A Hydroperoxide Method for 3,4-Xylenol Synthesis

Article abstract of DOI:10.1134/S0965544118050092

The aerobic oxidation reaction of 1,2-dimethyl-4-isopropylbenzene to a hydroperoxide in the presence of N-hydroxyphthalimide and its derivatives has been studied. It has been found that up to a hydrocarbon (HC) conversion of 25–30%, the selectivity for the tertiary hydroperoxide of 1,2-dimethyl-4-isopropylbenzene is over 90–95%. A method for assessing the catalytic activity of phthalimide compounds in liquid-phase oxidation reactions of 1,2-dimethyl-4-isopropylbenzene with the use of quantum-chemically calculated values for the energies of singly occupied molecular orbitals (ΔЕ_SOMO) has been proposed.

Full text of DOI:10.1134/S0965544118050092

ISSN 0965-5441, Petroleum Chemistry, 2018, Vol. 58, No. 5, pp. 451–456. © Pleiades Publishing, Ltd., 2018.
Original Russian Text © E.A. Kurganova, A.S. Frolov, G.N. Koshel’, T.N. Nesterova, V.A. Shakun, O.A. Mazurin, 2018, published in Neftekhimiya, 2018, Vol. 58, No. 3.
A Hydroperoxide Method for 3,4-Xylenol Synthesis
a
a
a,
b
E. A. Kurganova , A. S. Frolov , G. N. Koshel’ *, T. N. Nesterova ,
b
b
V. A. Shakun , and O. A. Mazurin
Yaroslavl State Technical University, Yaroslavl, 150023 Russia
Samara State Technical University, Samara, 443001 Russia
a
b
*
e-mail: koshelgn@ystu.ru
Received July 12, 2017
Abstract—The aerobic oxidation reaction of 1,2-dimethyl-4-isopropylbenzene to a hydroperoxide in the
presence of N-hydroxyphthalimide and its derivatives has been studied. It has been found that up to a hydro-
carbon (HC) conversion of 25–30%, the selectivity for the tertiary hydroperoxide of 1,2-dimethyl-4-isopro-
pylbenzene is over 90–95%. A method for assessing the catalytic activity of phthalimide compounds in liq-
uid-phase oxidation reactions of 1,2-dimethyl-4-isopropylbenzene with the use of quantum-chemically cal-
culated values for the energies of singly occupied molecular orbitals (ΔЕSOMO) has been proposed.
Keywords: N-hydroxyphthalimide, hydroperoxide, oxidation, 3,4-xylenol, 1,2-dimethyl-4-isopropylbenzene
DOI: 10.1134/S0965544118050092
INTRODUCTION
synthesis of alkylphenols via the reaction of arenes
with phthaloyl peroxide followed by the hydrolysis
of the resulting phthaloyl ester is described in [6]. A
method for the production of mixtures of dimethyl-
Xylenols (dimethylphenols) are high-production
volume products of the basic organic and petro-
chemical synthesis. They are widely used in the
manufacturing of plasticizers, synthetic resins, vita- phenol isomers using the hydroxylation of xylenes
mins [1], and monomers for the production of poly- in the presence of a molybdenum catalyst [7] or
mers and plastics with more valuable properties in
comparison with similar materials obtained on the
basis of phenol [2, 3]. The value of the individual
xylenol isomers, including 3,4-xylenol on the basis
of which high-performance plasticizers (e.g., trixy-
lyl phosphates) and high-quality electrical products
vanadium phosphotungstate [8] is also known. In
the papers cited, it is shown that the reactant con-
version does not exceed 18% over 4 h of the reac-
tion. Thus, the development of an effective method
for 3,4-xylenol production that will comply with the
are produced, increases to a significant extent. 3,4- contemporary operating and environmental
Xylenol also holds promise for using in the synthesis requirements is a demanding task.
of 3,3',4,4'-benzophenoxytetracarboxylic acid, a
The so-called oxidative method based on avail-
able petrochemical feedstock and the well-proven
monomer for the production of liquid-crystalline
thermotropic polymers [4].
