Ductile Pd-Catalysed Hydrodearomatization of Phenol-Containing Bio-Oils Into Either Ketones or Alcohols using PMHS and H2O as Hydrogen Source

Article abstract of DOI:10.1002/adsc.201800614

A series of phenolic bio-oil components were selectively hydrodearomatized by palladium on carbon into the corresponding ketones or alcohols in excellent yields using polymethylhydrosiloxane and water as reducing agent. The selectivity of the reaction was governed by the water concentration where selectivity to alcohol was favoured at higher water concentrations. As phenolic bio-oil examples cardanol and beech wood tar creosote were studied as substrate to the developed reaction conditions. Cardanol was hydrodearomatized into 3-pentadecylcyclohexanone in excellent yield. From beech wood tar creosote, a mixture of cyclohexanols was produced. No hydrodeoxygenation occurred, suggesting the applicability of the reported method for the production of ketone-alcohol oil from biomass. (Figure presented.).

Full text of DOI:10.1002/adsc.201800614

Title: Ductile Pd-catalysed hydrodearomatization of Phenol Containing
Bio-oils into either ketones or alcohols using PMHS and H2O as
hydrogen source
Authors: Davide Di Francesco, Elena Subbotina, Sari Rautiainen, and
Joseph Samec
This manuscript has been accepted after peer review and appears as an
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content of this Accepted Article.
To be cited as: Adv. Synth. Catal. 10.1002/adsc.201800614
Link to VoR: http://dx.doi.org/10.1002/adsc.201800614

10.1002/adsc.201800614
Advanced Synthesis & Catalysis
FULL PAPER
DOI: 10.1002/adsc.201((will be filled in by the editorial staff))
Ductile Pd-catalysed hydrodearomatization of
Phenol-Containing Bio-oils into either ketones or alcohols using
PMHS and H2O as hydrogen source
Davide Di Francesco, Elena Subbotina, Sari Rautiainen, and Joseph S. M. Samec*
Department of Organic Chemistry, Arrhenius laboratory, Stockholm University SE-106 91 Stockholm, Sweden
E-mail: joseph.samec@su.se
Received: ((will be filled in by the editorial staff))
Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/adsc.201######.((Please
delete if not appropriate))
Abstract. A series of phenolic bio-oil components were
selectively hydrodearomatized by palladium on carbon into
the corresponding ketones or alcohols in excellent yields
using polymethylhydrosiloxane and water as reducing agent.
The selectivity of the reaction was governed by the water
concentration where selectivity to alcohol was favoured at
higher water concentrations. As phenolic bio-oil examples
cardanol and beech wood tar creosote were studied as
substrate to the developed reaction conditions. Cardanol was
hydrodearomatized into 3-pentadecylcyclohexanone in
excellent yield. From beech wood tar creosote, a mixture of
cyclohexanols was produced. No hydrodeoxygenation
occurred, suggesting the applicability of the reported method
for the production of ketone-alcohol oil from biomass.
Keywords: Beech wood tar creosote; Bio-oil; Cardanol;
Heterogeneous catalysis; Hydrodearomatization; Palladium.
catalyst [8] and gaseous hydrogen.[9] Palladium on
different supports has been investigated in HDA of
phenols, showing 99% conversion of the substrate
with 99% selectivity to the corresponding ketone at
relatively mild reaction conditions.[10–14] On the other
hand, ruthenium based catalysts demonstrated >99%
selectivity to the corresponding alcohols with
excellent activity.[12,15] Palladium-based catalysts can
also afford such selectivity to alcohol through the
optimization of different parameters (e.g. polarity of
support, solvent system, high pressure of
hydrogen).[7,16] Furthermore, no studies have showed
the possibility to use the same catalytic system for
either the production of cyclohexanones and
cyclohexanols independently. Such a ductile catalytic
system would be a useful tool in the bio-oil phenolic
fraction valorisation, since it would enable to steer the
production of valuable chemicals easily without
changing the existing infrastructure.
