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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


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

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


the synthesis of ionones [4]. The natural product, obtained
chlorophyll
n CO2 n H2 O ! CH2 On n O2 from citrics and particularly from lemongrass, has been
light
largely replaced by its synthetic counterpart, produced
They contain highly functionalized molecules, which can from isobutene [5]. Other products that were obtained
be used directly after a number of steps of isolation and from plants, such as caffeine, ephedrine, coumarin,
purification or can be further transformed into other papaverine, and L-dopa are now mostly produced
molecules with specific groups responsible for the commercially by synthetic routes [6].
desired property, while in many other applications, Fortunately, there has recently been an increasing
isolation of a single species is not necessary. These search for new catalytic processes for fine chemicals
molecules (secondary metabolites) are used in a variety production based on renewable resources. Many of
of industries such as those of pharmaceuticals, cos- these processes rely on the fact that switching from
metics, flavors, fragrances, pesticides, and pigments homogeneous (as mostly practiced nowadays) to hetero-
(table 1). geneous catalysis may contribute to solving the problem
The World Health Organization (WHO) estimates of waste disposal, besides avoiding or simplifying steps
that 80% of the world population uses plants as a source such as separation, neutralization, recycling, etc.
of medicines, in one way or another. Most of the drugs
obtained from plants were developed from knowledge
that has been transferred along generations. 3. Fine chemicals from terpenes
On the other hand, environmental, social, political, Terpenes present in plants are generally composed of
and economical aspects cannot be neglected. Loss of several isoprene units joined in a regular, head-to-tail
biodiversity, natural forests clearing, competition with way, the so-called isoprene rule (figure 1). Compounds
fiber- or food-oriented agriculture, policies for land use, that have two isoprene units are called monoterpenes. In
farmers unwillingness to change their methods, and nature, the isoprene units that build up terpenes are
land reforming in developing countries are but a few of synthesized from acetic acid by way of the important
the pieces that form a mosaic of real or potential biochemical intermediate, isopentenyl pyrophosphate.
problems to be faced if chemicals are to be produced on They are the most abundant components of the essential
a large scale from agriculture. oils of many plants and flowers. Turpentine oleoresin
In the past, the impossibility of maintaining a con- obtained from coniferous trees and terebinth and
tinuous and steady year-round supply of raw materials and essential oils from citrics are two of the most important
increasing production costs led many industries to replace sources of terpenes. Table 2 summarizes some of those
natural products with petrochemical-derived ones. This is 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 industry (figure 3). This isomerization was performed
leading either to bi- and tricyclic products (camphene, over silica-supported nickel/tin catalysts at 393 K with a
-pinene, tricyclene, etc.) or to monocyclic compounds conversion of 48% (a value close to thermodynamic
(limonene, terpinene, terpinolene, p-cymene) (figure 2). equilibrium), producing -2-carene with a 91%
The yields along the two routes strongly depend on the selectivity (by-products are cymenes, caranes, and
acidity and on the pore structure of the catalyst, the trimethylcycloheptenes). The same reaction can be
nature of the acidic sites (Brnsted or Lewis), and the carried out in strongly basic solutions but with a serious
operating conditions [14,15]. Besides camphene, limo- problem of disposal of residues.
nene is also a very attractive product that is widely Besides the isomerization of the terpenes themselves,
employed in the synthesis of oxygenated compounds of the isomerization of their epoxides yielding aldehydes
interest to perfumery. and alcohols also produces useful intermediates for fine
Limonene and camphene were the main products chemical synthesis. For instance, the isomerization of -
observed in the liquid-phase isomerization of -pinene pinene epoxide into campholenic aldehyde (figure 4), an
over dealuminated mordenite and faujasite zeolites at intermediate in the production of fragrances with
393 K [16]. The best results were obtained with the sandalwood scent, has been studied by several authors.
mordenite sample with Si=Al 50, which gave a 68% The main problem is that -pinene oxide is very reactive
combined yield of camphene limonene with a selectivity and rearranges easily into many other products. The
of camphene=limonene camphene greater than 0.54. usual process applies ZnCl2 or ZnBr2 as homogeneous
Lesage et al. [17] studied the isomerization of -3- catalysts [18] with a selectivity of about 85%, but
carene, a monoterpene present in turpentine, into -2- growing concern with disposal problems of the Zn-
carene, an intermediate for the synthesis of -trans- contaminated aqueous residues has stimulated the
isolimonene and -menthol, used in the perfume 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 173

