Topics in Catalysis Vol. 27, Nos.

14, February 2004 (# 2004) 169

Catalytic conversion of terpenes into fine chemicals

Jose Luiz F. Monteiro
and Claudia O. Veloso
NUCAT/PEQ/COPPE, Universidade Federal do Rio de Janeiro, Rio de Janeiro, CP 68502, CEP21945-970, Brasil

This work reviews the use of terpenes available from renewable resources in the fine chemicals industry. Different products and
processes are discussed. Transformations of terpenes involving isomerization, hydration, condensation, hydroformylation,
hydrogenation, cyclization, oxidation, rearrangement, and ring contraction/enlargement are routes to produce a variety of
compounds of interest to the pharmaceutical, agrochemical, and flavors and fragrances industries.
KEY WORDS: terpenes; renewable resources; catalysis; fine chemicals.

1. Introduction Renewable resources can be used as such or as raw

The chemical industry has flourished, and most of the
processes have been developed in a period when
commitment to sustainable growth was not the main
concern. In such a framework, as also happened in the
field of power generation, the use of renewable resources
has often been neglected. As a consequence, the
chemical industry is often associated with the depletion
of the environment, and at least in a number of cases,
this cannot be denied. What has been considered the cry
of a few fierce ecologists in the past has now become
part of our everyday life. Reducing the impact of
chemical processing on the environment is a must for the
chemical industry either to meet increasingly strict
regulations, to fulfill the expectations of the consumers,
or both. The continuous growth of the world popula-
tion, the necessity to provide the means for people to
maintain or to increase their standards of living,
particularly in developing countries, and the steadily
growing demand for the consumption of products,
stimulated by new technologies and intense advertising,
represent an increasing burden on the environment.
Meeting the present needs cannot be accomplished at
the expense of the future generations, particularly when
soil, air, and water resources clearly show signs of
saturation. The fact that the available oil and gas
reserves are limited, that crop-based technologies con-
tribute to decrease net CO2 emissions, so reducing the
so-called greenhouse effect, and that agricultural feed-
stocks are biodegradable and usually nonhazardous
leads to the conclusion that moving to green chemistry is
inevitable. Producing fuels or chemicals from crops also
creates employment in rural areas [1] and provides
income for rural populations.
materials for producing a variety of chemicals (fine and
bulk) and fuels such as
. fine chemicals (fragrances, flavors, perfumes, pharma-
ceuticals) from essential oils (terpenes) or carbohy-
drates;
. soaps, detergents, surfactants, emulsifiers, plasticizers,
and lubricants from animal and vegetable oils and fats
(triglycerides);
. ethanol (chemical/fuel), acetaldehyde, and acetone
from fermentation of carbohydrate-containing crops
(such as sugar cane, corn, sweet sorghum, rice or
beetroot) and a variety of chemicals derived from the
previous ones;
. methanol (chemical/fuel) via synthesis gas from the
gasification of biomass;
. hydrogen for fuel cells from bioethanol or biometha-
nol;
. fuels (biodiesel) from transesterification of vegetable
oils (soybean, corn, sunflower), even recycled ones, or
from hydrothermolysis of wood or residues [2];
. polyols for the food industry from hydrogenation/
hydrogenolysis of carbohydrates.
Recently, Okkerse and van Bekkum [2] showed that
the production of the top eight organic materials
(polyethylene, polypropylene, polyvinyl chloride, poly-
ethylene terephthalate, polystyrene, butadiene/copoly-
mers, phenol resins and polyamides) from biomass is
technologically feasible, though novel synthetic routes
need to be developed.
This paper addresses one of the above issues: the
production of fine chemicals from terpenes available
from renewable resources.

2. Fine chemicals from renewable resources

Plants are chemical factories under genetic and

To whom correspondence should be addressed. biochemical control [3], which efficiently convert solar
E-mail: monteiro@peq.coppe.ufrj.br energy into stored biomass, by the photosynthesis