Introduction
Bio-oil, produced by thermochemical conversion of
biomass, has great potential as sustainable and
renewable source of aromatic compounds.[1] However,
the presence of phenolic compounds from lignin
depolymerization,[2] such as alkyl and methoxy
substituted phenols,[3] and the high oxygen content
hinder the direct utilization of this promising product.
Two different strategies have been proposed to
valorise the aromatic fraction of bio-oil.
Hydrodearomatization (HDA) of phenols yields cyclic
aliphatic ketones that can be transformed into
important precursors for the production of nylon 6,
nylon 66 and polyamidic resins,[4] as well as into
ε-caprolactone for polycaprolactone production.[5]
Alternatively, phenols can be fully hydrogenated to
alcohols followed by hydrodeoxygenation (HDO) to
cycloalkanes to produce biofuel.[6] Both strategies can
be performed in liquid phase using a reducing agent,
resulting in formation of cyclohexanones as final or
intermediate step.[7] Several reports use catalytic
systems with noble metal-based heterogeneous
Due to safety concerns, highly demanding
requirements for handling of hydrogen gas limits the
implementation of bio-refineries.[17] As an alternative,
different hydride donors are known to be effective for
reduction of phenols; formic acid,[18] formates,[19,20]
1
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10.1002/adsc.201800614
Advanced Synthesis & Catalysis
and alcohols[21] have been studied. In addition, silanes
have been used in the hydrogenation of cyclo-
hexanones.[22] Polymethylhydrosiloxane (PMHS) is an
easy to handle and non-toxic hydride source. Currently,
it is generated as a by-product from silicone and
dimethicones manufacturing.[23,24] Therefore, PMHS
has recently attracted attention as a cheap and widely
available alternative to molecular hydrogen.[25–28]
Enthaler and Döhlert proposed an industrial strategy
for recycling spent PMHS to meet concerns about its
sustainability.[29]
Table 1. Optimization of meta-cresol HDA.
PMHS
[equiv]
Conv.
[%]
Ketone
[%]
Alcohol
[%]
Entry
[M]
t [h]
1a)
Pdd)
6
3
>99
97
3
2a)
Pdd)
20
3
99
85
15
In this work, we present a new tuneable
Pd-catalysed HDA strategy using PMHS and water as
hydrogen source to selectively produce either
cyclohexanones or cyclohexanols from phenols and
bio-oils.
3a)
4a)
Pdd)
Rue)
Ruf)
Ptd)
18
6
5
3
5
5
5
5
3
3
>99
20
65
3
35
97
>99
80
>99
64
2
5a)
24
24
18
6
>99
>99
>99
>99
97
-
6a)
20
-
7b)
8b)
9b)
10c)
Pdd)
Pdd)
Pdd)
Pdd)
Results and Discussion
36
98
97
In order to optimize our system, meta-cresol (1) was
selected as model substrate in the HDA. Different
catalysts and reaction conditions were screened in
order to reach high selectivities to both 3-methyl-
cyclohexanone (1a) and 3-methylcyclohexanol (1b)
(Table 1). The presence of water is essential since it
acts as a proton donor during the in-situ hydrogen
production,[30] confirmed by the initial mild
pressurization of the reaction vessel (ESI, Table S4).
Palladium showed the most promising results; full
conversion and 97% of selectivity towards ketone
were achieved when reacting meta-cresol at 80 °C for
6 hours in the presence of 3 equivalents of PMHS
(Table 1, entry 1). The transformation of 1 into 1b
seems to follow a cascade reaction, first 1a is
generated and then further hydrogenated to the
corresponding alcohol, also confirmed by the presence
of 1a in the reaction mixture of an incomplete reaction
optimized for 1b production (Table 1, entry 8). Even
if HDA of phenol can be performed in only water, the
scarce solubility of the chosen model compounds
forced us to screen different organic solvents for the
reaction; aproticity, boiling point below 80°C and
availability were chosen as parameters for practical
reasons (ESI Table S2). THF and Me-THF gave the
highest yields, in line with results reported by Fan and
co-workers.[30] Due to its better water miscibility, THF
was selected as the optimal solvent.[31] In excess of
water, the ratio PMHS/water seems to influence the
amount of molecular hydrogen generated during the
reaction (ESI Table S4). The effect of water as proton
donor was studied by substituting it with MeOH in
different molar ratios (Figure 1). While the proton
donor composition did not affect the conversion, a
clear dependence of ketone selectivity to H2O
concentration was shown. Also, in the absence of
water, the hydrogen formation occurs dramatically
faster resulting in vigorous bubbling detected
immediately after reactant mixing. Furthermore, the
by-product from the reaction between MeOH and
PMHS is soluble in organic solvent, making the work-
up of the reactions tedious.