Figure 4. -Pinene oxide isomerization.

such as Na-mordenite [20], USY [21] and Ti-BEA [22],


silica-impregnated with zinc triflate [23], amorphous Figure 5. Hydration of dihydromyrcene.
silica-aluminas [24], and sulfated metal oxides such as
alumina, titania, and zirconia [25] have been tested at Dihydromyrcenol is a terpene alcohol extensively
mild conditions. The use of Ca-A zeolite to isomerize used because of its excellent stability and powerful lime-
limonene-1,2-epoxide to carvenone at 423483 K with like aroma. It is industrially obtained from dihydro-
90% yield has also been reported [20]. Here, outer myrcene (prepared from pinane by thermal ring opening
surface catalysis is assumed to operate. reaction) by hydration with concentrated sulfuric acid
The acid-catalyzed hydration and isomerization of - solutions at 273 K (figure 5). There have been various
pinene yields a complex mixture of monoterpenes, reports on other potential catalytic systems for this
alcohols, and hydrocarbons. The main products are - reaction such as Keggin-type heteropolyacids [30],
terpineol, limonene, and terpinolene. Minor amounts of cationic resins [31], and mordenite [32], but the yields
camphene, - and -terpinene, - and -fenchol, were usually low. By using a single-phase system, with
isoborneol, borneol, -terpineol, and 1,8-terpine are acetone as solvent, dihydromyrcenol yields of 50% with
also formed (figure 2). a selectivity close to 100% were obtained when hydro-
-Terpineol is one of the most important monocyclic phobic beta zeolites were used as catalysts [33].
monoterpenic alcohols and one of the top 30 commonly Keggin-type heteropolyacids H3 PW12 O40 were also
used flavor compounds. It is produced on an industrial used as catalysts for the combined liquid-phase hydra-
scale by hydration of -pinene or turpentine oil to the tion and acetoxylation of limonene, - and -pinenes in
cis-terpin hydrate with aqueous mineral acids, followed acetic acid solutions, either dissolved or supported on
by its partial dehydration to -terpineol [26]. This silica, exhibiting much higher activity than sulfuric acid
process presents some difficulties such as the production or Amberlyst 15 [34]. At room temperature under
of complex mixtures and the disposal of mineral acids. optimized conditions, the pinenes form a mixture of -
The hydration/isomerization of -pinene at 329 K terpineol and -terpenyl acetate (desired products) with
catalyzed by zeolite H-beta [27] is fast and leads mainly to 85% selectivity at 90% substrate conversion, while
monocyclic terpenes and alcohols with -terpineol as the limonene gives the desired products with 85% selectivity
main product (up to 48%). The selectivity toward the at 50% conversion. The catalyst can be separated
commercially interesting bicyclic products (such as without neutralization by precipitating with a hydro-
borneol and camphene) is about 26%, which is signifi- carbon and reused.
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
3.2. Condensation
of the zeolite; the selectivities are, however, not sig-
nificantly affected. -Terpineol has also been obtained Condensation reactions form a very important class
from the hydration of -pinene at 323 K over poly- of reactions for the formation of new CC bonds.
dimethylsiloxane (PDMS) membranes loaded with either Examples in fine chemicals production are the aldol
USY or beta zeolites, or with a surface-modified condensation of citral and acetone (figure 6) forming
activated carbon [28,29], but the composite membranes pseudoionone, the first step for the synthesis of -
exhibited lower activities than the free catalysts. ionone, an important compound for the perfume and

Figure 6. Aldol condensation of citral and acetone.


