Preparation of α-terpineol and perillyl alcohol using zeolites beta

Article abstract of DOI:10.1007/s11164-021-04515-6

The preparation of α-terpineol by direct hydration of limonene catalyzed by zeolites beta was studied. The same catalyst was used to prepare perillyl alcohol by isomerization of β-pinene oxide in the presence of water. The aim was to optimize the reaction conditions to achieve high conversions of starting material and high selectivity to the desired products. In the case of limonene, it was found that the highest selectivity to α-terpineol was 88% with conversion of 36% under the conditions: 50?wt% of catalyst beta 25, 10% aqueous acetic acid (10?mL) (volume ratio limonene:H₂O = 1:4.5), temperature 50?°C, after 24?h. In the case of β-pinene oxide, it was found that the highest selectivity to perillyl alcohol, which was 36% at total conversion, was obtained in the reaction under the following conditions: dimethyl?sulfoxide as solvent (volume ratio β-pinene oxide:DMSO = 1:5), catalyst beta 25 without calcination (15?wt%), demineralized water (molar ratio β-pinene oxide:H₂O = 1:8), temperature 70?°C, 3?h. The present study shows that the studied reactions are suitable for the selective preparation of chosen compounds.

Full text of DOI:10.1007/s11164-021-04515-6

Research on Chemical Intermediates
https://doi.org/10.1007/s11164-021-04515-6
Preparation of α‑terpineol and perillyl alcohol using
zeolites beta
1
1
1
Kateřina Zítová · Eliška Vyskočilová · Libor Červený
Received: 12 April 2021 / Accepted: 8 June 2021
©
The Author(s), under exclusive licence to Springer Nature B.V. 2021
Abstract
The preparation of α-terpineol by direct hydration of limonene catalyzed by zeo-
lites beta was studied. The same catalyst was used to prepare perillyl alcohol by
isomerization of β-pinene oxide in the presence of water. The aim was to opti-
mize the reaction conditions to achieve high conversions of starting material and
high selectivity to the desired products. In the case of limonene, it was found that
the highest selectivity to α-terpineol was 88% with conversion of 36% under the
conditions: 50 wt% of catalyst beta 25, 10% aqueous acetic acid (10 mL) (volume
ratio limonene:H O=1:4.5), temperature 50 °C, after 24 h. In the case of β-pinene
2
oxide, it was found that the highest selectivity to perillyl alcohol, which was 36%
at total conversion, was obtained in the reaction under the following conditions:
dimethyl sulfoxide as solvent (volume ratio β-pinene oxide:DMSO=1:5), catalyst
beta 25 without calcination (15 wt%), demineralized water (molar ratio β-pinene
oxide:H O=1:8), temperature 70 °C, 3 h. The present study shows that the studied
2
reactions are suitable for the selective preparation of chosen compounds.
Keywords Hydration · Zeolites · α-Terpineol · Perillyl alcohol · Heterogeneous
catalysis
Introduction
Zeolites belong to crystalline aluminosilicate materials containing orderly distrib-
uted micropores [1]. The number of structural types of zeolites exceeds one hundred
[
2]. The well-known zeolites are, e.g., mordenite, faujasite, Y, ZSM-5, and beta.
Because of their high hydrothermal stability, low production costs, and unique char-
acteristics, zeolites have been widely used as highly eꢀcient catalysts, detergents,
adsorbents, and ion exchangers in many chemical processes [1, 3]. Besides these
*
Eliška Vyskočilová
eliska.vyskocilova@vscht.cz
1
Department of Organic Technology, University of Chemistry and Technology Prague, Technicka
5
, 166 28 Prague 6, Czech Republic
Vol.:(012
1
3456789)
3

