J Am Oil Chem Soc (2021) 98: 305–316

DOI 10.1002/aocs.12468

ORIGINAL ARTICLE

Production of Industrially Useful and Renewable p-Cymene by

Catalytic Dehydration and Isomerization of Perillyl Alcohol
Bryan R. Moser1 · Michael A. Jackson2 · Kenneth M. Doll1

Received: 6 November 2020 / Revised: 3 December 2020 / Accepted: 28 December 2020

Published 2021. This article is a U.S. Government work and is in the public domain in the USA.

Abstract We report the dehydration and isomerization of
renewable perillyl alcohol to industrially useful p-cymene
in 91% yield utilizing 2.0 mol% para-toluenesulfonic acid
(pTsOH) catalyst at 110  C as a 3.0 M solution in toluene.
Lower reaction temperatures, catalyst loadings, and/or
starting concentrations resulted in lower yields of p-cymene
as well as longer reaction times. Conversion of perillyl
alcohol to p-cymene yielded atom and carbon economies of
88.1% and 100% as well as an E-factor of 2.7, thereby indi-
cating that the process was both green and sustainable. A
lower yield of 86% was observed when the reaction was
performed neat, but a lower E-factor of 0.4 indicated that
neat conditions were more desirable from an environmental
perspective. Application of the optimized parameters to
3.0 M solutions of dl-limonene led predominantly to oligo-
merization (92%) as opposed to dehydroisomerization
(5%), which was attributed to the strong Brønsted acidity of
pTsOH. In addition, camphene (44%), terpinene isomers
(15%), and limonene (14%) were obtained when
dehydroisomerization was attempted on 3.0 M solutions of
α- and β-pinene, which was once again attributed to the
acidity of the catalyst. Oligomerization was strongly
favored when dehydroisomerization of dl-limonene, α- and
β-pinene was attempted neat. In summary, synthesis of
renewable p-cymene was readily achieved from perillyl
alcohol with catalytic pTsOH but competing side reactions
suppressed yield when dehydroisomerization of dl-limo-
nene, α- and β-pinene was attempted due to the strong
Brønsted acidity of the catalyst.
Keywords p-Cymene
Isomerization
Limonene

Perillyl alcohol
Pinene
Renewable
Terpene

J Am Oil Chem Soc (2021) 98: 305–316.

Supporting information Additional supporting information may be
found online in the Supporting Information section at the end of the
article.
Introduction
* Bryan R. Moser
bryan.moser@usda.gov p-Cymene [1; 4-isopropyltoluene; 1-methyl-4-(propan-2-yl)
1
benzene] is a naturally occurring aromatic monoterpenoid that
United States Department of Agriculture, Agricultural Research
Service, National Center for Agricultural Utilization Research, consists of a benzene ring para-substituted with methyl and
Bio-Oils Research Unit, 1815 N. University Street, Peoria, IL iso-propyl groups. Noteworthy natural sources of 1 are essen-
61604, USA tial oils from cumin (Cuminum cyminum L.) and thyme (Thy-
2
United States Department of Agriculture, Agricultural Research mus vulgaris L.) (Asbaghian et al., 2011; Wanner et al., 2010).
Service, National Center for Agricultural Utilization Research, Industrial applications include as a precursor for terephthalic
Renewable Products Technology Research Unit, 1815
N. University Street, Peoria, IL 61604, USA acid, p-cresol, p-menthane, pesticides, fungicides, herbicides,
and pharmaceuticals. Other uses are as a green solvent, heat
Mention of trade names or commercial products in this publication is transfer medium, ligand for catalysts, and as a constituent in
solely for the purpose of providing specific information and does not
imply recommendation or endorsement by the U.S. Department of
fragrances and perfumes (Fig. 1) (Arockiam et al., 2012; Du
Agriculture. USDA is an equal opportunity provider and employer. et al., 2005; Gandeepan et al., 2019; Volanti et al., 2019).