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


Figure 13. Reduction and cyclization of citronellal.
corresponding aldehydes using dinuclear rhodium com-
plexes as catalysts in different solvents at low pressures prepared by coimpregnation has been shown to be
(0.51.7 MPa) and temperatures (358 K) with good selective to the unsaturated alcohols, geraniol, and nerol
conversion and selectivity. (96%), at 80% conversion [47]. These values are similar
Rhodium and cobalt carbonyls were also used as to those obtained for catalysts prepared from organo-
catalysts in the hydroformylation of pinenes to their metallic precursors [52].
respective aldehydes and alcohols at 333403 K, 600 psi Catalytic transfer hydrogenation between carbonyl
and CO=H2 1 [45]. 3-Formylpinane was the main compounds and secondary alcohols, known as the
product when mononuclear rhodium complexes, dico- Meerwein-Ponndorf-Verley (MPV) reaction, is highly
balt carbonyls, and phosphine-modified hexarhodium sensitive, takes place under mild conditions, and has
carbonyls were used, while 10-formylpinane was formed often been used to produce alcohols. A classical example
with hexarhodium carbonyls. In all cases, low conver- of this reaction is the reduction of citronellal with
sions were achieved. isopropanol to citronellol (figure 13) over alkali metal-
In another study, --pinene, R--limonene, and exchanged X-zeolite at 423 K [49]. Cyclization to
-camphene were regiospecifically hydroformylated at isopulegol is a competing reaction, and the yields
373403 K, 9 MPa and CO=H2 1 in the presence of obtained depend on the cation used. When the zeolite
platinum (II)/SnCl2 /phosphine catalysts to exclusively is exchanged with lithium or sodium, the reaction
give the linear isomers of the corresponding aldehydes produces 86% isopulegol and 14% citronellol at a
with high stereoselectivities [46]. The hydroformylation conversion of 87%. If the compensating cation is cesium,
of -pinene yielded trans-10-formylpinane with a 98% the reaction now produces 92% citronellol at a conver-
diastereoisomeric excess (de), while limonene and sion of 77%. These results are probably due to
camphene gave the diastereoisomers of the correspond- differences in acidity/basicity of the zeolites. The
ing aldehydes in approximately equal amounts (de of ca. transfer hydrogenation of citral with 2-alkanols, 3-
10 and 15% respectively). Under optimized conditions, alkanols, and cycloalkanols on basic catalysts, MgO and
chemoselectivities for aldehyde formation as high as CaO, produced nerol and geraniol with no change in
90% have been attained for all monoterpenes studied. 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
3.4. Hydrogenation hydrogen donors.
Terpene alcohols (used in the perfume and pharma-
ceutical industries) are also obtained directly from the
3.5. Cyclization
hydrogenation of aldehydes/ketones or from unsatu-
rated alcohols. Examples are the production of citro- Hydroformylation/cyclization of terpenes are routes
nellol, geraniol, and nerol from citral [47,48], of for the production of cyclic alcohols of interest for
citronellol from citronellal [49], of carvomenthol from perfumes and fragrances.
carvone [50], and of linalool from dehydrolinalool [51]. Mitsubishi Co. [53] reported that 4,8-dimethyl-
The liquid-phase hydrogenation of citral (figure 12) bicyclo[3.3.1]non-7-en-2-ol and its derivatives, which
at 5 MPa and 399 K on RhSn silica-supported catalysts are useful as perfumes can be synthesized via cyclization
J.L.F. Monteiro and C.O. Veloso/Catalytic conversion of terpenes into fine chemicals 177