K. Zítová et al.
traditional applications, zeolites are promising in the ꢁelds of renewable energy and
environmental improvements, such as biomass conversion, fuel cells, air pollution
remediation, and water puriꢁcation [1]. Nevertheless, this work is focused on the
usage of zeolites in catalysis. The successful (even industrial) applications of zeo-
lites beta include the following: (1) aromatic Friedel–Crafts acylation [4], (2) ali-
phatic and aromatic alkylation [5–7], (3) aromatic nitration [8], (4) intramolecular
Prins cyclization [9], and (5) oil-reꢁning (ꢂuid catalytic cracking) [10]. The men-
tioned processes are important in various areas of the ꢁne chemical industry, e.g., in
the production of dyes, pharmaceuticals and fragrances [11], and the petrochemical
industry [1]. Still, many processes in ꢁne chemical production involve the traditional
Brønsted (H SO , HF, HCl, PTSA) and Lewis acids (AlCl , ZnCl , BF ) as catalysts
2
4
3
2
3
in a homogeneous liquid system [3, 12]. However, the usage of strong mineral acids
causes serious problems, especially environmental ones. A possible solution is to
replace the homogeneous catalysts with recyclable heterogeneous ones. In addition,
the use of solid catalysts allows the easier separation of the catalyst from the reac-
tion mixture and the possibility of recycling and reuse [12].
This paper describes two examples of using zeolites as catalysts for ꢁne chemi-
cal production: preparation of α-terpineol by acid-catalyzed direct hydration of
limonene and preparation of perillyl alcohol by acid-catalyzed isomerization of
β-pinene oxide in the presence of water.
α-Terpineol is one of the most important monocyclic terpenes [13]. It is used,
e.g., as a ꢂavor compound in the perfume and food industry. α-Terpineol has antimi-
crobial, insecticidal, and antifungal activity. In medicine, α-terpineol is valued for its
anti-inꢂammatory activity, due to its ability to suppress the production of inꢂamma-
tory mediators, and its analgesic activity due to its inhibitory eꢃect on inꢂammatory
cytokines responsible for the development of neuropathic pain [14]. α-Terpineol
is produced on an industrial scale by hydration of pinene or turpentine oil to cis-
terpine hydrate with aqueous mineral acids, followed by its partial dehydration
to terpineol [13]. α-Terpineol can also be obtained by bioconversion and hydra-
tion of limonene. Among the possible by-products belong terpinolene, p-cymene,
α-terpinene, γ-terpinene, or α-terpinyl acetate. The initial conditions of this work
resulted from the conditions found in the literature [15].
Perillyl alcohol, 4-(1-methylethenyl)-1-cyclohexenyl-1-methanol, is a monocyclic
terpene occurring in cumin, lavender, mint, and lilac oil [16]. It is used in the chemi-
cal and food industry, due to its antibacterial and antifungal activity [17], in the per-
fume industry [18], and it is used in the pharmaceutical industry as well. A recent
study [16] showed that perillyl alcohol could inhibit the growth of tumor cells; thus,
it can be potentially used in cancer treatment. Perillyl alcohol can be prepared via
the reaction of β-pinene oxide with acetic anhydride, forming perillyl acetate fol-
lowed by saponiꢁcation using catex or other acid catalysts [19–21]. Another option
is a direct rearrangement of β-pinene oxide. In this process, two rings of β-pinene
oxide have to be opened, one is an oxirane ring, and the other is a four-membered
carbon ring in the structure of β-pinene oxide [19]. In the previous works, the eꢃect
of solvents on the selectivity to perillyl alcohol [22] was studied, the inꢂuence of Fe
loading in zeolite beta on the reaction course in β-pinene oxide rearrangement [19],
and also the addition of nitric acid to the reaction mixture [19].
1
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Preparation of α-terpineol and perillyl alcohol using zeolites…
Table 1 Properties of zeolite
Zeolite
Si/Al ratio
Surface
from the producer
area
2
(
m /g)
Beta 25
Beta 38
25
38
680
710
Table 2 Characterization
pyridine
Zeolite
Tmax1 (°C)
Tmax2 (°C)
Acid sites n
μmol/g
ads
of materials obtained from
temperature programmed
desorption of pyridine
(
)
cat
Σ
Weak
Strong
Beta 25
Beta 38
257
245
606
617
2229
821
432
318
1797
503
Chosen catalytic reactions were carried out over zeolites beta. The inꢂuence of
reaction conditions on the reaction course was studied, showing some interesting
results. Both products obtained are very important compounds, and their production
catalyzed by available zeolite beta was simple. These two reactions should demon-
strate the possibility of the usage of these processes as an alternative method for the
preparation of chosen compounds on an industrial scale.
Experimental
Limonene (purity 96%) and β-pinene oxide (technical) were obtained from Aroma
a.s. (Czech Republic). β-Pinene oxide was distilled prior its use to obtain a purity of
9
0%. Dimethyl sulfoxide (p.a.), toluene (p.a.), formic acid (85%, p.a.), sulfuric acid
(
96%, p.a.) and acetic acid (99%, p.a.) were purchased from Penta (Czech Republic).
p-Toluenesulfonic acid (monohydrate, p.a.) was purchased from Lachema (Czech
Republic). Demineralized water was taken from UCT Prague sources (<1 μS/mL).
Zeolites beta 25 and beta 38 were purchased from Zeolyst Int. (USA). Values of Si/
Al ratio and speciꢁc surface area (Table 1) were obtained from the producer (Zeo-
lyst Int.; USA). Information about acidity of zeolites beta was obtained using tem-
perature programs desorption of pyridine (Table 2).
Zeolites beta were activated at 450 °C for 4 h prior its use in a catalyzed reaction
in some cases. In a typical experiment (limonene hydration), the activated catalyst
(
50 wt% based on the weight of limonene) was inserted into two-necked round bot-
tom ꢂask (25 mL) ꢁtted with a condenser and then 10 mL of 10% aqueous acid,
prepared by mixing with demineralized water, was added. The reaction mixture
was heated to the desired temperature and the magnetic stirrer provided vigorous
stirring. Finally, 2 mL of limonene was added into the ꢂask. The reaction mixture
formed a two-phase system. Samples were taken from the organic layer. All sam-
ples were centrifuged to isolate the solid catalyst and the residual aqueous phase.
Then, the samples were diluted and analyzed by GC. Gas chromatograph Shimadzu
1
3