Published online: 19 February 2021

J Am Oil Chem Soc (2021) 98: 305–316
306
Fig 1 Uses of p-cymene depicting production of (a) cresol and acetone, (b) p-terephthalic acid, and (c) p-menthane as well as direct uses as a
green solvent, heat transfer medium, ligand for well-defined catalysts, and as a component in fragrances and aroma therapies
Due to the industrial utility of 1 combined with its lim-
ited biological availability from high-value culinary
sources, petrochemical routes have been developed to aug-
ment supply. The most prominent is the Friedel-Crafts
alkylation of toluene with propene or 2-propanol, which is
historically catalyzed by highly toxic and corrosive Lewis
and Brønsted acids such as AlCl3, BF3, FeCl3, FeSO4-HCl,
HF, and H2SO4 (Fig. 2) (Barman et al., 2005). However,
under these conditions the meta isomer is thermodynamically
Fig 2 Petrochemical production of p-cymene from toluene via
Friedel-Crafts alkylation with propene or 2-propanol. Yield-reducing
transalkylation with toluene to give n-propyltoluene (para isomer
depicted) is also shown
J Am Oil Chem Soc
preferred (Perego et al., 1999). As a result, industrial mixtures
typically contain 65% m-cymene, 30% 1, and 5% of the steri-
cally hindered ortho isomer (Brzozowski et al., 2002).
Adsorptive separation of the mixture utilizing the Cymex
process is thus necessary to isolate 1 on an industrial scale,
with positional isomer ratio greatly affecting separation cost
and yield (Johnson and Kabza, 1990).
Solid acid catalysts such as zeolites, mesoporous molec-
ular sieves, and mixed metal oxides are safer, less corro-
sive, and more selective alternatives to the homogenous
Friedel-Crafts approach (Odedairo and Al-Khattaf, 2011;
Perego and Ingallina, 2002; Zilkova et al., 2016). However,
byproducts such as n-propyltoluene (Fig. 2), arising from
transalkylation of 1 with toluene and m- and o-cymene, are
often produced. n-Propyltoluene is not produced during tra-
ditional homogenous Friedel-Crafts alkylation but is prob-
lematic with H-ZSM-5, H Y zeolite, and H-mordenite due
to the effects of zeolitic channel geometry and pore size on
reactivity and selectivity (Perego and Ingallina, 2002;
Wichterlova and Cejka, 1994; Zilkova et al., 2016).
The petrochemical approach suffers from several signifi-
cant drawbacks, such as the utilization of toxic starting
materials, production of less useful ortho- and meta- iso-
mers that require expensive separation, generation of
n-propyltoluene, energy-intensive reaction temperatures in
excess of 300  C, employment of hazardous and corrosive
catalysts, and the inherently poor long-term sustainability
and negative environmental impact of a non-renewable
approach. Consequently, bio-based routes have been
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devised that mitigate one or more of these disadvantages.
Such methods primarily focus on the dehydroisomerization
of monoterpenes (Fig. 3) such as limonene (2), α-pinene
(α-3), and β-pinene (β-3), which represent improvements
over the petrochemical approach regarding renewability,
sustainability, and environmental impact.
Limonene and pinene are architecturally similar to 1 and
enjoy wide natural availability. Found in citrus rind, (+)-2 (d-
limonene) is the primary constituent of essential oils from
orange, lemon, mandarin, grapefruit, and lime. The other iso-
mer, (−)-2 (l-limonene), is less common, has a turpentine-like
odor, and is a component of volatiles emitted by oaks and
pines (Ciriminna et al., 2014). A racemic mixture of (+)- and
(−)-2 is referred to as dipentene or dl-limonene and is a con-
stituent of crude sulfate turpentine that is produced during
processing of wood into paper products. The most naturally
abundant monoterpenes are α-3 and β-3 (Fig. 3), which are
the primary components of turpentine oil and pine and coni-
fer resins (Winnacker, 2018).
Fig 3 Chemical pathway to p-cymene (1) from limonene (2), α-pinene
[α-3; (1R)-(+)-α-pinene depicted], and β-pinene [β-3; (1R)-(+)–βpinene
depicted] showing key carbocationic and p-menthadienoic intermediates
J Am Oil Chem Soc (2021) 98: 305–316
307
Transformation of monoterpenes to 1 is typically accom-
plished utilizing solid acid catalysts and is conducted in the gas
phase at high temperatures (≥300  C) with a continuous flow
of H2 or N2 gas. Examples are summarized in Table 1 with
the reaction sequence depicted in Fig. 3. In most cases, the
catalyst requires energy-intensive calcination at >500  C for
several hours before sufficient activity is realized. In some
examples, clay catalysts require activation with mineral acids
such as HCl or H2SO4. In addition, catalysts containing
expensive and/or toxic metals such as palladium or chromium
are often employed along with pressures exceeding ambient.
Such metals are also known to catalyze unproductive side
reactions such as disproportionation that yield complex mix-
tures of 1, p-menthane and other compounds (Lesage
et al., 1996; Tavera Ruiz et al., 2019; Thomas and
Bessiere, 1989). Thus, a new bio-based approach is of interest
that avoids expensive metals, corrosive mineral acids,
unproductive side reactions, and elevated temperatures and
pressures while simultaneously achieving a high yield of 1 in
an environmentally sustainable fashion.
The objective of the current investigation was the cata-
lytic production of 1 from perillyl alcohol [4;
(4-isopropenyl-1-cyclohexen-1-yl)methanol] utilizing mild
reaction conditions. Principally found in the essential oils
of lavender, sage, and peppermint, 4 is a monoterpene
metabolite of 2 (Anis et al., 2018; Erland et al., 2016). Con-
version of 2 to 4 is accomplished in vivo by hydroxylation
enzymes that belong to the superfamily of cytochrome
P450 proteins. Biocatalytic in vitro production of 4 from
2 is achieved using cytochrome P450 hydroxylases
expressed in Pseudomonas putida (van Beilen et al., 2005).
The chemical synthesis of 4 from 2 in four steps has also
been reported (Geoghegan and Evans, 2014). Although 4 is
currently less abundant and more expensive than both
1 and 2, we became interested in 4 as a precursor to 1 due
to the serendipitous discovery that 1 can be produced from
4 in the presence of a homogenous Brønsted acid catalyst
while attempting an unrelated transformation. We thus
report herein the optimization of 1 from 4 and attempt to
apply the optimized methodology to 2, α-3, and β-3 to
enhance the supply of renewable and industrially useful 1.
Experimental
Materials
Camphene (95%), 3-carene (90%), o-cymene (98%),
m-cymene (99%), p-cymene (99%), eucalyptol (99%), dl-
limonene (1:1 mixture of (+)/(−)-limonene; 100%),
mesitylene (98%), S-(−)-perillyl alcohol (96%),
α-phellandrene (>95%), (+)-α-pinene (98%), (−)-β-pinene
308 J Am Oil Chem Soc

