Prime Research on Medicine (PROM)

ISSN: 2315-5302. Vol. 2(5), pp. 120-123, November 8th, 2012

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Full Length Research

Study of homogeneous acid catalysis for the hydration

of -Pinene
1
Nanik Wijayati, 2Harno Dwi Pranowo and 3Jumina Triyono
1
Student of Doctorate Program, Department of Chemistry, Faculty of Mathematics and Natural Sciences, Universitas
Gadjah Mada, Yogyakarta
2
Department of Chemistry, State University of Semarang, Jl. Raya Sekaran Gunungpati Semarang
3
Department of Chemistry, Faculty of Mathematics and Natural Sciences, Universitas Gadjah Mada, Yogyakarta
th
Accepted 18 October, 2012

Homogenous acid was used as catalyst for the hydration of -pinene using water as hydroxyl donor, which is
soluble in aqueous and organic solvents. -pinene is the main component of most turpentine oils. In order to
obtain more valuable products, -pinene in the turpentine can be hydrated in dilute mineral acid solutions to
produce - terpineol, which can be used as perfume, repellent of insect, antifungal and disinfectant. The
Highest selectivity of terpineol was 74% with a convertion of 88% after 30 min of reaction at 70 oC.

Keywords: pinene, homogeneous acid, and terpineol.

INTRODUCTION

Turpentine is generally produceed in places having vast
tracts of pine. Chemically, turpentine is a mixture of cyclic
monoterpene hydrocarbons, C10H16, such as -pinene,
camphene. -pinene and 3-carene being -pinene the
predominant constituent. The chemical reactivity of
turpentine varies with its composition but generally is the
characteristic of -pinene. -Pinene is known to react
readily in the presence of acids through hydration
reaction (M. Aguirre et al, 2005; Avilla et al, 2010).
The hydration of -pinene via acid catalysis is an
important method for alcohol synthesis, and has several
applications in the perfume and pharmaceutical industries
(Bhatia, 2008). -Terpineol, 4-terpineol and terpineol
hydrate are from commercial viewpoints, the most
interesting derivatives of -pinene. -Terpineol exhibits
anticonsulvant and antimicrobial activity and is used for
wound healing and insect bites (Damaiao et al, 2007;
Liauw, et al, 2010).
There exists an important amount of publications in
which the hydration of -pinene is studied using different
catalysts. Pakdel et al, (2001) used aqueous solutions of
sulfuric acid as catalyst in the presence of acetone to
obtain terpineol from crude sulphated pine oil. Robles-
Dutenhefner et al. (2001) used HPW 12O40 as catalyst and
mixture of acetic acid and water as solvent for hydrating
-pinene. Vital et al, (2001) reported the use of solid acid
catalysts such as zeolites and impregnated
phosphomolibdic acid (HPMo) on polymeric membranes
for -pinene hydration. Yadav et al. (2009) reported the
use cation-exchange zeolite beta to acetoxylation and
hydration of limonene and -pinene.
The objective of this work is to study the role of
trichloroacetic acid, monochloroacetic acid and sulfuric
acid catalysts to hydrate -pinene to terpineol using
water as the hydroxyl group donor.
MATERIALS AND METHODS
Experimental
Materials
-Pinene was obtained from fractination distillation of
turpentine oil. Trichloroacetic acid (TCA),
monochloroacetic acid (MCA) and sulfuric acid (SA)
were Fisher Science products. The reagents were not
purified before its use.
Instrumentation
Analysis of the reaction products was performed by Gas
Chromatography (GC) (Hewlett Pacard 5890 Series II
equipped with flame ionization detector/FID). The column
used was HP5 (% Phenyl Methyl Siloxane). The temper-
ature of the column was adjusted to be 70oC for 5 min and
o o
then increased to 280 C by 10 C/min. The carrier gas
121 Prim. Res. Med.

Table 1: Hydration of -pinene over the homogeneous catalyst a

Catalyst Time -pinene (%) Camphene (%) Limonene (%) Terpinolene (%) Terpineol (%)
H2SO4 30 27.4 3.7 8.91 14.89 35.05
60 7.71 4.05 20.29 12.5 40.19
120 0.27 2.53 22.63 11.79 35.71
240 0.04 2.52 26.8 11.97 11.04
a
MCA 30 84.77 3.74 1.88 0.24 7.89
60 71.41 2.98 3.16 2.93 18.25
120 63.06 4.08 3.68 4.4 23.09
240 45.35 3.6 6.4 4.36 33.98
b
TCA 30 11.63 1.59 21.4 8.69 21
60 10.27 8.2 20.16 8.35 20.73