K. Zítová et al.
GC-2010 equipped with a ꢂame ionization detector (FID) and non-polar column
was used. The identiꢁcation of the products was performed using GC/MS.
In a typical experiment (hydration of β-pinene oxide (BPO)), activated cata-
lyst (25 wt% based on the weight of BPO) was inserted into a two-necked round
bottom ꢂask (25 mL) ꢁtted with a condenser. Then, a solvent (volume ratio
BPO:solvent=1:5) and demineralized water (molar ratio BPO:H O=1:8) were
2
added. The reaction mixture was heated to the desired temperature and the magnetic
stirrer provided vigorous stirring and then ꢁnally, 0.8 mL of β-pinene oxide (BPO)
was added to the ꢂask. All taken samples were centrifuged to isolate the solid cata-
lyst, diluted and analyzed by GC. Gas chromatograph Agilent equipped with a ꢂame
ionization detector (FID) and chiral column was used. The identiꢁcation of the prod-
ucts was performed using GC/MS.
The conversion (x) and selectivity (s) were calculated according to Eqs. 1 and 2:
c − c
0
ꢀ
x =
× 100
(1)
c
0
where c refers to the initial relative concentration of reactant, c refers to the rela-
0
τ
tive concentration of reactant at time τ.
c
P
s = ∑ c × 100
(2)
where c refers to the relative concentration of the desired product, Σc refers to the
P
sum of the concentrations of all reaction products.
Results and discussions
The inꢂuence of reaction conditions on the reaction course was studied to optimize
these conditions to achieve the highest possible conversion of reactants and the
highest possible selectivity to the desired products. The studied parameters included
temperature, the type and the amount of catalyst, and an addition of acid.
Catalysts characterization
Table 1 describes the properties of used zeolites, and Table 2 shows the characteri-
zation data obtained from TPD of pyridine.
Temperature programmed desorption (TPD) of pyridine was carried out [17]
using an AutoChem II Micromeritics Instrument 2920. For desorbed pyridine detec-
tion, a thermal conductivity detector (TCD) and quadrupole mass spectrometer
(
MKS Cirrus 2 Analyzer) with a capillary coupling system were used. Catalyst sam-
ple (0.1 g) was placed in a quartz U-shaped tube. Prior to adsorption of pyridine,
−
1
the catalyst was heated under a helium ꢂow (30 mL min ) up to 450 °C and kept
at 450 °C for 60 min to remove impurities from the sample and clean the catalyst
surface. In the following step, the sample was cooled down to an adsorption tem-
perature of 150 °C. Measured pulses of pyridine (pulse volume, 5 mL) were injected
1
3