1022-5528/04/02000169/0 # 2004 Plenum Publishing Corporation

170 J.L.F. Monteiro and C.O. Veloso/Catalytic conversion of terpenes into fine chemicals

reaction the case, for instance, of citral, a terpene (aldehyde) used in

chlorophyll
n CO2 n H2 O ! CH2 On n O2
light
They contain highly functionalized molecules, which can
be used directly after a number of steps of isolation and
purification or can be further transformed into other
molecules with specific groups responsible for the
desired property, while in many other applications,
isolation of a single species is not necessary. These
molecules (secondary metabolites) are used in a variety
of industries such as those of pharmaceuticals, cos-
metics, flavors, fragrances, pesticides, and pigments
(table 1).
The World Health Organization (WHO) estimates
that 80% of the world population uses plants as a source
of medicines, in one way or another. Most of the drugs
obtained from plants were developed from knowledge
that has been transferred along generations.
On the other hand, environmental, social, political,
and economical aspects cannot be neglected. Loss of
biodiversity, natural forests clearing, competition with
fiber- or food-oriented agriculture, policies for land use,
farmers unwillingness to change their methods, and
land reforming in developing countries are but a few of
the pieces that form a mosaic of real or potential
problems to be faced if chemicals are to be produced on
a large scale from agriculture.
In the past, the impossibility of maintaining a con-
tinuous and steady year-round supply of raw materials and
increasing production costs led many industries to replace
natural products with petrochemical-derived ones. This is
the synthesis of ionones [4]. The natural product, obtained
from citrics and particularly from lemongrass, has been
largely replaced by its synthetic counterpart, produced
from isobutene [5]. Other products that were obtained
from plants, such as caffeine, ephedrine, coumarin,
papaverine, and L-dopa are now mostly produced
commercially by synthetic routes [6].
Fortunately, there has recently been an increasing
search for new catalytic processes for fine chemicals
production based on renewable resources. Many of
these processes rely on the fact that switching from
homogeneous (as mostly practiced nowadays) to hetero-
geneous catalysis may contribute to solving the problem
of waste disposal, besides avoiding or simplifying steps
such as separation, neutralization, recycling, etc.
3. Fine chemicals from terpenes
Terpenes present in plants are generally composed of
several isoprene units joined in a regular, head-to-tail
way, the so-called isoprene rule (figure 1). Compounds
that have two isoprene units are called monoterpenes. In
nature, the isoprene units that build up terpenes are
synthesized from acetic acid by way of the important
biochemical intermediate, isopentenyl pyrophosphate.
They are the most abundant components of the essential
oils of many plants and flowers. Turpentine oleoresin
obtained from coniferous trees and terebinth and
essential oils from citrics are two of the most important
sources of terpenes. Table 2 summarizes some of those
sources.

Table 1
Some plant-derived products or intermediates

Application Product/intermediate Plant

Pharmaceuticals and cosmetics Vincristine, vinblastine Catharanthus roseus

Digitoxin, digoxin Digitalis lanata
Atropine Atropa belladona
Taxol Taxus brevifolia
Tetrahydrocannabinol Cannabis sativa
Lapachol Tabebuia impetiginosa
Levodopa Mucuna sp
Ajmalicine Catharanthus roseus
Morphione, codeine Papaver somniferum
Flavors and fragrances Citral Cymbopogon citratus (lemongrass)
Safrole Sassafras albidum
Jasmine Jasminum grandiflorum
Rose oxide Rosa damascena
Angelica oil Angelica sylvestris
Spearmint oil Mentha virdis
Vanillin Vanilla planifolia
Stevioside Stevia rebaudiana
Pesticides Pyrethrin Chrysanthemum cinerariaefolium
Coumarin Dipteryx odorata (tonka bean)
Pigments Bixin (annatto) Bixa orellana
Saffron Crocus sativus
 J.L.F. Monteiro and C.O. Veloso/Catalytic conversion of terpenes into fine chemicals 171