“
cumene process” for the simultaneous synthesis of
The main source for the industrial production of
xylenols is cresol (phenol) fractions formed during
the thermal treatment of fuels. Currently known
phenol and acetone can become the most promising
industrial and technically acceptable process for the
synthetic methods for the production of 3,4-xyle- production of 3,4-xylenol. The process proposed
nol, such as diazotization of xylidines and the sul- comprises three steps, namely, the synthesis of 1,2-
fonate process, did not find wide application due to
the low yields and high consumption of auxiliary
materials [2]. There is information in the literature
on direct regioselective oxidation of o-xylene to 3,4-
xylenol with hydrogen peroxide in the presence of a
catalyst. Despite high selectivity, the conversion of
dimethyl-4-isopropylbenzene
(1,2-dimethyl-4-
IPB), its liquid-phase oxidation to tertiary hydrop-
eroxide (tert-HP), and subsequent acid-catalyzed
decomposition of the tert-HP of 1,2-dimethyl-4-
IPB to 3,4-xylenol and acetone according to the
the HC over 1 h of the reaction is below 1% [5]. The scheme
451

4
52
KURGANOVA et al.
OOH
CH3 CH CH3
CH3
CH3
C
CH3
OH
O
C
O2
H+
+
CH3 CH CH2
+ CH3
CH3
CH3
CH3
CH3
CH3
CH3
CH3
CH3
The key step, on which the effectiveness of the pro- spectra were recorded on a Bruker DRX 400 NMR
cess as a whole depends to a large extent, is the liquid- spectrometer (400.4 MHz). The solvent was a DMSO-
phase oxidation of 1,2-dimethyl-4-IPB to the tert-HP.
d –CCl mixture and the internal standard was
6
4
tetramethylsilane.
EXPERIMENTAL
The oxidation of 1,2-dimethyl-4-IPB was carried
out on a closed-loop flow unit which makes it possible
to meter the amount of oxygen absorbed during the
reaction [9]. The oxidation with air under pressure was
carried out in an apparatus of the UOSUG type in a
reactor made of a 18KhN9T steel [10]. The scheme of
1
,2-Dimethyl-4-isopropylbenzene (1,2-dimethyl-
4
-IPB) was obtained via the alkylation of o-xylene
according to a known procedure [9]. The synthesized
product had the following constants: T = 201–203°C,
b
2
0
20
D
d4 = 0.8802, and n = 1.5034. IR spectrum (KBr), the unit is depicted in Fig. 1.
–1
cm : 2961, 2925, 2890, 2870 (ν CH ), 1382, 1362
3
The oxidates were analyzed for the concentration
of the HP of 1,2-dimethyl-4-IPB via iodometric titra-
tion. The hydroperoxide was isolated from the oxida-
tion products by the extraction with a 90% aqueous
methanol solution. The process was carried out in a
two-neck flask equipped with a magnetic stirrer, a
water bath, a reflux condenser, and a thermometer.
(
1
δ‒CH(CH ) ), 3039, 3006, (=CH arom.), 1505,
578 (the aromatic ring). The 1,2,4 substitution is
3 2
–
1
indicated by the bands at 818 and 879 cm . The IR
spectrometric analysis was carried out on an RX-1
Fourier-transform IR instrument. The spectra were
processed using a Spektrum program provided by Per-
kin-Elmer. The spectra were recorded in the region of
1
00 mL of the initial mixture and 100 mL of the
000–400 cm– in a film between potassium bromide
1
4
extracting agent were charged to the flask, after which
the flask contents were vigorously stirred for 20 min at
plates or in a potassium bromide cell with d =
1
0
.0011 cm. H NMR spectrum, δ, ppm: 7.02 d (1H, 20°C. Then the reaction mixture was left until com-
3
4
H-6, J = 7.68 Hz), 6.98 d (1H, H-3, J = 1.33 Hz), plete separation. The HP was isolated from the extract
3
4
by vacuum rectification. The characteristics of the
obtained HP of 1,2-dimethyl-4-IPB were as follows:
6
2
1
.92 dd (1H, H-3, J = 7.68 and J = 1.33 Hz), 2.82–
.75 m (1H, H-4), 2.18 s (3H, 2-CH ), 2.16 s (3H,
3
1
20
20
-CH ), 1.19–1.13 m (6H, 4'-CH , 4''-CH ). H NMR Т = 90–93°C at 1 mmHg, n = 1.5232, and d
=
3
3
3
b
D
4
–
1
1
2
.014. IR spectrum (KBr), cm : 3349 (ν –O–OH),
963, 2925, 2896, 2872 (ν CH ) 1382, 1362 (δ
3
CH ), 1460, 1510, 1600 (aromatic ring), 1220, 1168
3
(
C–O–O).