Preparation of α-terpineol and perillyl alcohol using zeolites…
into the helium gas and carried through the catalyst sample until adsorption satura-
tion. Then, the sample was ꢂushed with helium for 120 min to remove physisorbed
−
1
pyridine. Afterward, the linear temperature program (5 °C min ) was started at a
temperature of 150 °C and the sample was heated up to a temperature of 900 °C.
The amounts of desorbed pyridine were determined by calibration of the intensity of
the 76 amu MS response [9, 23].
Preparation of α‑terpineol
Preparation of α-terpineol by hydration of limonene was carried out using aqueous
acetic acid (based on literature [15]) and a catalyst zeolite beta 25. Product distri-
bution shows that α-terpineol was the main product of this reaction (Fig. 1). By-
products of hydration of limonene in the presence of acetic acid included mainly
eucalyptol, α-terpinene, p-cymene (Fig. 1) and α-terpinyl acetate. The inꢂuence of
the temperature was evaluated together with the inꢂuence of the amount of catalyst
and inꢂuence of the type and the amount of added acid.
In the ꢁrst attempt, a temperature range 50–100 °C was studied. The lowest con-
version after 24 h was achieved when the reaction was carried out at 50 °C (36%).
The achieved conversion increased with increasing temperature (43% at 70 °C, 48%
at 100 °C, Fig. 2A). But the diꢃerence between the temperature 70 and 100 °C was
almost in the range of measurement error. This trend may be observed in checking
the reaction rate based on the achieved conversion of limonene (Fig. 2A), the dif-
ference between these two temperatures seemed negligible. On the other side, it has
been found that the temperature signiꢁcantly inꢂuenced the selectivity to the desired
α-terpineol. Although the highest conversion was achieved at 100 °C, the selectivity
to α-terpineol was low at this temperature (Fig. 2B). In this ꢁgure, the dependence of
the selectivity to α-terpineol on the conversion of limonene is depicted. The strong
inꢂuence of the temperature on the selectivity is given by the fact that with increas-
ing temperature the side reactions preferably took place. The most important by-
product was in all cases α-terpinene that is produced either directly from limonene
by isomerization or by dehydration of the desired α-terpineol. The latter mentioned
reaction was probably the main reason of decrease of selectivity to α-terpineol with
increasing conversion under the temperature 100 °C. The same explanation may be
applied on the temperature 70 °C, where the decrease of selectivity to α-terpineol
with increasing conversion was also visible. Thus, it can be concluded that the
Fig. 1 Products of limonene rearrangement
1
3

K. Zítová et al.
5
0 °C
70 °C
00 °C
B 100
A 60
50 °C
7
1
0 °C
00 °C
1
5
4
3
2
1
0
0
0
0
0
80
6
4
2
0
0
0
0
0
0
10
20
30
40
50
60
0
4
8
12 16 20 24
Time[h]
Conversion[%]
Fig. 2 Inꢂuence of temperature-dependence of A—conversion of limonene on the reaction time and B—
selectivity to α-terpineol on conversion of limonene. Conditions: limonene (2 mL), 10% aqueous acid
(
demineralized water) (10 mL), activated catalyst (50 wt%)
consecutive reactions took place under the temperatures 70 °C and higher, resulting
in a decrease of selectivity to α-terpineol.
The highest selectivity to α-terpineol (88%) and the highest yield (32%) was
achieved after 24 h at 50 °C, when the conversion reached 36%. The selectiv-
ity increased with increasing conversion using 50 °C, which is in accordance with
the results of the experiments with varying amount of catalyst (Fig. 3B). All these
experiments were carried out at 50 °C and the amount 10, 20, 30 and 50 wt% of zeo-
lite beta 25 based on the amount of limonene were tested. The reaction using only
aqueous acetic acid without zeolite beta was carried out for comparison and only
3
% conversion of limonene was achieved after 24 h. The conversion of limonene
increased as expected with the increasing amount of catalyst. The highest conversion
B 100
A 50
1
2
3
5
0 wt.%
0 wt.%
0 wt.%
0 wt.%
80
4
3
2
1
0
0
0
0
60
40
20
0
10 wt.%
20 wt.%
30 wt.%
50 wt.%
0
0
4
8
12
16
20
24
0
10
20
30
40
Time [h]
Conversion [%]
Fig. 3 Inꢂuence of catalyst amount-dependence of A—conversion of limonene on reaction time, B—
selectivity to α-terpineol on conversion of limonene. Conditions: limonene (2 mL), 10% aqueous acid
(
demineralized water) (10 mL), activated catalyst beta 25: amount 10 wt%, 20 wt%, 30 wt% and 50 wt%
based on the weight of limonene, temperature: 50 °C
1
3