Table 2
Some terpenes and the plants they are obtained from

isoprene Substance Plant

Pinenes Coniferous trees, terebinth

Limonene Citrics (lemon, orange, etc.)
CH 2OH Citronellal Citronella, eucalyptus
OH Citral Lemongrass, citrics
Geraniol Geranium
Citronellol Citronella
Menthol Peppermint
Eugenol Clove
vitamin A Linalool Lavender
citronellol
Figure 1. Isoprene and two examples of terpenes and their isoprene
units. product. Table 3 shows the extraction technique used for
some essential oils [7]. Due consideration must also be
Terpenes constitute a class of natural products that given to the fact that the physiological properties of a
can be transformed into novel and valuable compounds given terpene (and so its application to the synthesis of
commercially important for the industrial production of pharmaceuticals, agrochemicals, flavors, and fragrances)
fragrances, perfumes, flavors, and pharmaceuticals as are dependent on the relative proportions of the different
well as useful synthetic intermediates and chiral building enantiomers usually present.
blocks. However, many natural oils are nowadays more There is a vast literature on catalytic transformations
expensive than their synthetic components. In the case of of terpenes into valuable chemicals. These transforma-
flavors, natural products are usually preferred since they tions comprise reactions such as isomerization, hydra-
are ingested, and their odor and flavor are usually more tion, condensation, hydroformylation, hydrogenation,
sophisticated than those of synthetics (cf. vanilla beans cyclization, oxidation, rearrangement, and ring contrac-
versus vanillin). This is not the case for fragrances, and tion/enlargement. Some examples of recent studies
most of them are based on synthetics, which, in general, comprising these reactions will now be given.
try to mimic structures found in nature. In the field of
fragrances, one can distinguish the following:
3.1. Isomerization/hydration
essential oils, natural packages of many compounds;
some of them, such as rose oil and geranium oil, are The production of camphor, largely used in the
expensive and are applied as they are; fragrance and the pharmaceutical industry, involves the
natural chemicals, isolated from natural mixtures, isomerization of
-pinene to camphene as an inter-
e.g., limonene and
- and -pinene, which are mediate step.
-Pinene is a very reactive substrate, being
inexpensive starting materials for further synthesis; abundant in the monoterpene fraction of natural
nature-identical compounds, synthetic compounds essential oils such as pine and eucalyptus resins.
with a natural counterpart; Industrially, the isomerization reaction is usually
artificial compounds, which are synthetic with no performed in the liquid phase at temperatures of about
natural counterpart. 423 K over weakly acidic TiO2 catalysts [8], although at
a relatively low rate. For this reason, this reaction has
A perfume, e.g., Chanel-5, is often a mixture of many also been studied over a number of different catalysts,
essential oils and synthetics. usually acidic, such as clays [9], zeolites [1012], and
Once the plant is harvested, its storage and the method
Table 3
used to extract the essential oil may deeply affect the final
Some essential oils and their production method
flavor and odor. The odor and the flavor of natural
extracts are further affected by the specific variety used Oil and production method Plant
and by the local climate characteristics, soil, water
availability, age of the plant, and the way it is cultivated. Sweet orange oil cold-pressed Citrus sinensis
Essential oils are extracted from the plant (leaves, barks, Lemon oil cold-pressed Citrus limon
Lime oils distilled and cold-pressed Citrus aurantifolia
stems, flowers, fruits, etc.) usually by cold expression Tangerine oil cold-pressed Citrus reticulata
( juice oils), steam distillation (peppermint oil, lemon- Peppermint oil steam-distilled Mentha piperita
grass oil), infusion (coffee, tobacco, rum, and chocolate Cornmint oil steam-distilled Mentha arvensis
flavors), solvent extraction (lilac flower, thyme), vacuum Spearmint oil steam-distilled Mentha spicata
distillation (orange oil terpenes, pine oil), or a combina- Clove bud, stem, leaf oils steam-distilled Eugenia caryophyllata
Eucalyptus oil steam-distilled Eucalyptus globulus
tion of these techniques. The choice of the extraction Litsea oil steam-distilled Litsea cubeba
technique may deeply affect the properties of the final
172 J.L.F. Monteiro and C.O. Veloso/Catalytic conversion of terpenes into fine chemicals

Figure 2. Isomerization/hydration of
-pinene.

carbon [13]. It proceeds along two parallel routes
leading either to bi- and tricyclic products (camphene,
-pinene, tricyclene, etc.) or to monocyclic compounds
(limonene, terpinene, terpinolene, p-cymene) (figure 2).
The yields along the two routes strongly depend on the
acidity and on the pore structure of the catalyst, the
nature of the acidic sites (Brnsted or Lewis), and the
operating conditions [14,15]. Besides camphene, limo-
nene is also a very attractive product that is widely
employed in the synthesis of oxygenated compounds of
interest to perfumery.
Limonene and camphene were the main products
observed in the liquid-phase isomerization of
-pinene
over dealuminated mordenite and faujasite zeolites at
393 K [16]. The best results were obtained with the
mordenite sample with Si=Al 50, which gave a 68%
combined yield of camphene limonene with a selectivity
of camphene=limonene camphene greater than 0.54.
Lesage et al. [17] studied the isomerization of -3-
carene, a monoterpene present in turpentine, into -2-
carene, an intermediate for the synthesis of -trans-
isolimonene and -menthol, used in the perfume
industry (figure 3). This isomerization was performed
over silica-supported nickel/tin catalysts at 393 K with a
conversion of 48% (a value close to thermodynamic
equilibrium), producing -2-carene with a 91%
selectivity (by-products are cymenes, caranes, and
trimethylcycloheptenes). The same reaction can be
carried out in strongly basic solutions but with a serious
problem of disposal of residues.
Besides the isomerization of the terpenes themselves,
the isomerization of their epoxides yielding aldehydes
and alcohols also produces useful intermediates for fine
chemical synthesis. For instance, the isomerization of
-
pinene epoxide into campholenic aldehyde (figure 4), an
intermediate in the production of fragrances with
sandalwood scent, has been studied by several authors.
The main problem is that
-pinene oxide is very reactive
and rearranges easily into many other products. The
usual process applies ZnCl2 or ZnBr2 as homogeneous
catalysts [18] with a selectivity of about 85%, but
growing concern with disposal problems of the Zn-
contaminated aqueous residues has stimulated the
search for Lewis solid acids as substitutes [19]. Zeolites

