Anda di halaman 1dari 5

Prime Research on Medicine (PROM)

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

Full Length Research

Study of homogeneous acid catalysis for the hydration

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


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

MCA = monochloroacetic acid
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
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
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,
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
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

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

Avila MC, Nora A, Cornelli E, Rodriguez-Castellon A.
Jimenez-Lopez. Study of solid acid catalysis for the
hydration of -pinene. J.Mol. Catal. A: Chemical.
2010., 322, (1-2), 106-112.
Bhatia SP. Fragrance Material Review on Terpineol.
Food.chem.toxico. 2008, 46: 5275-5279.
Damaiao P, de S, Lucindo Q, Jr. Reinaldo N, de A.
Fig. 3: Reaction scheme for the hydration of -pinene Evolution of the anticonsulvant Activity of -terpineol.
over homogeneous catalysts Pharm. Biol. 2007, 45 (1): 69-70.
Liauw ET, dan Liu KJ. Synthesis of terpinyl acetate by
lipase catalized esterification in supercritical carbon
alcohols, but the acid had to be recovered from the dioxide. Bioresource techno. 2010, 101 : 3320-3324.
reaction liquid due to its strong acidity and contamination Pakdel H, Sharron S, dan Roy C. -Terpineol from
problems. Aguirre et al., also demonstrated that the Hydration of Crude Sulfate Turpentine Oil. J. Agric.
hydration of -pinene with homogeneous catalysed. The Food Chem., 2001, 49 (9), pp 43374341.
higher conversion was 90% with selectivity of 70% after 4 Robles-Dutenhefner PA, Kelly A, Da Silva M, Rafig
h of reaction at 70 C. Siddiqui H, Ivan Kozhevnikov V, Elena V,
Chloroacetic acid is misible with pinene and also Gusevkaya. Hydration and acetoxylation of
soluble in water, due to these two factors, this catalyst, monoterpenes catalyzed by heteropoly acid, J. Mol.
beside s the formation of the proton to form the Catal. A: Chemical. 2001, 175 (1-2): 33-42.
carbocation, fsvors the transfer of OH- to organic phase Roman Aguirre M, De la Torre-Senz L, Antinez Flores
and as a result, hydration yield is the highest of the W, Robau-Snchez A, Aguilar Elguzabal A.
studied catalysts. Chloroacetic acid was found as good Synthesis of terpineol from -pinene by
catalyst for the production of terpineol from -pinene. The homogeneous acid catalysis. Catal. Today. 2005,
good results are due to strong acidity and high solubility 107-108 :310-314.
and affinity with aqueous and organic phases during Vital J, Ramos AM, Silva IF, Valente H, Castanheiro JE.
reaction. The obtained yield with this catalyst is The effect of -terpineol on the hydration of -pinene
123 Prim. Res. Med.

over zeolites dispersed in polymeric membranes,

Catal. Today. 2001, 67, 217-223.
Yadav MK, Patil MV, dan Jasra RV. Acetoxylation and
hydration of limonene and -pinene using cation-
exchanged zeolite beta. J. Mol. Catal. A:Chemical.
2009, 297 (2): 101-109.