Preparation of α-terpineol and perillyl alcohol using zeolites…
of limonene was achieved in the case of using 50 wt% of beta 25 after 24 h (Fig. 3A).
−
1
−1
−1
−1
The reaction rate increased (0.032 mmol h mL <0.040 mmol h mL <0.043
−1
−1
−1
−1
mmol h mL <0.061 mmol h mL ) with the increasing amount of catalyst.
−1
−1
The highest reaction rate 0.061 mmol h mL was observed using 50 wt% of zeo-
lite. For this purpose, it was suitable to use the catalyst in an amount of 50 wt%. We
expect that the higher amount of catalyst would cause even higher conversion and
the same eꢃect would have the prolonged time of the reaction. Nevertheless, the
higher amount of catalyst would cause the stirring problems, thus we decided to use
5
0 wt% of catalyst based on limonene amount for further experiments. Dealing the
selectivity, its value was not at all inꢂuenced by the catalyst amount as expected.
Furthermore, the necessity of the presence of acetic acid in the reaction mixture
was studied. 10% and 30% aqueous acetic acid solutions were used in these experi-
ments and the reaction without the addition of acid was carried out, for comparison.
The results showed the same values of the conversion of limonene (43%) achieved
after 24 h for reactions using 10% and 30% acid solutions in the reaction mixtures. It
means that the higher amount of acetic acid in the reaction mixture did not acceler-
ate the reaction. This result conꢁrmed that the acetic acid did not act literally as a
catalyst in the reaction mixture. On the other side, a similar course of conversion
growth, but with half the values, was observed in the reaction without acid (only
2
2% after 24 h). So acetic acid accelerates somehow the conversion, but the rate was
not dependent on the increasing amount of acetic acid in the reaction mixture.
Reaction with the presence of 10% acetic acid solution was the most selective
toward desirable α-terpineol. In the case of the reaction with 30% acid solution in
the reaction mixture, the selectivity to α-terpineol was aꢃected by the formation of
corresponding ester. This conclusion was also supported by the literature [4], where
it was described that the usage of glacial acetic acid led to the preferential formation
of α-terpinyl acetate. From terpinyl acetate the desired terpineol may be obtained
by hydrolysis, nevertheless to avoid one reaction step is always advantageous. On
the other side, the lowest selectivity to α-terpineol was observed under the acid-free
reaction. The results claim that the presence of even a small amount of acetic acid
was crucial for achieving higher selectivity to α-terpineol in the limonene hydration.
It is possible that acetic acid served only as an activator for hydration, or terpinyl
acetate might be the intermediate of the reaction supposing that the hydrolysis of
terpinyl acetate was preferred under used reaction conditions.
To ꢁnd more details about the role of acetic acid in the reaction mixture, a series
of experiments were carried out using diꢃerent acids to ꢁnd suitable acid for the
hydration of limonene. Selected acids included sulfuric acid, p-toluenesulfonic acid
(
PTSA), formic acid and acetic acid. The strength of acids represented by pKa value
is shown in Table 3.
All acids were used as 10% aqueous solutions. The dependence of limonene
conversion on time (Fig. 4A) shows that the conversion increased over time in
all cases. As the strong acids may deꢁnitely serve as catalysts of hydration reac-
tion, the conversion growth was dependent on the acid´s pKa. The most signiꢁ-
cant growth of the conversion was observed for p-toluenesulfonic acid. p-Tol-
uenesulfonic acid was the strongest organic acid tested (Table 1). Sulfuric acid
that possesses by the highest pKa is oppositely to other used acids preferably
1
3