5
3
7
3,4-Xylenol was obtained via the acid decomposi-
6
Vent
tion of the tert-HP of 1,2-dimethyl-4-IPB. 50 mL of
the HP of 1,2-dimethyl-4-IPB, 50 mL of acetone, and
H O
2
4
0
.14 mL of concentrated sulfuric acid (the weight frac-
8
tion of 95%) were charged to a three-neck flask
equipped with a stirrer and a thermometer. The pro-
cess was carried out at 45°C and constant stirring until
complete decomposition of the HP. The chromato-
graphic analysis of the products of the acid decompo-
sition of the HP was performed on a Chromatec
Kristall 5000.2 chromatograph equipped with a flame
ionization detector. The column was an SK-5 capil-
lary column with a length of 30 m and a diameter of
1
H O
2
2
Fig. 1. A unit for liquid-phase oxidation: (1) autoclave,
(
(
(
2) electric oven, (3) magnetic stirrer, (4) electromagnet,
5) condenser, (6) rheometer, (7) pressure reducer, and
8) compressed air cylinder.
0
.32 mm (the phase composition was as follows: 5%
phenyl- and 95% dimethylpolysiloxane). The carrier
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A HYDROPEROXIDE METHOD FOR 3,4-XYLENOL SYNTHESIS
453
Table 1. The effect of temperature on the selectivity for the tert-HP of 1,2-dimethyl-4-IPB and the conversion of 1,2-
dimethyl-4-IPB during its liquid-phase oxidation. The concentration of the catalyst (NHPI) is 1.7 wt %
Selectivity for 1,2-dimethyl-4-IPB
1,2-Dimethyl-4-IPB
conversion, %
Temperature, °C
Reaction time, h
1
tert-HP, %
1
10
20
30
40
97.8
94.9
91.7
93.8
6.4
15.7
28.6
23.2
1
1
1
0.5
3
gas was nitrogen and the flow rate was 2 cm /min. The the catalyst is due to the availability of the initial sub-
stances and ease of its production.
programmed heating was from 80 to 200°C at a rate of
°C/min. The constants of synthesized 3,4-xylenol
8
The effect of temperature on the aerobic oxidation
of 1,2-dimethyl-4-IPB in the presence of NHPI was
studied within a range from 110 to 140°C on a closed-
loop flow unit under atmospheric pressure.
2
0
were as follows: Т = 64°C and d = 1.023. IR spec-
m
1
4
–
trum (KBr), cm : 3222, 3017 (ν O–H), 1509, 1379
(
the aromatic ring), (δ CH ), 1240 (C–O–H). The
3
As is seen from Table 1, an increase in temperature
1
,2,4 substitution was confirmed by the presence of
from 110 to 130°C leads to an even increase in the rate
–1 1
bands at 852 and 810 cm . H NMR spectrum, δ, of oxidation. The maximum conversion of the HC is
3
ppm: 8.95 s (1H, OH), 6.88 d (1H, H-5, J = 8.02 Hz), achieved over 1 h of the reaction at 130°C and is about
4
3
29%. The indices of the rate of oxidation and accumu-
lation of the HP (Fig. 2) achieved in this case are fully
compliant with the similar indices of the liquid-phase
initiated oxidation of IPB and are superior to them in
6
8
4
.56 d (1H, H-2, J = 2.92 Hz), 6.47 dd (1H, H-6, J =
4
.02 and J = 2.92 Hz), 2.12 s (3H, 3-CH ), 2.08 s (3H,
3
-CH ).