Table 1 Literature survey of catalyst, reaction conditionsa, and p-cymene yield from various terpenes under heterogeneous conditions

Terpene Catalyst Calcb Temp Time Pressure p- Ref

( C; hour) ( C) Cymene (%)

α-Limonene (Ce/Pd)ZSM-5 550; 6 250 contc1 1 bar 80.8 Weyrich and

Holderich, 1997
Dipentene Pd/SiO2 550; 8 300 contc1 1 bar 90.0 Buhl et al., 1998
α/β-Pinene Pd/D-11-10 540; 6 300 contc2 1.01 bar 67.0 Roberge et al., 2001
Dipentene Zn/SBA-15 550; 5 450 contc2 1 atm 85.7 Du et al., 2005
Limonene HCl/bentonite 150; 16 80 15 min 1 atm 15.0 Fernandes et al., 2007
α-Pinene ZnO/Cr2O3 300; 5 350 contc1 1 atm 78.0 Al-Wadaani et al., 2009
α-Limonene Ni, Fe, Mn sepiolite 400; 6 165 20 min 1 atm 100 Martin-Luengo et al., 2010
α-Limonene TiO2 – Anatase 400; 6 300 contc2 1 atm 90 Kamitsou et al., 2014
α-Limonene mesoporous Si Al 300; 5 225 20 min 1 atm 100 Martin-Luengo et al., 2008
oxides
α-Limonene H2SO4/mordenite – 140 7 hours 1 atm 63 Makarouni et al., 2018
α-Limonene Pd PVP nanoparticles – >150 3 hours 2 bar H2 76 Zhao et al., 2008
α-Pinene Pd-Zn/Al-SBA-15 550; 6 300 contc2 1 atm 77 Golets et al., 2013
dl- Pd/Al2O3 – 300 30 s 8.0 MPa 80 Yilmazoglu and
Limonene Akgun, 2018
α-Pinene Au-Ni-TiO2/SBA-15 550; 5 300 3 hours 1 atm 55.9 Ajaikumar et al., 2013
dl- HCl/mordenite – 140 7 hours 1 atm 65 Lycourghiotis et al., 2018
Limonene
a
Catalyst and reaction conditions that provided the highest yield of p-cymene; 1 atm refers to atmospheric pressure.
b
Calcination temperature ( C) and time (hour).
c
cont, continuous process under a constant flow of (c1) N2 or (c2) H2 gas.

(99%), α-terpinene (85%), γ-terpinene (97%), δ-terpinene
(≥90%), and para-toluenesulfonic acid (pTsOH; 98%) were
purchased from Millipore Sigma Corp. (St. Louis, MO,
USA) and n-propyltoluene (≥99%) was obtained from
VWR International, Inc. (Radnor, PA, USA). All other
materials were purchased from Millipore Sigma Corp. and
used as received.
Gas Chromatography–Mass Spectroscopy
Reaction progress was monitored with an Agilent (Santa Clara,
CA, USA) 7890A GC equipped with a 5975C quadrupole
electron impact (EI) mass detector and a Phenomenex Zebron
ZB-35HT column (30 m × 0.32 mm × 0.25 μm) with He as
carrier gas at 1.4 mL min−1 with inlet and detector temperatures
of 340 and 230  C. The oven held at 40  C for 3 min, ramped
to 90  C at 5  C min−1, ramped to 190  C at 10  C min−1, held
for 5 min, and ramped to 340  C at 25  C min−1. Aliquots were
diluted in heptane to give signals that were identified by com-
parison to reference standards and by mass spectral analysis.
Retention times (min) of reference standards and response fac-
tors relative to p-cymene (indicated in parenthesis) were 6.50
for α-3 (0.782), 7.20 for camphene (0.771), 8.22 for β-3
(0.789), 8.98 for mesitylene (0.953), 9.30 for α-phellandrene,
9.65 for α-terpinene (0.782), 10.07 for (+/−)-2 (0.726), 10.48
for m-cymene, 10.56 for 1 (1.00), 11.11 for o-cymene, 11.25
for γ-terpinene (0.780), 11.56 for n-propyltoluene, 12.15 for
δ-terpinene (0.781), and 18.17 for 4 (0.719).
NMR and FTIR Spectroscopy
Nuclear magnetic resonance (NMR) spectra were collected at
26.9  C on a Bruker Avance-500 spectrometer (Billerica, MA,
USA) operating at 500 (1H) and 125 (13C) MHz using a 5 mm
broadband observe probe. Samples were dissolved in CDCl3
(Cambridge Isotope Laboratories, Andover, MA, USA) and
chemical shifts (δ) were reported as ppm from tetramethylsilane
and multiplicity indicated by s (singlet), bs (broad singlet), d
(doublet), or m (multiplet). FTIR (Fourier transform infrared)
spectra were obtained on a Thermo-Nicolet Nexus 470 FTIR
spectrometer (Madison, WI, USA) with a scanning range of
600–4000 cm−1 for 64 scans at a spectral resolution of 4 cm−1.
Synthesis of 1
To a flask containing 4 (1.0 g, 6.57 mmol) and a magnetic stir
bar was added catalytic pTsOH (1.0 or 2.0 mol%) and the
mixture stirred (600 rpm) at 100  C or 110  C for 3–24 hours.
Reactions were performed solventless (neat) or as 1.0, 2.0, or
3.0 M solutions of 4 in toluene with mesitylene (10 mol%) as
an internal standard. Aliquots were periodically removed for
GC–MS determination of reaction progress. Yield data for

