The conditions for the condensation of C5–C7-
alkyl- and cycloalkyl-substituted cyclopentanone and
vicinal glycols (ethane-1,2- and propane-1,2-diols) to
the corresponding spiroacetals with participation of
polyoxomolybdenum modified with rare-earth oxides
were studied.
When compiling the equations, the esterification rates
on the basis of additional experiments and analyzes of
the reaction products were equated to zero. The rates of
transformation of the initial ketone and glycol, as well as
the reaction products obtained from routes I – VI, were
calculated using the following equations:
(2) Kinetic patterns were studied and kinetic equations
and a step-by-step kinetic model were compiled describing
the main reaction routes. It has been established that
the corresponding spiroacetal from ketone and diol is
formed both directly, in one stage, and according to a
two-stage scheme, through the stages of the preparation
of hemiacetal.
W1 = –r1–r2,
W2 = –r1–r2–r4–r5–2r6,
W3 = r1–r3–r4–r5,
W4 = r2 + r3,
(7)
(8)
(9)
(10)
(11)
(12)
REFERENCES
W5 = r4 + r5,
W6 = r6.
1. Traven’, V.F., Organicheskaya khimiya (Organic
where W1–W6 are the experimentally found rates listed in
Table. 2
Chemistry), vol. 2, Moscow: Binom, 2013.
2. Kheyfits, L.A. and Dashunin, V.M., Dushistyye veshchestva
i drugiye produkty dlya parfyumerii (Perfumes and Other
Perfumery Products), Moscow: Khimiya, 1994.
The rate constants were calculated by a modified fourth-
order Runge–Kutta method using the Matlab-6.5 program. The
experimental values of the constants were found graphically
and refined by minimizing the standard deviations between the
observed and calculated data for Eqs. (7)–(12). Pre-exponential
values of the constants and activation energy were calculated
for the individual stages of the condensation reaction of
2-n-pentylcyclopentanone and ethanediol-1,2, having the
following form:
3. Osnovy organicheskoi khimii dushistykh veshchestv dlya
prikladnoi estetiki i aromaterapii (Basics of Organic
Chemistry of Fragrant Substances for Applied Aesthetics
and Aromatherapy), Soldatenkov, A.T., Ed., Moscow:
IKTS “Akademkniga,” 2006.
4. Mashkovskii, M.D., Lekarstvennyye sredstva (Drugs),
ch. 1, Moscow: Meditsina, 2000.
k1 = 1.65 × 102exp(–9465/RT) M–1 min –1,
k2 = 6.1 × 104exp(–16907/RT) M–1 min –1,
k3 = 7.07 × 104exp(–22822/RT) M–1 min–1,
k4 = k5 ≈ 0,
5. Nedumaran, D. and Pandurangan, A., Micropor. Water,
2013, vol. 169, pp. 25–34.
6. Miyake, H., Nakao, Y., and Sasaki, M., Chem. Lett., 2007,
vol. 36, no. 1, pp. 104–105.
k6 = 2.29 × 102exp(–13451/RT) M–1 min –1,
7. USSR Byull. Izobr. 587839, 1978, no. 1; Herbicidal
Composition.
where R is the universal gas constant, 8.3144 J mol–1 K–1.
The standard deviation for the main route I was 12.5%;
for routes II–IV, 15–21%. The zero value of the constants
k4 and k5 indicates that the main direction for the
transformation of semi-acetal is route III.
8. Shui-Jin, Y., Qiang, W., and Guo-bin, D., J. Xuzhou
Institute Technol. Natural Sci. Ed., 2012, vol. 3, pp. 25–28.
9. Zhang, F., Xu, D., Luo, Sh., Liu, B., and Xu, Z., J. Chem.
Ind. Eng., 2004, vol. 55, pp. 2047–2050.
RUSSIAN JOURNAL OF APPLIED CHEMISTRY Vol. 91 No. 11 2018

KINETIC PATTERNS OF CONDENSATION
1889
10. Waller, D.L., Stephenson, C.R.J., and Wipf, P., Org.
Biomol. Chem., 2007, vol. 5, pp. 58–60.
15. Yang, Z., Lei, C., Zhao, X., Liu, R., Wei, H., Ma, Y.,
Meny, S., Cao, Q., Wei, J., Wang, X., Chem. Select., 2017,
vol. 2, pp. 9377–9386.
11. Vyglazov, O.G., Chuiko, V.A., Izotova, L.V.,
Vintarskaya, Z.V., and Yudenko, R.Y., Russ. J. Appl.
Chem., 2001, vol. 74, no. 11, pp. 1888–1891].
16. Alimardanov, Kh.M., Sadigov, O.A., Abbasov, M.F.
Suleymanova, E.T., Jafarova, H.A., Abdullayeva, M.Y.,
and Abbasova, S.M., Russ. J. Org. Chem., 2011, vol. 47,
pp. 1136–1143.
12. Eshghi, H., Rahimzadeh, M., and Saberi, S., Catal.
Commun., 2008, vol. 9, pp. 2460–2466.
17. Garibov, N.I., Alimardanov, Kh.M., Dadashova, N.R.,
Sadiqov, O.A., Almardanova, M.B., Quliyev, A.D., Russ.
J. Gen. Chem., 2015, vol. 85, no. 5, pp. 1025–1033.
13. Kanai, S., Nagahara, Kita, Y., Kamata, K., and Hara, M.,
Chem. Sci., 2017, vol. 8, pp. 3146–3153.
14. Sayama, S., Tetrahedron Lett., 2006, vol. 47, no. 24,
18. Abbasov, M.F., Alimardanov, Kh.M., and Suleymano-
pp. 4001–4005.
va, E.T., Zh. Prikl. Khim., 1997, vol. 70, no. 4, pp. 648–655.
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