3
The quantum chemical calculations were per- some cases.
formed by a PM7 semiempirical quantum-chemical
method (unrestricted Hartree–Fock method) with
the use of the software suite MOPAC 2012 [11].
The selectivity of the formation of 1,2-dimethyl-4-
IPB tert-HP was no less than 92–95% in all the exper-
iments, which to a significant extent exceeded this
index in the case of the use of the initiator. In the case
of the oxidation of 1,2-dimethyl-4-IPB with air under
a pressure of 5 atm at 125–130°C for 1 h, the conver-
sion of the HC was 24.2%, which was similar to the
indices of the oxidation of this HC with oxygen under
atmospheric pressure in a glass reactor.
RESULTS AND DISCUSSION
It has been found that during the oxidation of 1,2-
dimethyl-4-IPB in the presence of the HP of isoprop-
ylbenzene (IPB) as the initiator at 130°C, the conver-
sion of the HC is 12–14% over 1 h of the reaction, and
A change in the concentration of NHPI from 0.8 to
the selectivity of the formation of the tert-HP of 1,2- 1.7 wt % leads to an increase in the rate of oxidation of
dimethyl-4-IPB, does not exceed 85% [12]. Together the HC (Table 2) and accumulation of the HP (Fig. 3).
with the tert-HP of 1,2-dimethyl-4-IPB dimethylxy- Further increase in the concentration of the catalyst is
lylcarbinol, dimethylacetophenone, xylylic acid, and unfavorable due to its limited solubility. It is known
formaldehyde are formed under the selected condi- that the use of polar solvents such as acetonitrile in the
tions. Until recently, the above-specified disadvan- aerobic oxidation of IPB and cyclohexylbenzene
tages have failed to be eliminated, which, holds in to a makes it possible to increase the solubility of NHPI
significant extent the development of the oxidative and decrease the reaction temperature to 40–60°C
method for the joint synthesis of 3,4-xylenol and ace- [21–23]. However, in our opinion, the use of solvents
tone.
in the processes of liquid-phase oxidation of 1,2-
dimethyl-4-IPB and IPB is unreasonable because it
will lead to a significant complication of the technol-
ogy of concentration of the HP.
It turned out to be possible to increase the rate of
oxidation of 1,2-dimethyl-4-IPB 2−3-fold and the
selectivity of the formation of the tert-HP of 1,2-
dimethyl-4-IPB to 90–95% by means of the use of
It is seen from Table 3 that, in the case of the reuse
N-hydroxyphthalimide (NHPI) which successfully of NHPI in the process of liquid-phase oxidation of
manifested itself as a catalyst in the processes of oxida- 1,2-dimethyl-4-IPB, its catalytic activity does not
tion of aromatic HCs [13–20]. The choice of NHPI as decrease for at least five cycles.
PETROLEUM CHEMISTRY Vol. 58 No. 5 2018

4
54
KURGANOVA et al.
30
25
20
30
3
4
3
2
2
5
0
4
2
15
2
1
15
10
10
5
0
1
5
0
10
20
30
40
50
60
Time, min
10
20
30
Time, min
40
50
60
Fig. 3. Effect of the NHPI concentration on the liquid-
phase oxidation reaction of 1,2-dimethyl-4-IPB.
The catalyst concentration is (1) 0.8, (2) 1.1, (3) 1.7, and
Fig. 2. Effect of temperature on the liquid-phase oxidation
reaction of 1,2-dimethyl-4-IPB. The concentration of the
NHPI catalyst is 1.7 wt %. T is (1) 110, (2) 120, (3) 130, and
(
4) 3.3 wt % of the charge. The reaction time is 60 min, and
the temperature is 130°C.
(4) 140°C.