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most reactions were obtained using GC–MS taking into con-
sideration the internal mesitylene standard and relative
response factors. In some cases, isolation of 1 and related
byproducts was achieved by equilibrating the reaction mixture
to room temperature, filtering through a short (< 1 in.) pad of
silica gel (70–230 mesh, Sigma-Aldrich Corp.) to remove cat-
alyst, and solvent was recovered (if applicable) via reduced
pressure rotary evaporation (50 mbar, 35  C) to give a color-
less liquid: 1H NMR (CDCl3) δ 7.16 (4H, bs, 4 × Ar-H), 2.92
(1H, septet, J = 6.9 Hz, CH3CH(Ar)CH3), 2.36 (3H, s, Ar-
CH3), 1.28 (6H, d, J = 6.9 Hz, CH3CH(Ar)CH3); 13C NMR
(CDCl3) δ 145.9, 135.2, 129.1, 126.3, 33.7, 24.1, 21.0; IR
(neat) νmax 2958, 2912, 2869, 1515, 1462, 1382, 1362, 1302,
1109, 1056, 1020, 813, 720, 540 cm−1; MS (EI) m/z calcd for
C10H14 134.1, found 134.1 [M]+, 119.1 [M – CH3]+, 91.1 [M
– Pr]+, 77.1 [M – CH3 – Pr]+. 3-Isopropyl-6-methylcyclohex-
2-en-1-one (5) was periodically identified as a minor compo-
nent (3–5%) via GC–MS and confirmed by NMR spectros-
copy: 1H NMR (CDCl3) δ 5.90 (1H, s, >C CH ),
2.46–2.42 (1H, m, CH(CH3)2), 2.39–2.37 (2H, m,
CH2 ), 2.35–2.34 (1H, m, CH2CH(CH3)C( O)CH ),
2.13–2.09 (1H, m, >CHCH2CH2 ), 1.69–1.67 (1H, m,
>CHCH2CH2 ), 1.19 (3H, d, J = 6.9 Hz, CH2CH(CH3)C
( O)CH ), 1.15 (3H, d, J = 6.9 Hz, CH(CH3)2), 1.14 (3H,
d, J = 6.9 Hz, CH(CH3)2); 13C NMR (CDCl3) δ 202.8,
170.7, 123.1, 41.1, 35.6, 31.1, 27.3, 20.6, 19.9, 15.2; MS
(EI) m/z calcd for C10H16O 152.1, found 152.1 [M]+, 137.1
[M – CH3]+, 110.1 [M – Pr]+, 95.1 [M – CH3 – Pr]+.
Green Metrics
Renewable carbon content (RCC; %) was calculated as the
ratio of the number of renewable carbons to total carbons
in the product. Atom economy (AE; %) was determined by
dividing the MW of product by the MW of all stoichiomet-
ric products (Trost, 1991). Carbon economy (CE; %) was
calculated as the ratio of the mass of carbon in the product
by the total mass of carbon in the stoichiometric reactants
(Curzons et al., 2001). The environmental factor (E-factor)
was determined as the ratio of the mass of non-product to
the mass of product (Sheldon, 2007).
Results and Discussion
Serendipitous Discovery of p-Cymene from Perillyl
Alcohol
As part of our continuing efforts to produce aliphatic poly-
esters from renewable starting materials (Moser
et al., 2019, 2020), we were originally attempting to ester-
ify 9-decenoic acid with 4 in the presence of catalytic
J Am Oil Chem Soc (2021) 98: 305–316
309
pTsOH in refluxing toluene to give the corresponding tris-
unsaturated perillyl decenoate as a monomer for subsequent
acyclic diene metathesis polymerization and thiol-ene pho-
tochemical polycondensation. The esterification procedure
had proven simple and effective for several previous con-
densations involving different alcohol/acid combinations
(Moser, 2014; Moser et al., 2019, 2020), but in this case
the expected ester was not observed. Instead, a mixture
comprised of 4, unreacted 9-decenoic acid, and a curiously
high amount of 1 (31%) was noted. With this serendipitous
discovery in hand, we set out to improve the yield of indus-
trially useful 1 from 4 utilizing catalytic pTsOH. We chose
pTsOH because it is simple, inexpensive, less corrosive,
and less toxic than mineral acids such as sulfuric acid and
is less likely to sulfonate our alkenoic substrates and
products.
Synthesis of p-Cymene from Perillyl Alcohol at 100  C
Initial efforts directed at optimization of 1 from 4 were con-
ducted neat at 100  C with catalyst loadings of 1.0 and
2.0 mol% pTsOH. Consumption of 4 was complete by
2 hours under these conditions. At a 2.0 mol% catalyst,
maximum yield of 1 was achieved (86%) within 2 hours,
whereas 6 hours was required to give a lower yield of 84%
when 1.0 mol% catalyst was utilized (Fig. 4d). Most of the
remaining material was non-aromatic dimeric species (16%
and 13% for 1.0 and 2.0 mol% pTsOH, respectively). It
was speculated that dilution of 4 in an inert solvent would
favor intramolecular conversion to 1 while suppressing
intermolecular dimerization. Therefore, a 1.0 M solution of
4 (14.9 wt.%) in toluene was investigated. Toluene was
selected due to its relatively high boiling point and chemi-
cally inert nature under these conditions.
As seen in Fig. 4a, consumption of 4 and accumulation
of 1 were slower at 1.0 M relative to neat conditions, espe-
cially with 1.0 mol% catalyst. The yield of 1 was only 22%
after 24 hours at 1.0 mol% pTsOH with 12% unreacted
4 remaining as well as a considerable amount (53%) of
dimeric species. Maximum yield (85%) was reached faster
(16 hours) when the catalyst load was doubled to 2.0 mol
%. As a result, the starting concentration of 4 was increased
from 1.0 to 2.0 M (29.8 wt.%) to accelerate conversion
while attempting to mitigate dimerization.
Consumption of 4 and accumulation of 1 at 1.0
(24 hours) and 2.0 mol% pTsOH (6 hours) were faster at
2.0 M than 1.0 M, as indicated in Fig. 4b. Furthermore,
dimeric species were limited to less than 8% at maximum
yield of 1 at both catalyst loadings, which was an improve-
ment over neat and 1.0 M conditions. Lastly, 3.0 M con-
centrations of 4 (44.7 wt.%) in toluene were studied to
further reduce the time required to reach maximum yield.
As shown in Fig. 4c, a maximum yield of 89% was attained
310 J Am Oil Chem Soc