120 9.26 8.7 21.73 7.66 20.61

240 5.47 7.11 23.63 7.37 23.68

a
MCA = monochloroacetic acid
b
TCA = trichloroacetic acid

120 0.25 mol of -pinene, 0.6 mol of water and 20 mL of

aceton were first placed. After heating to the desired
100 temperature (70oC), 0.11 mol of the catalyst was added.
Aliquots were extracted with a micropipette and
conversion (%)

80 immediately analyzed with GC. Conversion (X) was

60 defined here as moles of monoterpene converted per 100
SA moles of monoterpene feed. The selectivities of -
40 MCA terpineol (S) were defined as moles of -terpineol
formed per 100 moles of -pinene converted.
20 TCA
0 RESULTS AND DISCUSSION
Alkenes having carbon number more than four are
30 60 120 240 transformed not only to alcohols but also to isomerized
reaction time (min) alkene when the alkenes are treated with water in the
presence of acid catalyst. In this case or a-pinene, more
complicated products are formed because of ring
opening. They could be classified into groups as
Fig. 1: -Pinene conversion vs reaction time curves,
monocyclic alcohols, monocyclic hydrocarbon, and
(SA=Sulfuric Acid; MCA=Monochloric Acetic Acid;
and TCA=Trichloro Acetic Acid) bicyclic hydrocarbons (see Table 1).
Conversion and selectivity to terpineol curves, plotted
against time for each catalyst are shown in Figs. 1 and 2,
respectively. As was mentioned before, chloroacetic acid
used was helium (He) (0.1L/min flow). The injection and is completely soluble on the system at 70oC and showed
o
detection temperatures were set to be 280 and 300 C, a conversion of 99%, with selectivity of 59%. The good
respectively and the split mode was 1/100. The various performance of chloroacetic acid as catalyst must be due
components were characterized by FTIR and GC-MS to the high affinity for both phases organic and aqueous,
instrument. since this promotes the transfer of hydroxyl anion to
organic phase in such a way, that the carbocation
Procedure hydration reaction is faster than rearrangement reactions
The catalytic tests were performed in a 100-cm3 three- which produce -pinene isomers. A similar research was
necked-glass reactor with condenser and thermocouple. observed by Robles-Dutenhefner et al., a conversion of
The reactor was submerged in thermostatic bath with 90% was observed in the homogeneous reactions, with
silicone oil and magnetic stirring. In batch experiment, selectivites araound 85% for monocyclic and bicyclic
 Wijayati et al., 122

70 interesting for industrial application, mainly due to the

absence of chlorinated compounds and for the easy
60 separation and purification of this catalyst from the
Selectivity (%)

50 reaction media if compared with sulfuric acid. No other

40 co-catalyst as ion exchange resins is necessary to obtain
30 SA good selectivity and high conversion on the hydration of -
20 MCA pinene to terpineol with chloroacetic acid. This result is
10 notable for industrial purposes, other advantages with
TCA this catalyst are the absence of chlorinated by- product,
0
and the capability to recover catalyst by simple
30 60 120 240 recristalization.
reaction time (min) CONCLUSION
The homogeneous catalyst converted -pinene into
hydrocarbons, while the chloroacetic acid catalyst was
active and selective for producing alcohols, with a
Fig. 2: Selectivity to terpineol vs reaction time curves
conversion of 88% and showed 74% selectivity for
o
terpineol after 30 min of reaction at 70 C. The good
results were due to its strong acidity during reaction and
its easy separation from reaction products. The yield
obtained by using this catalyst was interesting for
+ industrial application.
H+ Hydration

ACKNOWLEGMENTS
-H +
OH The authors would like to thank to Directorate General of
-pinene
Higher Education (DIKTI), Department of National
Isomerization -terpineol
Education Republic Indonesia for the Fundamental
Research grant.

camphene
limonene
terpinolene
Fig. 3: Reaction scheme for the hydration of -pinene
over homogeneous catalysts
alcohols, but the acid had to be recovered from the
reaction liquid due to its strong acidity and contamination
problems. Aguirre et al., also demonstrated that the
hydration of -pinene with homogeneous catalysed. The
higher conversion was 90% with selectivity of 70% after 4
o
h of reaction at 70 C.
Chloroacetic acid is misible with pinene and also
soluble in water, due to these two factors, this catalyst,
beside s the formation of the proton to form the
carbocation, fsvors the transfer of OH- to organic phase
and as a result, hydration yield is the highest of the
studied catalysts. Chloroacetic acid was found as good
catalyst for the production of terpineol from -pinene. The
good results are due to strong acidity and high solubility
and affinity with aqueous and organic phases during
reaction. The obtained yield with this catalyst is
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