6
6
>99
3
Reaction conditions: 80 °C, 600 r.p.m. magnetic stirring,
a)
substrate 0.46 mmol.
THF 500µL, H2O 125µL.
b) THF 500µL, H2O 500µL. THF 312µL, H2O 312µL.
c)
d)Metal loading 10%, catalyst amount 5 mol%. Metal
e)
loading 5%, catalyst amount 2.5 mol%. f) Metal loading 5%,
catalyst amount 5 mol%.
Figure 1. Proton donor composition versus conversion and
3-methylcyclohexanone yield. Reaction conditions: 80 °C,
600 r.p.m. magnetic stirring, meta-cresol 0.46 mmol,
hydride donor 3 equiv, THF 500 µL, total proton donor 6.94
mmol, Pd/C 10% 24.5 mg.
For all these reasons, we selected H2O as proton donor
for our study.
Interestingly, the hydrodearomatization of 1 was
very selective towards 1a; even after 20 hours, only
15% of the corresponding alcohol was produced
(Table 1, entry 2). When the amount of hydride donor
was increased, the yield of 1b changed marginally
(Table 1, entry 3). However, using ruthenium on
carbon instead of palladium, 1 was selectively
hydrodearomatized into the corresponding alcohol
(Table 1, entries 4 and 5). Similar selectivity to
2
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10.1002/adsc.201800614
Advanced Synthesis & Catalysis
alcohols has previously been reported with Ru/C using
hydrogen gas.[15] Platinum on carbon showed excellent
conversion but lower selectivity (80% alcohol) under
the same reaction conditions (Table 1, entry 6).
Unexpectedly, 99% selectivity to alcohol was
achieved with palladium by increasing the water
content and amount of hydride donor (Table 1,entry 7).
This demonstrates how the selectivity to ketone or
alcohol is affected by water content in the solvent
fraction, amount of hydride donor, and reaction time
(Table 1, entries 8–10). Blank reactions showed no
conversion without one of the components of the
Table 2. Transformation of phenols to cyclohexanones.
Entry
1a)
Substrate [X]
t [h] Ketone [Xa], yield [%]
1
2
3
4
5
6
7
8
6
3
1a, 97
2a, 90
3a, 95
4a, 93
5a, 95
6a, 85
7a, 85
8a, 93
2a)
3a)
4a)
5b)
6b)
7a)
8a)
proposed
catalytic
system,
even
in
prolonged reactions (114 hours; ESI Table S1).
The Pd/C-PMHS catalytic system was applied for
the HDA of phenolic bio-oil model compounds,[3]
firstly for selective ketone production (Table 2).
Phenol (2) was found to be more reactive than the
benchmark meta-cresol (1), giving 97% selectivity to
cyclohexanone (2a) already in 3 hours, versus 78%
conversion obtained in the same time while reacting 1
(Table 2, entry 1 and 2 and ESI Figure S2-b). Para and
meta alkyl substituted phenols such as para-cresol (3),
4-ethylphenol (4), 3-ethylphenol (5), 4-isopropyl-
phenol (6) and 4-tertbuthylphenol (7) produced the
corresponding ketones from excellent to very good
yield under the optimized conditions (Table 2, entries
3–7). Disubstituted phenols with free ortho position,
e.g. 5-indanol (8) and 3,5-dimethylphenol (9), showed
high reactivity under the employed reaction conditions
generating the corresponding ketones (mixture of
isomers) in excellent conversion and selectivity (Table
2, entries 8 and 9). Ortho-substituted phenols are
challenging substrates.[10] Gratifyingly, ortho-cresol
(10) reacted smoothly to generate the corresponding
ketone in a very good yield (Table 2, entry 10). In this
case, a slightly longer reaction time and an increase in
hydrogen amount were required. Also, 2-ethylphenol
(11) showed high reactivity and gave the
corresponding product in excellent yield (Table 2,
entry 11). Phenols substituted in both ortho positions
are reported to be less reactive substrates. Noteworthy,
2,6-dimethylphenol (12) and 2,4,6-trimethylphenol
(13) underwent HDA to give the corresponding
ketones in very high yields (Table 2, entries 12 and 13).