Fig 4 Conversion of perillyl alcohol (PA) to p-cymene (CY) at 100  C catalyzed by 1.0 and 2.0 mol% para-toluenesulfonic acid in the presence
of (a) 1.0 M toluene, (b) 2.0 M toluene, (c) 3.0 M toluene, and d) no solvent (neat). Molarities were calculated with respect to PA

after 24 and 4 hours at 1.0 and 2.0 mol% catalyst, respec-
tively. Consumption of 4 was complete after 6 and 2 hours
at 1.0 and 2.0 mol% pTsOH, respectively, with dimer pro-
duction limited to less than 7% at maximum yield of 1. The
early accumulation of dimers followed by their sharp
decline (see Fig. 4b, c and d), except for 1.0 mol% pTsOH
at 1.0 M (Fig. 4a), led us to believe that they served as
intermediates during conversion of 4 to 1. The incongruous
results obtained at 1.0 M with 1.0 mol% pTsOH were
attributed to a reduced reaction rate caused by lower reac-
tant and catalyst concentrations relative to other conditions.
Dimer production is discussed in more detail in the “Pro-
posed Mechanism”.
In summary, the optimum reaction parameters at 100  C
were a catalyst loading of 2.0 mol% and a 3.0 M
concentration of 4. Under these conditions, 4 was consumed
after 2 hours, the maximum yield of 1 was achieved in
4 hours, and accumulation of dimers was minimized. Investi-
gation of a higher temperature (110  C) was of interest to
both shorten the reaction time and further improve the
yield of 1.
Synthesis of p-Cymene from Perillyl Alcohol at 110  C
Based on the promising results obtained at 100  C, reac-
tions at 110  C were conducted for 3 hours with a starting
concentration of 3.0 M utilizing 1.0 and 2.0 mol% pTsOH
(Fig. 5). The yield of 1 approached 80% with 1.0 mol%
pTsOH at 3 hours (Fig. 5a), which was a significant
improvement over otherwise similar conditions at 100  C