K. Zítová et al.
Table 3 Strength of acids
Acid
pKa
represented by pKa values [24,
2
5]
CH COOH
4.75
3.75
− 1.30
3
HCOOH
PTSA
H SO
− 3.00
2
4
HCOOH
H2SO4
PTSA
A 60
B 100
5
4
3
2
1
0
0
0
0
0
8
6
4
2
0
0
0
0
CH3COOH
HCOOH
H2SO4
PTSA
CH3COOH
0
0
0
1
2
3
4
5
0
10
20
30
40
50
Time [h]
Conversion [%]
Fig. 4 Inꢂuence of acid type-dependence of A—conversion of limonene on reaction time, B—selectivity
to α-terpineol on conversion of limonene. Conditions: limonene (2 mL), 10% aqueous acid (demineral-
ized water) (10 mL), activated catalyst beta 25 (50 wt%), temperature: 70 °C
dissolved in the water phase, thus the reaction course was probably aꢃected by
this fact. The use of formic acid was not very eꢃective, because this acid can-
not be included to the group of strong acids. Even though it has higher pKa
than acetic acid it was less eꢃective in both catalysis the hydration of limonene
and addition to limonene double bond (no formiate was detected in the reaction
mixture). The lower eꢃectivity of formic acid comparing acetic acid in the reac-
tion was already described elsewhere [26]. This corresponds to the results of the
experiment shown in Fig. 4A.
Figure 4B shows that under the stated conditions, the selectivity decreased
with increasing conversion, as it was explained in the paragraph dealing with the
inꢂuence of temperature. The results showed that the strong acids had a negative
eꢃect on the selectivity toward the desirable product, though high conversion of
limonene has been achieved using these acids. In contrast, weak acetic acid has
been shown to be suitable for the selective hydration of limonene. In the case of
strong acids, the low selectivity to α-terpineol can be explained by competitive
and consecutive reactions, which are supported by strong acids, especially by
dehydration of α-terpineol to form α-terpinene and terpinolene.
A comparison of catalytic activity of zeolites beta 25 with other types of cata-
lysts in the hydration of limonene in the literature is shown in Table 4.
1
3

Preparation of α-terpineol and perillyl alcohol using zeolites…
Table 4 Results of preparation of α-terpineol by hydration of limonene using various catalysts
Row Catalyst
Solvent
Tem-
Time (min) Conversion
(%)
Selectivity
(%)
References
This work
perature
(
°C)
1
Zeolite beta
Acetic acid/
50
1440
36
88
2
5
H O
2
2
3
Amberlyst 15 Acetic acid
25
50
40
3
0.15a,b
9
[27]
[15]
Fe-beta
Acetic acid
1440
19
zeolite
4
5
H PW O / Acetic acid
15
25
20
170
1560
420
16
57
54
0.64a,b
55
[27]
[27]
[28]
3
12 40
2
SiO
H PW O
Acetic acid/
3
12 40
H O
2
6
CF COOH
Toluene
82
3
a
mol/l
b
Selectivity to α-terpineol+α-terpinyl acetate
Preparation of perillyl alcohol
The following part of this work deals with the isomerization of β-pinene oxide
BPO) in the presence of water to obtain perillyl alcohol. In previous works [e.g.,
9], a lot of attention was paid to the isomerization of β-pinene oxide. Still, based
(
2
on our knowledge, the addition of water has not been studied in the literature so far.
Since the water was present in the reaction mixture, the hydration also took place,
forming p-menth-1-ene-7,8-diol as a product. Nevertheless, p-menth-1-ene-7,8-diol
can be easily transformed into perillyl alcohol by acid-catalyzed dehydration. Other
products identiꢁed in the reaction mixture were myrtanal and myrtenol (Fig. 5).
These products are also the products of β-pinene oxide acid-catalyzed isomeriza-
tion, thus we can say that in the reaction mixture at least two competitive reactions
take place—(1) acid-catalyzed isomerization leading to the formation of myrtanal,
myrtenol and perillyl alcohol, and (2) acid-catalyzed hydration leading to the forma-
tion of p-menth-1-ene-7,8-diol.
Fig. 5 Products of β-pinene oxide rearrangement
1
3