Figure 3. Isomerization of carene.

 J.L.F. Monteiro and C.O. Veloso/Catalytic conversion of terpenes into fine chemicals
Figure 4.
-Pinene oxide isomerization.
such as Na-mordenite [20], USY [21] and Ti-BEA [22],
silica-impregnated with zinc triflate [23], amorphous
silica-aluminas [24], and sulfated metal oxides such as
alumina, titania, and zirconia [25] have been tested at
mild conditions. The use of Ca-A zeolite to isomerize
limonene-1,2-epoxide to carvenone at 423483 K with
90% yield has also been reported [20]. Here, outer
surface catalysis is assumed to operate.
The acid-catalyzed hydration and isomerization of
-
pinene yields a complex mixture of monoterpenes,
alcohols, and hydrocarbons. The main products are
-
terpineol, limonene, and terpinolene. Minor amounts of
camphene,
- and -terpinene,
- and -fenchol,
isoborneol, borneol, -terpineol, and 1,8-terpine are
also formed (figure 2).

-Terpineol is one of the most important monocyclic
monoterpenic alcohols and one of the top 30 commonly
used flavor compounds. It is produced on an industrial
scale by hydration of
-pinene or turpentine oil to the
cis-terpin hydrate with aqueous mineral acids, followed
by its partial dehydration to
-terpineol [26]. This
process presents some difficulties such as the production
of complex mixtures and the disposal of mineral acids.
The hydration/isomerization of
-pinene at 329 K
catalyzed by zeolite H-beta [27] is fast and leads mainly to
monocyclic terpenes and alcohols with
-terpineol as the
main product (up to 48%). The selectivity toward the
commercially interesting bicyclic products (such as
borneol and camphene) is about 26%, which is signifi-
cantly better than that observed when H2 SO4 is used as
catalyst. The reaction rate increases with increasing Si/Al
ratio, which is possibly due to increased hydrophobicity
of the zeolite; the selectivities are, however, not sig-
nificantly affected.
-Terpineol has also been obtained
from the hydration of
-pinene at 323 K over poly-
dimethylsiloxane (PDMS) membranes loaded with either
USY or beta zeolites, or with a surface-modified
activated carbon [28,29], but the composite membranes
exhibited lower activities than the free catalysts.
Figure 6. Aldol condensation of citral and acetone.
173
Figure 5. Hydration of dihydromyrcene.
Dihydromyrcenol is a terpene alcohol extensively
used because of its excellent stability and powerful lime-
like aroma. It is industrially obtained from dihydro-
myrcene (prepared from pinane by thermal ring opening
reaction) by hydration with concentrated sulfuric acid
solutions at 273 K (figure 5). There have been various
reports on other potential catalytic systems for this
reaction such as Keggin-type heteropolyacids [30],
cationic resins [31], and mordenite [32], but the yields
were usually low. By using a single-phase system, with
acetone as solvent, dihydromyrcenol yields of 50% with
a selectivity close to 100% were obtained when hydro-
phobic beta zeolites were used as catalysts [33].
Keggin-type heteropolyacids H3 PW12 O40 were also
used as catalysts for the combined liquid-phase hydra-
tion and acetoxylation of limonene,
- and -pinenes in
acetic acid solutions, either dissolved or supported on
silica, exhibiting much higher activity than sulfuric acid
or Amberlyst 15 [34]. At room temperature under
optimized conditions, the pinenes form a mixture of
-
terpineol and
-terpenyl acetate (desired products) with
85% selectivity at 90% substrate conversion, while
limonene gives the desired products with 85% selectivity
at 50% conversion. The catalyst can be separated
without neutralization by precipitating with a hydro-
carbon and reused.
3.2. Condensation
Condensation reactions form a very important class
of reactions for the formation of new CC bonds.
Examples in fine chemicals production are the aldol
condensation of citral and acetone (figure 6) forming
pseudoionone, the first step for the synthesis of -
ionone, an important compound for the perfume and
174 J.L.F. Monteiro and C.O. Veloso/Catalytic conversion of terpenes into fine chemicals