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that required 16 hours to achieve comparable results (see
Fig. 4c). The yield of 1 increased to 91% at 3 hours when
the catalyst load was doubled to 2.0 mol% (Fig. 5b). Accu-
mulation of 1 increased sharply for the first 1.5 hours at cat-
alyst loadings of 1.0 (Fig. 5a) and 2.0 (Fig. 5b) mol % but
slowed thereafter. The slower accumulation of 1 after
1.5 hours was accompanied by a slow decrease in dimeric
species. The final percentage of dimers at 3 hours with
2.0 mol% pTsOH was 4%, whereas 18% dimers remained
when 1.0 mol% catalyst was utilized. Lastly, a small
amount of ketone 5 gradually accumulated to 3% with both
1.0 and 2.0 mol% pTsOH, which was not observed when
reactions were conducted at 100  C. The nature of 5 is dis-
cussed more extensively in the “Proposed Mechanism”. In
summary, the highest yield of 1 (91%) was achieved with a
starting concentration of 4 at 3.0 M in toluene in 3 hours at
110  C with 2.0 mol% pTsOH. Lower catalyst loadings
(1.0 mol%), concentrations (1.0 and 2.0 M) and/or tempera-
tures (100  C) gave lower yields of 1, even when longer
reaction times (up to 24 hours) were investigated.
Attempted Synthesis of p-Cymene from Limonene and
Pinene
The optimum reaction conditions for production of 1 from
4 (110  C, 2.0 mol% pTsOH, 3.0 M in toluene) were
applied to the synthesis of 1 from (+/−)-2 (Fig. 6a), α-3
(Fig. 6b) and β-3. As seen in Fig. 6a, synthesis of 1 from
(+/−)-2 did not proceed as readily as that for 1 from 4.
Although (+/−)-2 was consumed within 30 min, the maxi-
mum yield of 1 was only 5%, with the remainder consisting
Fig 5 Conversion of perillyl alcohol (PA) to p-cymene (CY) in 3.0 M toluene at 110  C catalyzed by (a) 1.0 and (b) 2.0 mol% para-
toluenesulfonic acid
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311
mostly of oligomeric species (92%). Oligomers continued
to accumulate at the expense of 1 as the reaction prog-
ressed, reaching a maximum of 99% at 3 hours.
Dehydroisomerization of (+/−)-2 was then attempted at
80  C in 3.0 M cyclohexane utilizing 2.0 mol% pTsOH in
an effort to suppress oligomerization. However, these con-
ditions resulted in accumulation of even more oligomers
(99%). Previous studies that utilized heterogeneous cata-
lysts such as zeolites and acid-activated clays also encoun-
tered significant oligomerization, which was attributed to
regions of strong Brønsted acidity on the catalytic surface
(Du et al., 2005; Fernandes et al., 2007; Golets et al., 2015;
Linnekoski et al., 2014; Lycourghiotis et al., 2018;
Makarouni et al., 2018). Thus, we speculated that the
strong Brønsted acidity of pTsOH (pKa −1.3; Berkowitz
and Grunwald, 1961) favored oligomerization over
dehydroisomerization, thereby resulting in production of
oligomers as opposed to the production of 1. Most of the
oligomers were dimeric (75%), with the remainder con-
sisting of trimers (20%) and tetramers (5%), as deter-
mined by GC–MS analysis. It is likely that such lower MW
oligomers arose via a cationic mechanism, given the acidic
reaction conditions employed herein. Cationic homo-
polymerization of 2 to high MW is normally performed
with Friedel-Crafts or Ziegler-Natta catalysts, and copoly-
merization with alkenoic comonomers proceeds by free
radical mechanisms (Zhang and Dube, 2014).
When the operational parameters of 110  C, 2.0 mol%
pTsOH, and 3.0 M in toluene were applied to α-3 (Fig. 6b),
only 3% of 1 was obtained after 6 hours. A significant
amount of camphene (44%), terpinenes (15%), 2 (14%),
312
Fig 6 Attempted dehydroisomerization of (a) dl-limonene (LIM) and (b) α-pinene (API) in 3.0 M toluene at 110  C catalyzed by 2.0 mol%
pTsOH
and a small percentage of oligomers (4%) were the primary
products. The presence of 2 and its terpinene derivatives
indicated incomplete conversion of α-3 to 1, as they repre-
sent intermediates in the mechanistic pathway of α-3 to
1 (Fig. 3). Camphene, however, was produced by
rearrangement of a key cationic intermediate resulting from
protonation of α-3, and its accumulation indicated that it
was preferred over 1 (and 2) under these conditions. Prior
reports noted that the ratio of camphene to 2 upon acid-
catalyzed isomerization of α-3 was dependent on acidity,
with stronger acids favoring camphene production
(Monteiro and Veloso, 2004; Volzone et al., 2001). Other
conditions, such as reaction temperature, the nature of the
acid (Brønsted vs. Lewis), and pore geometry (in the case
of zeolitic catalysts) reportedly impacted the ratio of cam-
phene to 2. Thus, we speculate that the strong Brønsted
acidity (pKa −1.3) of pTsOH favored the production of
camphene over 2 and its terpinene derivatives, thereby
suppressing the yield of 1.
Application of the same reaction conditions to β-3 gave
faster consumption of starting material and greater accumu-
lation of oligomers relative to α-3 (results not shown). Such