The modification of NHPI can become one of the
directions for increasing the effectiveness of the oxida-
tion of 1,2-dimethyl-4-IPB to the tert-HP. It is seen
from Table 4 that the presence of electron-donating
substituents (methyl and phenyl groups) in a NHPI
molecule promotes an increase in the rate of oxidation
of 1,2-dimethyl-4-IPB. At the same time, electron-
withdrawing substituents (chlorine and bromine) lead
to its decrease.
Similar results on the reuse of NHPI in the oxida-
tion of IPB were obtained in [21].
The earlier obtained results on the liquid-phase
oxidation of a wide range of alkylaromatic HCs [9,
2
4–26] in the presence of NHPI prove the possibility
for the use of the oxidative method as a universal tech-
nique for the production of not only 3,4-xylenol but
also other (methyl)phenols.
A mixture containing 97.2 wt % HP and 2.8% 1,2-
dimethyl-4-IPB was obtained via a four-stage
To estimate the catalytic activity of NHPI and its
extraction with a 90% aqueous methanol solution and derivatives, a quantum chemical calculation of the dif-
further subjected to the acid decomposition in the ference in the energy of a singly occupied molecular
presence of concentrated (95 wt %) sulfuric acid as the orbital of the radicals of the substrate (1,2-dimethyl-4-
catalyst. The reaction was carried out for 1 h. The sol-
vent (acetone) : HP : sulfuric acid ratio was 1 : 1 : 0.005
by weight. 3,4-Xylenol and acetone were isolated from
IPB) and catalysts, ΔЕ
, was used.
SOMO
It is seen from Table 4 that all the phthalimide
the reaction products via rectification and their yield compounds under study will exhibit catalytic proper-
was 90–95 and 80–85%, respectively.
ties in the aerobic oxidation of 1,2-dimethyl-4-IPB
Table 2. The effect of the catalyst (NHPI) concentration on the selectivity for the tertiary HP of 1,2-dimethyl-4-IPB and
conversion of 1,2-dimethyl-4-IPB during its liquid-phase oxidation. The reaction time is 1 h and the temperature is 130°C
Catalyst concentration, wt %
Selectivity for 1,2-dimethyl-4-IPB tert-HP, % 1,2-Dimethyl-4-IPB conversion, %
0
.8
.1
.7
96.1
92.3
91.7
90.9
91.2
14.4
26.3
28.6
29.4
29.5
1
1
2
.5
.3
3
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A HYDROPEROXIDE METHOD FOR 3,4-XYLENOL SYNTHESIS
455
Table 3. Reuse of the catalyst in the 1,2-dimethyl-4-IPB
oxidation process. The temperature is 120°C, the concen-
tration of the NHPI catalyst is 2.0 wt %, and the reaction
time is 1.5 h
Apparently, an electron-donating substituent in
●
the aromatic ring of the N-oxyl radical (PINO ) will
increase the spin density on the oxygen atom and,
because of this, its reactivity will increase. At the same
time, electron-withdrawing substituents decrease the
spin density on the oxygen atom, which is in agree-
ment with the earlier obtained results.
Selectivity for 1,2-dimethyl- 1,2-Dimethyl-4-
Cycle
4-IPB peroxide, %
IPB conversion, %
The mechanism of oxidation of HCs in the pres-
ence of NHPI is described in [21–23, 28, 29]. It has
been found that, during the interaction of a NHPI
molecule with a radical of the initiator or a peroxyl
1
2
3
4
5
96.4
96.2
96.4
96.4
96.7
14.9
14.8
15.1
15.1
14.7
●
radical (ROO ) of the substance being oxidized,
●
PINO is formed, which is capable of highly selec-
tively abstracting the hydrogen atom from the C–H
bond of alkylarenes (RH) to form corresponding alkyl
●
radicals (R ). In the presence of oxygen, the C-cen-
tered radical being formed is transformed to a peroxyl
radical which, in turn, interacts with NHPI to from
●
because the calculation values of ∆ Е
are within a PINO and HP (ROOH).
SOMO
range from 0 to 4 eV [27].