Methoxy substituted phenols are demanding substrates
due to the ether functionality.[11,13] Nonetheless, HDA
of 3-methoxyphenol (14) and 4-methoxyphenol (15)
gave high to excellent yields of 3-methoxy-
cyclohexanone (14a) and 4-methoxycyclohexanone
(15a) (Table 2, entries 14 and 15).
6
18
18
18
18
6
9a)
9
6
9a, 80
10b)
11c)
12c)
13c)
14a)
10
11
12
13
14
18
24
24
24
6
10a, 85
11a, >99
12a, 85
13a, 77
14a, 85
15a)
6
15a, 83
15
To further elucidate the different reactivity of cresol
isomers, preliminary kinetic study was run to compare
the initial rates of meta and ortho-cresol HDA (ESI
Figure S2). Results confirmed the previous
observations; the kinetic constant for meta-cresol is
approximately 4 times greater than for ortho-cresol.
According to transition state theory the associated
∆∆G‡ would be 1 kcal/mol. Unfortunately, due to the
small magnitude of the energy difference, even state-
of-the-art DFT calculation system would not be able to
elucidate the mechanism, leaving space for more
Reaction conditions: 80 °C, Pd/C 10 wt% (5 mol%),
substrate (0.46 mmol). a) THF:H2O (4:1 v/v, total solvent
volume 625 µL), PMHS (3 equiv). b) THF:H2O (4:1 v/v,
total solvent volume 625 µL), PMHS (5 equiv). c) THF:H2O
(1:1 v/v, total solvent volume 1 mL), PMHS (5 equiv).
3
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10.1002/adsc.201800614
Advanced Synthesis & Catalysis
advanced studies (ESI Figure S2-a).
Table 3. Transformation of phenols to cyclohexanols.
Next, the selective preparation of cyclic alcohols
from bio-oil model compounds was studied (Table 3).
The solvent system and the amount of hydride donor
were the crucial parameters in steering the selectivity
to the cyclic alcohol. Due to the cascade mechanism,
no stereoselectivity was shown. Using the conditions
optimized for compound 1, full conversion and high
selectivity were achieved for HDA of substrates 3 and
Entry
1
Substrate [X]
t [h] Alcohol [Xb], yield [%]
4
to yield the corresponding alcohols, 4-
18
18
18
24
24
1b, >99
3b, 95
4b, 93
5b, >99
6b, 95
1
methylcyclohexanol (3b) and 4-ethylcyclohexanol
(4b) (Table 3, entries 2 and 3). Even with bulkier
substituted phenols, such as molecules 5, 6 and 7, a
slightly increased reaction time enabled high yields of
3-ethylcyclohexanol (5b), 4-isopropylcyclohexanol
(6b) and 4-tertbutyl-cyclohexanol (7b), respectively
(Table 3, entries 4–6).
Recalcitrant disubstituted compound 9 showed
excellent conversion with slightly decreased
selectivity towards 3,5-dimethylcyclohexanol (9b)
(Table 3, entry 7). Less reactive ortho-substituted
phenols, such as compound 10, showed very good
yield towards alcohol, giving 90% yield to
2-methylcyclohexanol (10b) after 18 hours (Table 3,
entry 8). Biphenylic systems like [1,1'-biphenyl]-4,4'-
diol (17), led to [1,1'-bi(cyclohexane)]-4,4'-diol
(17b)[32] in 24 hours with the same reaction conditions
(Table 3, entry 10). Even the bulkier ortho-substituted
isomer, e.g. [1,1'-biphenyl]-2,2'-diol (16), gave very
good yield towards [1,1'-bi(cyclohexane)]-2,2'-diol
(16b) (Table 3, entry 9).[33]. No HDO takes place under
the studied reaction conditions, suggesting a possible
application of the proposed system in ketone-alcohol
(KA) oil production from phenols.