a result was attributed to the higher reactivity of β-3 due to
its more reactive terminal exocyclic double bond vs. the
more highly substituted endocyclic double bond of α-3.
When conducted neat but with otherwise similar condi-
tions, both α-3 and β-3 were converted entirely to oligo-
mers with MW > trimers. Oligomerization of α-3 and β-3
during dehydroisomerization was generally ignored in pre-
vious reports, but was noted in Nie et al., 2014 and
Roberge et al., 2001, who attributed it to strong Brønsted
acidity. Similar to (+/−)-2, α-3, and β-3 likely oligomerized
J Am Oil Chem Soc
via a cationic mechanism, given the acidic reaction condi-
tions utilized herein.
In summary, synthesis of 1 from (+/−)-2, α-3, and β-3
was hindered by the strong Brønsted acidity of pTsOH. At
a substrate concentration of 3.0 M in toluene, oligomeriza-
tion was favored over dehydroisomerization when conver-
sion of (+/−)-2 was attempted whereas camphene was
produced with α-3 and β-3. Under neat conditions, oligo-
merization of 2, α-3, and β-3 was strongly favored. Fur-
ther studies are necessary to elucidate conditions
favorable for production of 1 in high yield from (+/−)-2,
α-3, and β-3. It is likely that catalysts with lower Brøn-
sted acidity are needed to mitigate competing oligomeri-
zation and rearrangement side reactions.
Proposed Mechanism
Ideal dehydroisomerization of 2 and 3 proceeds through
numerous terpinene (α-, β-, γ-, and δ-) and phellandrene
(α- and β-) intermediates, ultimately resulting in the libera-
tion of equimolar H2 gas (Fig. 3) (Al-Wadaani et al., 2009;
Golets et al., 2013; Roberge et al., 2001; Thomas and
Bessiere, 1989). In contrast, the proposed mechanism for
conversion of 4 to 1 entails initial dehydration, followed by
a sequence of p-menthatriene intermediates (I–III) before
producing 1 (Fig. 7). Consequently, equimolar H2O as
opposed to H2 is liberated and terpinenes and phellandrenes
do not serve as intermediates during the mechanistic
sequence. Such mechanistic aspects were confirmed by GC–
MS, as terpinenes and phellandrenes were not observed dur-
ing production of 1 from 4 but compounds with molecular
weights (MW) corresponding to p-menthatrienes (I–III;
J Am Oil Chem Soc (2021) 98: 305–316
J Am Oil Chem Soc
Fig 7 Proposed mechanism for conversion of perillyl alcohol (4) to p-cymene (1) with liberation of water and gradual accumulation of dimer VII
(Fig. 5) were detected. Conversion of II to III and III to
1 involved a series of sigmatropic 1,3-hydride shifts, which
was similar mechanistically to the interconversion of ter-
pinenes and phellandrenes depicted in Fig. 3. The different
mechanisms involved in dehydroisomerization of (+/−)-2,
α-3, and β-3 (Fig. 3) vs. 1 (Fig. 7) as well as the higher reac-
tivity of (+/−)-2, α-3, and β-3 toward pTsOH relative to 4,
we propose were the primary reasons behind the excellent
yield of 1 from 4 but poor yield from (+/−)-2, α-3, and β-3.
As noted in Figs. 4 and 5, dimer production reached a
maximum before declining as 1 accumulated. Mass spectral
results indicated that 93% of dimers near the beginning of
the reaction had an MW of 286.2 while the remainder had
MW = 268.2. By the conclusion of the reaction, the dimer
MW was almost exclusively 268.2. We speculate that
dimers were produced via nucleophilic attack of 4 on sec-
ondary carbocation IV, as depicted in Fig. 7. Attack of the
nucleophilic oxygen of 4 on IV produced dimer V whereas
attack of the pi electrons of the isopropenyl moiety gave
dimer VI, both of which had an MW of 286.2. The nucleo-
philicity of the hydroxyl moiety was significantly greater
than the alkene, thereby resulting in a higher amount of
V produced vs. VI (13.2:1). Subsequent acid-catalyzed pro-
tonation of V resulted in decomposition to 4 and IV, which
J Am Oil Chem Soc (2021) 98: 305–316
313
could then proceed through intermediates I–III shown in
Fig. 7 before producing 1. However, decomposition of VI
to IV and 4 was not possible because cleavage of a carbon–
carbon double bond would have been necessary. Instead,
protonation and subsequent elimination of the hydroxyl
moiety of VI as water yielded relatively unreactive penta-
unsaturated dimer VII, which had an MW of 268.2. There-
fore, the dimer remaining at the conclusion of the reaction
was VII (or its isomers), which had slowly accumulated
from VI, which was the minor dimer formed by condensa-
tion of the alkenoic moiety of 4 with IV.
A minor amount of 3-isopropyl-6-methylcyclohex-2-en-
1-one (5) was produced during the synthesis of 1 from 4, as
shown in Fig. 5. The structure of 5 was indicated by mass
spectral analysis and confirmed by NMR spectroscopy.
Experiments conducted under an inert atmosphere (Argon)
utilizing carefully dried solvent and glassware provided 5 in
the same yield (3%) as reactions conducted less meticulously,
thereby suggesting that the oxygen from the ketone moiety of
5 originated from 4 as opposed to ambient H2O or O2.