pharmaceuticals industries (synthesis of vitamin A, for 100

Citral conversion (%)

example), and the Knoevenagel condensation between
the aldehyde derived from the hydroformylation of
limonene and ethyl acetoacetate.
Noda et al. [4] were the first to report on the aldol
condensation of citral and acetone over CaO, MgO, and
calcined hydrotalcites, aiming at finding heterogeneous
catalysts that could substitute for the homogeneous ones
(NaOH and KOH solutions) used industrially. The best
results were obtained with CaO and calcined hydro-
talcite at 398 K, with high conversions (98%) and
selectivities to pseudoionone (70%) observed over both
catalysts. These figures are comparable or superior to
those in homogeneous medium.
Roelofs et al. [35,36] studied this reaction over
rehydrated calcined hydrotalcite and ethanol-washed
rehydrated calcined hydrotalcite at 273 and 296 K with
the best conversions and selectivities to pseudoionone in
the range 9288% and 7987% respectively, but using an
excessively high acetone/citral molar ratio of 260. They
report that with an acetone/citral molar ratio of 20, no
reaction took place.
Corma et al. [37] obtained a citral conversion of 96%
and a selectivity to pseudoionone of 99% over rehy-
drated calcined hydrotalcites at 333 K with an acetone/
citral molar ratio of 2.7 and a catalyst concentration of
16.6 wt%.
Recent results of our group (figures 7, 8 and 9) show
that nearly complete conversion of citral can be
obtained using the mixed oxides derived from the
calcination of hydrotalcite Mg=Al 4 as catalyst in
a wide range of operating conditions. The selectivity to
pseudoionones seems to depend only on conversion, and
values as high as 95% were obtained at conversions close
to 100%.
X-zeolites exchanged with cesium and impregnated
with cesium species were active as catalysts for the
Knoevenagel reaction between the aldehyde obtained
by the hydroformylation of limonene and ethyl
80
60
303 K
40
323 K
343 K
20 398 K
0
0 2 4 6 8 10
Time (h)
Figure 8. Aldol condensation of citral with acetone over mixed oxides
derived from hydrotalcite for acetone=citral 5. Influence of reaction
temperature on conversion.
acetoacetate [38] (figure 10). The best results were
obtained for the sample with 14 cesium atoms impreg-
nated per unit cell, at 403 K and ethyl acetoacetate/
aldehyde molar ratio of 5. In such conditions, yields of
products of interest as intermediates for fine chemicals
production were as high as 90% after 4 h of reaction.
Volcho et al. [39] recently described the aldol self-
condensation of citronellal and the Knoevenagel reaction
of both citral and citronellal with malonitrile over Cs-beta
zeolite at room temperature. They also reacted malonitrile
with some other terpenes such as
-ionone and carvone,
obtaining products derived from both Michael and
Knoevenagel reactions, usually with low yields.
Compounds containing the pyranoquinolinone ske-
leton have wide biological applications (psychotropics,
antihistaminics, antiallergics, etc.). Manikandan et al.
[40] reported the chemoselective synthesis of those
compounds in basic medium by the intramolecular
domino Knoevenagel hetero DielsAlder reaction of
citronellal and quinolinones using microwave irradia-
tion. These same reactions and technique were used to
produce derivatives of coumarin also from citronellal
[41].

100

100 PSI
80
Citral conversion (%)

Selectivity (%)

80
60
60 303 K
323 K
40 343 K
40 398 K
Acetone/citral molar ratio
1 20
20 OCP
5
0
0 0 20 40 60 80 100
0 1 2 3 4
Citral conversion (%)
Time (h)
Figure 9. Aldol condensation of citral with acetone over mixed
Figure 7. Aldol condensation of citral with acetone over mixed oxides oxides derived from hydrotalcite for acetone=citral 5. Influence
derived from hydrotalcite at 398 K. Influence of acetone/citral molar of reaction temperature and conversion on selectivity (PSI
ratio on conversion. pseudoionone; OCP other condensation products).
 J.L.F. Monteiro and C.O. Veloso/Catalytic conversion of terpenes into fine chemicals 175

Figure 10. Knoevenagel condensation between the aldehyde derived from limonene and ethyl acetoacetate.