of the aldehyde derived from limonene with sulfuric acid for the production of p-cymene. Mixed terpenes are
or strongly acidic resins as catalysts. Dias et al. [54] renewable feedstocks, widely and cheaply produced in
performed this same reaction directly from limonene at the citrics juice industry and in the pulp and paper
403 K, 9 MPa, CO=H2 1 in one step using platinum/ industry. Buhl et al. [57] studied the gas-phase conver-
tin complexes. Selectivities up to 82% at 95% conversion sion of a feedstock composed of mixed terpenes to p-
of limonene were reported. cymene over both Ce-promoted palladium catalysts
Isopulegol is a terpene alcohol used in the manufac- supported on Na-ZSM-5 and pure silica impregnated
ture of fragrances with blossom scent and as an with palladium. The most promising catalyst, SiO2
intermediate in the synthesis of menthols, which have impregnated with 0.5 wt% of palladium, showed no
a characteristic peppermint smell. It can be obtained deactivation during a total time onstream of 100 h at
from the cyclization/isomerization of citronellal (figure 573 K and a constant yield of 90% of p-cymene. On the
13) in the presence of various homogeneous and other hand, when crude sulfate turpentine, the cheapest
heterogeneous catalysts. Among the former, various and the major source of terpenes in Europe and the
complexes of rhodium, molybdenum, and tungsten have United States nowadays, was used as reagent, its high
been used, but neoisopulegol was often preferentially sulfur level led to a severe deactivation of the palladium
formed. A large number of solid Lewis and Brnsted catalyst [15].
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
3.7. Oxidation
usually excessively large.
An yield of 91% was attained when the reaction was A common approach toward the functionalization of
carried out over Zr-exchanged montmorillonite in monoterpenes is the epoxidation of the respective
acetonitrile at 353 K, with a stereoselectivity of 90% to double bond and rearrangement of the resulting three-
-isopulegol [55]. This isomer is particularly attractive membered highly strained epoxide ring system under the
since it can be hydrogenated to -menthol, the only influence of various catalysts [61]. The main rearrange-
menthol isomer that exerts a cooling effect. ment products thus obtained are usually alcohols,
Chuah et al. [56] compared the behavior of zirconia, carbonyl compounds, and skeletally rearranged pro-
phosphated zirconia, sulfated zirconia, beta zeolite, ducts. This selective oxyfunctionalization process is an
montmorillonite, sulfonic resins, and silica gel in the attractive route to commercially important intermedi-
cyclization of citronellal to isopulegol at 383 K in ates for pharmaceuticals, flavors, perfumes, and chiral
toluene with 5 wt% of catalyst with respect to citronellal. building blocks. Gusevskaya et al. [62] studied the
The best results were achieved for the zirconia derived oxidation of the bicyclic monoterpenes - and -pinene
from zirconium hydroxides, which were digested for a and camphene (figure 14) using different catalysts and
few days, and for the phosphated zirconia. For those oxidants in aqueous acetic acid solutions. The best
catalysts, both conversions and selectivities of up to 99% results were obtained with hydrogen peroxide as the
were observed after 1 h of reaction. 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
3.6. Dehydrogenation
camphene gave camphene glycol monoacetate with a
The valuable p-cymene is used in the fragrance and 90% selectivity at 80% conversion when small amounts
the polymer industry and as an intermediate in p-cresol of benzoquinone were added to the reaction mixture. No
production. It is also a raw material for the synthesis of selective oxidation of -pinene was observed under these
nonnitrated musks, which nowadays tend to replace conditions.
nitrated ones [57]. It is mainly produced via the Suh et al. [63] reported the synthesis of campholenic
alkylation of toluene with propylene, but dehydrogena- aldehyde in a single step from -pinene (figure 4) over
tion of various terpenes such as limonene [58], 3-carene Ti-HMS (mesoporous molecular sieve) in the liquid
[59], and -pinene [60] can also be used to produce p- phase at 350 K and acetonitrile as solvent. Selectivities
cymene. Buhl et al. [58] showed that the activity of the of about 82% were attained after 24 h with tert-butyl
support does not influence the transformation of hydroperoxide (TBHP) as oxidant. The only by-
limonene into p-cymene over palladium supported on products were the epoxide and the isomeric aldehyde
silica at about 573 K, a purely hydrogenation/dehydro- when the reaction was performed in the absence of water
genation mechanism being operative. On the other and oxygen. TBHP was also used by Berlini et al. [64] to
hand, the catalyst acidity plays a key role in the epoxidize a series of unsaturated terpenic alcohols at
dehydrogenation of bicyclic compounds such as pinenes 358 K over catalysts containing titanium either in the
to p-cymene [15]. Besides the pure terpenes themselves, framework or grafted onto MCM-41. The influence of
their mixtures are particularly attractive raw materials 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 while p-cymene formed a mixture of two alcohols, an
double bond on the rate and on the selectivity were aldehyde, a carboxylic acid, and thymoquinone (figure
explored. 15).
Different types of Mg/Al-layered double hydroxides The epoxidation of (R)-limonene to terpinolene oxide
(LDH) (as-synthesized, calcined, intercalated) were followed by the isomerization/ring enlargement of the
active for the reaction of limonene epoxidation with latter over montmorillonite at 303 K for 6 h gives
hydrogen peroxide in the presence of nitriles [65]. The karahanaenone with 71% yield (figure 16). Reduction
best conversion and selectivity to epoxides (about 98 of this prochiral ketone with lithium aluminum hydride
and 74%, respectively) were achieved with the as- in dry tetrahydrofuran produces karahanaenol, whose
synthesized Mg/Al-LDH after 2 h in the presence of individual enantiomers are known to possess varying
dicyanobenzenes. degrees of fruity and woody odor [68].
The use of manganese (III) porphyrin complexes as Recently, Ferraz et al. [69] reported excellent yields in
catalysts for the oxidation of various terpenes by the epoxidation of both 4 -octalin derivatives and
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, Figure 16. Karahanaenone synthesis.
J.L.F. Monteiro and C.O. Veloso/Catalytic conversion of terpenes into fine chemicals 179

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