K. Zítová et al.
As in the previous part of this work, zeolite beta was used as a catalyst. Firstly,
the catalytic activity of beta zeolites 25 and 38 was compared. In general, the
number of acid centers in the structure of zeolites, which are essentials for the
catalytic activity of the material, decreases with increasing Si/Al ratio. Values
of Si/Al ratio and information about the acidity of the used zeolites are shown
in Tables 1 and 2. Therefore, the often-valid rule is based on the fact: the lower
the Si/Al ratio, the higher the catalytic activity; this conꢁrmed TPD of pyridine
measurement. Furthermore, the eꢃect of calcination of zeolite beta on its catalytic
activity was investigated. The calcination removes absorbed substances, espe-
cially water, from the zeolite structure. On the other site, in the case of hydration,
the adsorbed water could have a positive eꢃect on the reaction course. A com-
parison of the results for calcined zeolites beta 25 and 38 showed that the reac-
tion with beta 25 ran faster as expected than the reaction over beta 38 (Fig. 6).
Selectivities toward perillyl alcohol and toward by-products in both reactions
were comparable. Figure 6 shows that the reactions catalyzed by non-activated
zeolites ran slower than reactions catalyzed by the activated ones. The results
conꢁrmed that water absorbed on the surface and in the structure of non-activated
zeolites aꢃected the catalytic activity of the zeolite. The transport of the substrate
to catalytic center was decreased by the presence of water on the surface. On the
other side, the usage of non-activated beta zeolites inꢂuenced the composition of
the reaction mixture diꢃerently. Water molecules present on the catalyst surface
helped with the hydration of BPO producing a higher amount of p-menth-1-ene-
7
,8-diol (Table 5). Also, the selectivity to perillyl alcohol slightly increased that
is in the accordance with our supposition that perillyl alcohol may be formed in
the reaction mixture either by direct isomerization or dehydration of p-menth-1-
ene-7,8-diol. Nevertheless, still relatively high amount of myrtanal and myrtenol
was present in the reaction mixture showing that BPO acid-catalyzed isomeri-
zation took place faster comparing the acid-catalyzed hydration. Isomerization
under conditions that we used (excluding the presence of water) is the reaction
that proceeds fast as can be seen from literary data [19, 22].
Fig. 6 Inꢂuence of catalyst
type-dependence of conver-
sion of BPO on reaction time.
Conditions: BPO (0.8 mL),
demineralized water (molar
100
80
ratio BPO:H O=1:8), solvent:
2
6
4
2
0
0
0
0
dimethylsulfoxide (volume ratio
BPO:DMSO=1:5), catalyst
(
25 wt%), temperature: 70 °C
beta 25 acꢀvated
beta 38 acꢀvated
beta 25
beta 38
0
5
10
15
20
25
30
Time [min]
1
3

Preparation of α-terpineol and perillyl alcohol using zeolites…
Table 5 Selectivities toward products of the reaction. Conditions: BPO (0.8 mL), demineralized water
(
mol.ratio BPO:H O=1:8), solvent: DMSO (volume ratio BPO:DMSO=1:5), catalyst (25 wt%), tem-
2
perature:70 °C
Catalyst
Selectivity (%)
Perillyl alcohol
p-Menth-1-en-7,8- Myrtanal
Myrtenol
diol
Beta 25 activated
Beta 38 activated
Beta 25
30
30
36
34
5
5
9
9
23
24
19
17
18
18
10
12
Beta 38
Thus, particular attention was given to the inꢂuence of the amount of water in
the reaction mixture that can positively inꢂuence the amount of p-menth-1-ene-7,8-
diol and perillyl alcohol. Series of experiments were carried out with molar ratios
BPO:H O=1:1, 1:5, 1:8 and 1:15. The total conversion was achieved faster as
2
expected with the increasing amount of water in the reaction mixture (as the reaction
mixture was homogeneous, Fig. 7). While the increasing amount of water did not
aꢃect the selectivity to perillyl alcohol, it aꢃected the selectivity toward p-menth-1-
ene-7,8-diol. The selectivity to p-menth-1-ene-7,8-diol increased with the increas-
ing amount of water (Table 6). These results indicate that the addition of a higher
amount of water supported the formation of p-menth-1-ene-7,8-diol, meaning the
BPO hydration. At the same time, the water present in the reaction mixture sup-
pressed the subsequent dehydration of p-menth-1-ene-7,8-diol into perillyl alcohol
as expected. But the rate of hydration was still signiꢁcantly lower comparing to
competitive isomerization.
Fig. 7 Inꢂuence of molar
100
ratio BPO:H O-dependence
2
of conversion of BPO on reac-
tion time. Conditions: BPO
80
(
(
0.8 mL), demineralized water
molar ratio BPO:H O), solvent:
2
dimethylsulfoxide (volume ratio
BPO:DMSO=1:5), non-acti-
vated catalyst beta 25 (25 wt%),
temperature: 70 °C
60
1
:1
4
2
0
0
1:5
1
1
:8
:15
molar raꢀo
BPO:H2O
0
0
5
10
15
20
25
30
Time [min]
1
3