3.3. Hydroformylation the synthesis of aldehydes of interest in the perfume

industry [42,43].
The hydroformylation of terpenes (figure 11) using Cipres et al. [44] hydroformylated limonene, iso-
rhodium complexes as catalyst is an important route to pulegol, isopulegyl acetate and pinenes (
- and -) to the

Figure 11. Hydroformylation of some terpenes.

176 J.L.F. Monteiro and C.O. Veloso/Catalytic conversion of terpenes into fine chemicals
Figure 12. Hydrogenation of citral.
corresponding aldehydes using dinuclear rhodium com-
plexes as catalysts in different solvents at low pressures
(0.51.7 MPa) and temperatures (358 K) with good
conversion and selectivity.
Rhodium and cobalt carbonyls were also used as
catalysts in the hydroformylation of pinenes to their
respective aldehydes and alcohols at 333403 K, 600 psi
and CO=H2 1 [45]. 3-Formylpinane was the main
product when mononuclear rhodium complexes, dico-
balt carbonyls, and phosphine-modified hexarhodium
carbonyls were used, while 10-formylpinane was formed
with hexarhodium carbonyls. In all cases, low conver-
sions were achieved.
In another study, --pinene, R--limonene, and
-camphene were regiospecifically hydroformylated at
373403 K, 9 MPa and CO=H2 1 in the presence of
platinum (II)/SnCl2 /phosphine catalysts to exclusively
give the linear isomers of the corresponding aldehydes
with high stereoselectivities [46]. The hydroformylation
of -pinene yielded trans-10-formylpinane with a 98%
diastereoisomeric excess (de), while limonene and
camphene gave the diastereoisomers of the correspond-
ing aldehydes in approximately equal amounts (de of ca.
10 and 15% respectively). Under optimized conditions,
chemoselectivities for aldehyde formation as high as
90% have been attained for all monoterpenes studied.
3.4. Hydrogenation
Terpene alcohols (used in the perfume and pharma-
ceutical industries) are also obtained directly from the
hydrogenation of aldehydes/ketones or from unsatu-
rated alcohols. Examples are the production of citro-
nellol, geraniol, and nerol from citral [47,48], of
citronellol from citronellal [49], of carvomenthol from
carvone [50], and of linalool from dehydrolinalool [51].
The liquid-phase hydrogenation of citral (figure 12)
at 5 MPa and 399 K on RhSn silica-supported catalysts
Figure 13. Reduction and cyclization of citronellal.
prepared by coimpregnation has been shown to be
selective to the unsaturated alcohols, geraniol, and nerol
(96%), at 80% conversion [47]. These values are similar
to those obtained for catalysts prepared from organo-
metallic precursors [52].
Catalytic transfer hydrogenation between carbonyl
compounds and secondary alcohols, known as the
Meerwein-Ponndorf-Verley (MPV) reaction, is highly
sensitive, takes place under mild conditions, and has
often been used to produce alcohols. A classical example
of this reaction is the reduction of citronellal with
isopropanol to citronellol (figure 13) over alkali metal-
exchanged X-zeolite at 423 K [49]. Cyclization to
isopulegol is a competing reaction, and the yields
obtained depend on the cation used. When the zeolite
is exchanged with lithium or sodium, the reaction
produces 86% isopulegol and 14% citronellol at a
conversion of 87%. If the compensating cation is cesium,
the reaction now produces 92% citronellol at a conver-
sion of 77%. These results are probably due to
differences in acidity/basicity of the zeolites. The
transfer hydrogenation of citral with 2-alkanols, 3-
alkanols, and cycloalkanols on basic catalysts, MgO and
CaO, produced nerol and geraniol with no change in
olefin bonds [48]. The conversion and the selectivity
exceeded 95 and 85%, respectively. MgO was the most
active catalyst, and the cycloalkanols were the better
hydrogen donors.
3.5. Cyclization
Hydroformylation/cyclization of terpenes are routes
for the production of cyclic alcohols of interest for
perfumes and fragrances.
Mitsubishi Co. [53] reported that 4,8-dimethyl-
bicyclo[3.3.1]non-7-en-2-ol and its derivatives, which
are useful as perfumes can be synthesized via cyclization
 J.L.F. Monteiro and C.O. Veloso/Catalytic conversion of terpenes into fine chemicals
of the aldehyde derived from limonene with sulfuric acid
or strongly acidic resins as catalysts. Dias et al. [54]
performed this same reaction directly from limonene at
403 K, 9 MPa, CO=H2 1 in one step using platinum/
tin complexes. Selectivities up to 82% at 95% conversion
of limonene were reported.
Isopulegol is a terpene alcohol used in the manufac-
ture of fragrances with blossom scent and as an
intermediate in the synthesis of menthols, which have
a characteristic peppermint smell. It can be obtained
from the cyclization/isomerization of citronellal (figure
13) in the presence of various homogeneous and
heterogeneous catalysts. Among the former, various
complexes of rhodium, molybdenum, and tungsten have
been used, but neoisopulegol was often preferentially