Therefore, a highly selective method for the syn-
thesis of the tertiary hydroperoxide of 1,2-dimethyl-4-
isopropylbenzene via the liquid-phase oxidation of
At the same time, compounds with the lowest value
will possess the highest activity. According
of ∆Е
SOMO
1
,2-dimethyl-4-isopropylbenzene in the presence of
to the quantum-chemical calculation results, 4-phe-
nyl-NHPI, 4-methyl-NHPI, 3-methyl-NHPI, and
NHPI can be compounds of this kind. The lowest cat-
N-hydroxyphthalimide which forms the basis for a
standard universal method for the joint production of
methylphenols and acetone complying with the mod-
alytic activity is exhibited by the analogues of NHPI ern environmental and economic requirements has
containing electron-withdrawing substituents in the been experimentally tested.
benzene ring. These results are in a good agreement
with the experimental data (Fig. 4 and Table 4), which
ACKNOWLEDGMENTS
confirms the appropriateness of the proposed method
for the estimation of the catalytic activity of phthalim-
This work was supported by the Ministry of Educa-
ide compounds in the process of oxidation of 1,2- tion and Science of the Russian Federation. The task
dimethyl-4-IPB.
of the Yaroslavl State Technical University
Table 4. Correlation of the values of ΔЕ
with the experimental data on the oxidation of 1,2-dimethyl-4-IPB to the HP.
SOMO
The temperature is 120°C, the reaction time is 1 h, and the concentration of the catalyst is 1.7 wt %
1
,2-Dimethyl-4-IPB
hydroperoxide
Selectivity for tert-HP
of 1,2-dimethyl-4-IPB,
%
∆
ЕSOMO
eV
,
1,2-Dimethyl-4-IPB
conversion, %
No.
Catalyst
concentration, wt %
1
2
3
4
5
6
7
4-Phenyl-NHPI
4-Methyl-NHPI
3-Methyl-NHPI
NHPI
1.85
1.83
1.82
1.90
2.06
2.08
2.21
18.4
21.7
19.9
14.9
10.4
9.9
95.9
94.7
94.8
94.9
96.3
96.7
97.2
19.2
22.9
20.1
15.7
10.8
11.4
7.4
4-Bromo-NHPI
4-Chloro-NHPI
1,2,3,4-Tetrabromo-NHPI
7.2
PETROLEUM CHEMISTRY Vol. 58 No. 5 2018

4
56
KURGANOVA et al.
. G. N. Koshel’, E. A. Kurganova, Yu. B. Rumyantseva,
9
0
0.2
0.4
0.6
0.8
25
et al., RU Patent No. 2466989 (2012).
2
1
0. N. M. Emanuel, E. T. Denisov, and Z. K. Maizus,
–
–
–
–
20
Chain Reactions of Liquid-Phase Oxidation of Hydrocar-
3
1
1
bons (Nauka, Moscow, 1965) [in Russian].
15
11. MOPAC
2012.
http://openmopac.net/
4
2
MOPAC2012.html.
2
R = 0.936
5
5
1
0
12. E. A. Kurganova, A. S. Frolov, and A. S. Danilova, Izv.
3
6
Vyssh. Uchebn. Zaved., Khim. Khim. Tekhnol. 57
4
7
7
6
(
10), 72 (2014).
5
0
–1.0
1
3. Y. Ishii, S. Sakaguchi, and T. Iwahama, Adv. Synth.
2
R = 0.982
Catal. 343, 393 (2001).
–1.2
1
.75 1.85 1.95 2.05 2.15 2.25
14. N. Koshino, Y. Cai, and J. H. Espenson, J. Phys.
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1
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dimethyl-4-IPB and the 1,2-dimethyl-4-IPB tert-HP
concentration in the presence of different phthalimide cat-
alysts on the energy of a singly occupied molecular orbital.
Figures 1–7 at the data points correspond to the entry
numbers in Table 4.
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Translated by E. Boltukhina
PETROLEUM CHEMISTRY
Vol. 58
No. 5
2018