Lastly, as expected, o- and m-cymene were not observed
during these reactions, nor was n-propyltoluene. Such
results indicated that unwanted isomerization and trans-
alkylation reactions either did not occur or did so in
314
imperceptible amounts. Avoidance of these byproducts rep-
resented an advantage over the traditional Friedel-Crafts
petrochemical approach as well as approaches using zeo-
litic heterogeneous catalysis.
Green Metrics
Conversion of 4 to 1 was an inherently green process since
it adhered to numerous principles of green chemistry
(Anastas and Eghbali, 2010; Sheldon, 2012). Several met-
rics measure sustainability and “greenness,” among those
are RCC, CE, and AE (Constable et al., 2002; Curzons
et al., 2001; Sheldon, 2018; Trost, 1991). The RCC and CE
of 1 were 100% since all carbons from 4 were incorporated
into 1. Because 4 was dehydrated to form 1, the AE was
88.1% due to loss of H2O. For comparison, the RCC, CE,
and AE calculated for dehydroisomerization of (+/−)-2, α-3,
and β-3 to 1 were 100, 100, and 98.5%, respectively. The
higher AE for (+/−)-2, α-3, and β-3 (98.5%) vs. 4 (88.1%)
was attributed to loss of H2 as opposed to H2O.
The E-factor is defined as the ratio of everything but the
desired product (waste) to the mass of product. It differs
significantly from the other green metrics because it takes
chemical yield into account and includes all reagents, sol-
vents, and processing aids. Lower E-factors are indicative
of less waste and lower environmental impact. Thus, the
ideal E factor is zero (Sheldon, 2007). E-factors for produc-
tion of 1 from (+/−)-2, α-3, β-3, and 4 were calculated
from the highest yielding reactions that employed a starting
substrate concentration of 3.0 M in toluene. Primarily
because H2 or H2O were eliminated and toluene was uti-
lized as solvent, the lowest (best) theoretical E-factors for
production of 1 in quantitative yield from (+/−)-2, α-3,
β-3, and 4 were 2.3, 2.3, 2.3, and 2.4, respectively. For
neat conditions, the theoretical optimum E-factors would
be much lower at 0.1, 0.1, 0.1, and 0.3, respectively,
thereby closely approaching the ideal E-factor of 0. The
experimental E-factors obtained from production of 1
from (+/−)-2 (64.5), α-3 (93.3), and β-3 (98.7) were con-
siderably higher than the corresponding value from 4 (2.7)
due to the significantly higher yield with 4 than from the
other monoterpenes. The E-factor determined for produc-
tion of 1 from 4 utilizing 3.0 M solvent (2.7) was close to
the theoretical optimum value (2.4) as a result of the high
observed yield of 91%. The E-factor utilizing neat condi-
tions (0.4) was also close to the corresponding theoretical
optimum value of 0.3 under neat conditions due to a yield
of 86%. Thus, from a green chemistry perspective, as indi-
cated by E-factor, neat conditions had a lower environ-
mental impact than otherwise similar processing
conditions at 3.0 M despite the lower yield when solvent
was not used.
J Am Oil Chem Soc
Conclusions
The highest yield of 1 (91%) was obtained when starting
with 4 as a 3.0 M solution in toluene in 3 hours at 110  C
with 2.0 mol% pTsOH. Lower catalyst loadings, concentra-
tions, and/or temperatures gave lower yields of 1, even
when longer reaction times of up to 24 hours were
attempted. From a green chemistry perspective, neat condi-
tions had a lower environmental impact (E-factor of 0.4)
than otherwise similar conditions at 3.0 M (2.7) despite a
lower yield of 1 (86%) when solvent was not used. Mecha-
nistically, the reaction entailed dehydration followed by a
series of p-menthatriene intermediates (I–III) and dimers
(V–VII) before giving 1. Such mechanistic aspects were
confirmed by GC–MS, as compounds with MW
corresponding to p-menthatrienes and dimers were detected
during production of 1.
Synthesis of 1 from (+/−)-2, α-3, and β-3 utilizing simi-
lar operational parameters was hindered (yield <5%) by the
strong Brønsted acidity (pKa −1.3) of the pTsOH catalyst.
At 3.0 M, oligmerization was favored over
dehydroisomerization when conversion of (+/−)-2 was
attempted whereas camphene, limonene, and terpinenes
were primarily produced with α-3 and β-3. Under neat con-
ditions oligomerization was strongly favored in all cases.
Given the acidic reaction conditions, it is likely that the
oligomers formed via a cationic mechanism. Thus, the
greater reactivity of (+/−)-2, α-3, and β-3 toward pTsOH
relative to 4 were the primary reasons behind the excellent
yield of 1 from 4 but poor yield from (+/−)-2, α-3, and β-3.
Acknowledgments This research was supported by the
U.S. Department of Agriculture, Agricultural Research Service. Ms
Benetria N. Banks and Ms Judy Blackburn are acknowledged for
excellent technical assistance and Dr Karl E. Vermillion is acknowl-
edged for acquisition of NMR spectra.
Conflict of Interest The authors declare that they have no conflict
of interest.
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