K. Zítová et al.
Table 6 Selectivities toward
products of the reaction.
Conditions: BPO (0.8 mL),
demineralized water (mol.
Molar ratio Selectivity (%)
BPO:H O
2
Perillyl alcohol p-Menth-1- Myrtanal Myrtenol
en-7,8-diol
ratio BPO:H O), solvent:
2
DMSO (volume ratio
1:1
30
30
29
29
0
3
5
21
19
22
19
24
22
18
19
BPO:DMSO=1:5), non-
activated catalyst beta 25
1
1
1
:5
:8
:15
(
25 wt%), temperature:70 °C
11
A comparison of catalytic activity of zeolites beta 25 and beta 38 with other
types of catalysts in the isomerization of β-pinene oxide presented in the literature is
shown in Table 7.
Conclusion
This work broadens the knowledge about the production of chosen terpenic
compounds—α-terpineol and perillyl alcohol. During the hydration of limonene,
it was found that the reaction rate increased with temperature, with the increasing
amount of catalyst, and with the speciꢁc amount of acetic acid. The selectivity to
α-terpineol (as the main hydration product) increased with conversion only at 50 °C;
at higher temperatures, the formation of consecutive products took place. The addi-
tion of a weak organic acid to the reaction mixture had a positive eꢃect on both
the reaction rate and the selectivity to α-terpineol. However, with a higher amount
Table 7 Results of preparation of perillyl alcohol by isomerization of β-pinene oxide using various cata-
lysts
Row Catalyst
Solvent
Tem-
Time (h) Conversion
(%)
Selectivity
(%)
References
perature
(
°C)
1
2
3
4
5
Zeolite beta 25 DMSO
70
80
80
2
1
1
6
6
100
50
14
35
34
36
34
5
13
22
This work
[30]
[30]
[31]
[31]
MCM-41
SiO2
Hexane
Hexane
USY
Nitromethane 80
Nitromethane 80
Dowex
5
0WX2
6
CrCl /IL1/
Hexane
70
4
100
25
[32]
3
ACC
7
8
9
1
1
FeCl3
DMSO
DMSO
Acetone
Toluene
DMSO
70
70
56
70
70
24
24
2
0.3
3
96
98.4
90
100
48.2
49.1
66.1
13
19
46.3
[22]
[22]
[33]
[29]
[19]
Sn-MCM-41
Sn-Beta
Sn-Y-12
Fe-beta-5
0
1
1
3

Preparation of α-terpineol and perillyl alcohol using zeolites…
of acid, the selectivity was aꢃected by the preferential formation of by-products.
The highest selectivity to α-terpineol was achieved under the following conditions:
5
0 wt% of beta 25, 10% aqueous acetic acid solution, 50 °C. After 24 h of the exper-
iment, 36% conversion and 88% selectivity to α-terpineol were achieved. The prepa-
ration of perillyl alcohol was performed by isomerization of β-pinene oxide. Due to
the presence of water in the reaction mixture, hydration of β-pinene oxide took place
as well as p-menth-1-ene-7,8-diol formation. Although the amount of p-menth-1-
ene-7,8-diol increased with an increasing amount of water, the reaction rate of its
formation was still signiꢁcantly low, and isomerization was the main reaction that
occurred. A total conversion of β-pinene oxide was usually achieved within 2 h of
the experiment. The reaction rate increased with the increasing amount of catalyst
and with the increasing amount of water in the reaction mixture. Zeolite beta 25
was evaluated as a more suitable catalyst for the reaction comparing zeolite beta
3
8. The highest selectivity to perillyl alcohol (36%) was achieved in the reaction
under the conditions: solvent dimethyl sulfoxide, non-activated catalyst beta 25 in
an amount of 15 wt%, demineralized water in a molar ratio of BPO:H O 1:8, tem-
2
perature 70 °C. The highest selectivity to the product of hydration p-menth-1-ene-
7
,8-diol (11%) was achieved using solvent dimethyl sulfoxide, non-activated catalyst
beta 25 (25 wt%), demineralized water in a molar ratio of BPO:H O 1:15, tempera-
2
ture 70 °C.
α-Terpineol is prepared in the industry mainly by hydration of α-pinene. How-
ever, this work conꢁrmed that hydration of limonene catalyzed by zeolite beta could
be an alternative method for the preparation of this important compound. The prob-
lem of the selective preparation of perillyl alcohol remains the competitive acid-
catalyzed isomerization forming myrtanal and myrtenol that proceeded with a high
rate. However, under the given conditions using zeolite beta, we were able to achieve
comparable results as reported in the literature.
Acknowledgements We thank Eva Vrbková, Ph.D. (Department of Organic Technology, UCT Prague)
for providing TPD measurements. This work was supported from the grant of Speciꢁc university
research—Grant No. A1_FCHT_2021_005.
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