formed. A large number of solid Lewis and Brnsted
acids have also been tested (ZnCl2 , ZnBr2 , SiO2 -Al2 O3 ,
ZrSO4 2 , zeolites) and high selectivities >90% have
been reported, but the amount of catalyst required was
usually excessively large.
An yield of 91% was attained when the reaction was
carried out over Zr-exchanged montmorillonite in
acetonitrile at 353 K, with a stereoselectivity of 90% to
-isopulegol [55]. This isomer is particularly attractive
since it can be hydrogenated to -menthol, the only
menthol isomer that exerts a cooling effect.
Chuah et al. [56] compared the behavior of zirconia,
phosphated zirconia, sulfated zirconia, beta zeolite,
montmorillonite, sulfonic resins, and silica gel in the
cyclization of citronellal to isopulegol at 383 K in
toluene with 5 wt% of catalyst with respect to citronellal.
The best results were achieved for the zirconia derived
from zirconium hydroxides, which were digested for a
few days, and for the phosphated zirconia. For those
catalysts, both conversions and selectivities of up to 99%
were observed after 1 h of reaction.
3.6. Dehydrogenation
The valuable p-cymene is used in the fragrance and
the polymer industry and as an intermediate in p-cresol
production. It is also a raw material for the synthesis of
nonnitrated musks, which nowadays tend to replace
nitrated ones [57]. It is mainly produced via the
alkylation of toluene with propylene, but dehydrogena-
tion of various terpenes such as limonene [58], 3-carene
[59], and
-pinene [60] can also be used to produce p-
cymene. Buhl et al. [58] showed that the activity of the
support does not influence the transformation of
limonene into p-cymene over palladium supported on
silica at about 573 K, a purely hydrogenation/dehydro-
genation mechanism being operative. On the other
hand, the catalyst acidity plays a key role in the
dehydrogenation of bicyclic compounds such as pinenes
to p-cymene [15]. Besides the pure terpenes themselves,
their mixtures are particularly attractive raw materials
177
for the production of p-cymene. Mixed terpenes are
renewable feedstocks, widely and cheaply produced in
the citrics juice industry and in the pulp and paper
industry. Buhl et al. [57] studied the gas-phase conver-
sion of a feedstock composed of mixed terpenes to p-
cymene over both Ce-promoted palladium catalysts
supported on Na-ZSM-5 and pure silica impregnated
with palladium. The most promising catalyst, SiO2
impregnated with 0.5 wt% of palladium, showed no
deactivation during a total time onstream of 100 h at
573 K and a constant yield of 90% of p-cymene. On the
other hand, when crude sulfate turpentine, the cheapest
and the major source of terpenes in Europe and the
United States nowadays, was used as reagent, its high
sulfur level led to a severe deactivation of the palladium
catalyst [15].
3.7. Oxidation
A common approach toward the functionalization of
monoterpenes is the epoxidation of the respective
double bond and rearrangement of the resulting three-
membered highly strained epoxide ring system under the
influence of various catalysts [61]. The main rearrange-
ment products thus obtained are usually alcohols,
carbonyl compounds, and skeletally rearranged pro-
ducts. This selective oxyfunctionalization process is an
attractive route to commercially important intermedi-
ates for pharmaceuticals, flavors, perfumes, and chiral
building blocks. Gusevskaya et al. [62] studied the
oxidation of the bicyclic monoterpenes
- and -pinene
and camphene (figure 14) using different catalysts and
oxidants in aqueous acetic acid solutions. The best
results were obtained with hydrogen peroxide as the
oxygen source and PdOAc2 as catalyst at 333 K. -
Pinene gave the allylic oxidation products (pinocarveol,
pinocarveyl acetate, and myrtenyl acetate) with selectiv-
ity up to 75% at virtually complete conversion, and
camphene gave camphene glycol monoacetate with a
90% selectivity at 80% conversion when small amounts
of benzoquinone were added to the reaction mixture. No
selective oxidation of
-pinene was observed under these
conditions.
Suh et al. [63] reported the synthesis of campholenic
aldehyde in a single step from
-pinene (figure 4) over
Ti-HMS (mesoporous molecular sieve) in the liquid
phase at 350 K and acetonitrile as solvent. Selectivities
of about 82% were attained after 24 h with tert-butyl
hydroperoxide (TBHP) as oxidant. The only by-
products were the epoxide and the isomeric aldehyde
when the reaction was performed in the absence of water
and oxygen. TBHP was also used by Berlini et al. [64] to
epoxidize a series of unsaturated terpenic alcohols at
358 K over catalysts containing titanium either in the
framework or grafted onto MCM-41. The influence of
the nature of the solvent (acetonitrile or ethyl acetate)
178 J.L.F. Monteiro and C.O. Veloso/Catalytic conversion of terpenes into fine chemicals