2
3
4
5
3
4
5
6
6
7
24
18
7b, >99
9b, >99
7
9
8
9
18
24
10b, 90
16b, 85
10
16
Cardanol is a complex mixture of substituted
phenols with an unsaturated C15 alkyl chain in meta
position. It is produced by thermochemical
transformation of anacardic acid, the main component
in cashew nut shell liquid (CNSL), that also already
contains some cardanol.[34] Previous study reported a
Raney nickel catalysed hydrogenation of the
unsaturated chain leading to 3-pentadecylphenol.[35]
A
10
24
17b, 83
17
recent study showed the possibility to hydro-
dearomatize cardanol into ketone in presence of a
catalyst under 30 bar of hydrogen.[36] HDA of cardanol
with the proposed hydrogen free Pd/C-PMHS system
produced the corresponding fully saturated alkyl chain
substituted ketone, 3-pentadecylcyclohexanone (18),
as the only product in excellent yield (Scheme 1). Even
though the model compounds study showed that the
reactivity is inversely proportional to the steric
hindrance of the substituents, the cardanol mixture was
fully converted into compound 18 with the same
catalytic system utilized earlier for the models. The
reaction required 72 hours and circa 10 equivalents of
PMHS at 80 °C to reach 99% conversion and >99% of
selectivity towards 18. The increased amount of
hydride donor was needed for full hydrogenation of
the double bonds. Our result demonstrates the
possibility to produce ketone 18 from a natural source
without the use of high pressure hydrogen gas.
3-pentadecylcyclohexanone can find applications in
Reaction conditions: 80 °C, in THF:H2O (1:1 v/v, total
solvent volume 1 mL), PMHS (5 equiv), Pd/C 10 wt% (5
mol%), substrate (0.46 mmol).
Scheme 1. Cardanol HDA into 3-pentadecylcyclohexanone.
4
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10.1002/adsc.201800614
Advanced Synthesis & Catalysis
polymer chemistry by producing pentadecyl
substituted caprolactam, caprolactone and adipic
acid.[36] Under the reaction conditions, no
3-pentadecylcyclohexanol was detected, probably due
to the highly sterically hindering chain that does not
allow 18 further hydrogenation.
Creosote produced by distillation of beech wood tar is
a representative example of bio-oil obtained by
thermochemical conversion of woody biomass. It is
mainly composed of alkyl substituted phenolic
compounds and other aromatics,[37] and has been
widely utilized for decades all over the world as wood
preservative.[38] HDA of beech wood tar creosote was
carried out using our catalytic system with
approximately 12 equivalents of PMHS. After 72
hours reaction at 80 °C, creosote was fully converted
into corresponding cyclohexanols (Scheme 2). By
using shorter reaction time, a mixture of ketones and
alcohols was observed since, as understood from the
model compound studies, different phenolic
compounds undergoes to HDA with different kinetics.
3-pentadecylcyclohexanone as the only product.
Furthermore, beech wood tar creosote was fully
hydrogenated to generate a mixture of substituted
cyclohexanols.
Experimental Section
In a typical experiment, 0.46 mmol of substrate was added
to a vial (2–5 mL) with 24.5 mg of Pd/C 10 wt%, 500 µL of
THF, 125 µL (for ketone selectivity) or 500 µL (for alcohol
selectivity) of deionized water and the required amount of
PMHS. The vial was sealed by using a cap crimper. The
reaction was stirred (600 r.p.m.) at 80 °C. After the required
time, the reaction mixture was cooled down to RT, the vial
was vented and the solvent was removed by flushing argon
through the septum. After solvent removal, the products
were extracted by CDCl3 and 10 µL of internal standard was
added. The solution was filtrated through a 0.45 µm PTFE
syringe filter to a NMR tube. The samples were analysed by
1H NMR spectroscopy.
Acknowledgements
We gratefully acknowledge the Swedish Energy Agency for the
financial support of this work and Cardolite for cardanol supply.
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