Figure 14. -Pinene and camphene oxidation.

Figure 15. p-Cymene and carvacrol oxidation.

and of the distance between the hydroxyl group and the
double bond on the rate and on the selectivity were
explored.
Different types of Mg/Al-layered double hydroxides
(LDH) (as-synthesized, calcined, intercalated) were
active for the reaction of limonene epoxidation with
hydrogen peroxide in the presence of nitriles [65]. The
best conversion and selectivity to epoxides (about 98
and 74%, respectively) were achieved with the as-
synthesized Mg/Al-LDH after 2 h in the presence of
dicyanobenzenes.
The use of manganese (III) porphyrin complexes as
catalysts for the oxidation of various terpenes by
aqueous hydrogen peroxide was studied at room
temperature in acetonitrile, using ammonium acetate
as cocatalyst [66,67]. Complete conversion of 3-carene
was observed after 1.5 h, yielding epoxides and ketones
as major products. From nerol and geraniol, 100%
conversion was attained after 2 h. Only epoxides (mono-
and di-) were detected with the former, while geraniol
also gave the epoxyaldehyde. Thymoquinone, a dike-
tone with high commercial value, was the only product
obtained from the oxidation of carvacrol and thymol,
while p-cymene formed a mixture of two alcohols, an
aldehyde, a carboxylic acid, and thymoquinone (figure
15).
The epoxidation of (R)-limonene to terpinolene oxide
followed by the isomerization/ring enlargement of the
latter over montmorillonite at 303 K for 6 h gives
karahanaenone with 71% yield (figure 16). Reduction
of this prochiral ketone with lithium aluminum hydride
in dry tetrahydrofuran produces karahanaenol, whose
individual enantiomers are known to possess varying
degrees of fruity and woody odor [68].
Recently, Ferraz et al. [69] reported excellent yields in
the epoxidation of both
4 -octalin derivatives and
Figure 16. Karahanaenone synthesis.
 J.L.F. Monteiro and C.O. Veloso/Catalytic conversion of terpenes into fine chemicals
monoterpenes with dimethyldioxirane at 273 K, very
good diastereoselectivities being observed in some
cases.
4. Conclusion
The perception that satisfying the increasing needs of
our society cannot be done at the expense of the planet
resources has triggered the shift toward the so-called
green chemistry. Using renewable resources in the
chemical industry not only helps avoid the complete
depletion of fossile raw materials but also contributes to
reduce the impact of chemical processing on the
environment. This seems to be the only safe route to
make sure that the future generations will also have the
means to satisfy their needs.
Catalysis plays a fundamental role in the develop-
ment of technologies that may meet these demands. This
is particularly evident in the case of fine chemicals
production in which a large number of steps is usually
involved, and selectivity (chemo-, regio-, and stereo-) is
often the key to success. Terpenes from plants are a class
of products that can supply the raw materials or the
intermediates used in the fine chemicals industry even if
new technologies must be developed or adapted. This
paper has given some examples of the vast number of
catalytic systems and transformations that are or may be
used to transform terpenes into valuable chemicals. This
is a field that is extremely fertile for the development of
new ideas.
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