Sustainable Production of o-Xylene from Biomass-Derived Pinacol and Acrolein

Article abstract of DOI:10.1002/cssc.201700823

o-Xylene (OX) is a large-volume commodity chemical that is conventionally produced from fossil fuels. In this study, an efficient and sustainable two-step route is used to produce OX from biomass-derived pinacol and acrolein. In the first step, the phosphotungstic acid (HPW)-catalyzed pinacol dehydration in 1-ethyl-3-methylimidazolium chloride ([emim]Cl) selectively affords 2,3-dimethylbutadiene. The high selectivity of this reaction can be ascribed to the H-bonding interaction between Cl^? and the hydroxy group of pinacol. The stabilization of the carbocation intermediate by the surrounding anion Cl^? may be another reason for the high selectivity. Notably, the good reusability of the HPW/[emim]Cl system can reduce the waste output and production cost. In the second step, OX is selectively produced by a Diels–Alder reaction of 2,3-dimethylbutadiene and acrolein, followed by a Pd/C-catalyzed decarbonylation/aromatization cascade in a one-pot fashion. The sustainable two-step process efficiently produces renewable OX in 79 % overall yield. Analogously, biomass-derived crotonaldehyde and pinacol can also serve as the feedstocks for the production of 1,2,4-trimethylbenzene.

Full text of DOI:10.1002/cssc.201700823

Accepted Article
Title: Sustainable Production of o-Xylene from Biomass-Derived
Pinacol and Acrolein
Authors: Yancheng Hu, Ning Li, Guangyi Li, Aiqin Wang, Yu Cong,
Xiaodong Wang, and Tao Zhang
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To be cited as: ChemSusChem 10.1002/cssc.201700823
Link to VoR: http://dx.doi.org/10.1002/cssc.201700823
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ChemSusChem
10.1002/cssc.201700823
COMMUNICATION
Sustainable Production of o-Xylene from Biomass-Derived
Pinacol and Acrolein
[
a]
[a,b]
[a]
[a,b]
[a]
[a]
[a,b]
Yancheng Hu, Ning Li,*
Guangyi Li, Aiqin Wang,
Yu Cong, Xiaodong Wang, Tao Zhang*
Abstract: o-Xylene (OX) is a large-volume commodity chemical that
is conventionally produced from fossil fuels. Herein, we report an
efficient and sustainable two-step route to OX from biomass-derived
pinacol and acrolein. In the first step, the phosphotungstic acid
process, other valuable chemicals such as aromatic carboxylic
[
4a‒g]
[4h]
[4i]
acids
, toluene , and styrene can also be obtained from
biobased furanics and dienophiles. Despite these impressive
advances, the exploration of new sustainable routes to other
bulk fossil-derived aromatics is still in great demand.
(HPW) catalyzed pinacol dehydration in 1-ethyl-3-methylimidazolium
chloride ([Emim]Cl) selectively afforded 2,3-dimethylbutadiene. The
high selectivity of this reaction can be ascribed to the H-bonding
o-Xylene (OX) is a bulk chemical that is industrially produced
by the fractional distillation of xylenes from catalytic reforming of
petroleum naphtha (Scheme 1). Currently, the world demand for
-
interaction between Cl and the hydroxyl group of pinacol. Besides,
[
5]
the stabilization of the carbocation intermediate by the surrounding
OX was approximately 6 million metric tons per year. Most of
OX (about 90%) is consumed for the preparation of phthalic
anhydride, which is an important monomer for the industrial
production of plasticizers for PVC products (such as bis(2-
ethylhexyl) phthalate, DEHP), unsaturated polyesters, and alkyd
resins. To fulfill the need of sustainable development, it is highly
desirable to exploit a renewable process for the production of
OX from biomass.
-
anion Cl may be another reason for the high selectivity. Notably, the
good reusability of the HPW/[Emim]Cl system can reduce the waste
output and production cost. In the second step, OX was selectively
produced by the D-A reaction of 2,3-dimethylbutadiene and acrolein,
followed by the Pd/C-catalyzed decarbonylation/aromatization
cascade in a one-pot fashion. The sustainable two-step process
could efficiently produce renewable OX in 79% overall yield.
Analogously, biomass-derived crotonaldehyde and pinacol can also
serve as the feedstocks for the production of 1,2,4-trimethylbenzene.
Pinacol is a renewable vic-diol that can be easily prepared by
[
6]
[7]
the metal-mediated coupling
or electrolytic reduction
of
acetone from the ABE (acetone-butanol-ethanol) fermentation of
[
8]
lignocellulose . Notably, Zhu et al. reported a sustainable
The dwindling reserves of fossil resources (such as petroleum,
coal and natural gas) and the increasing social concerns about
global warming make it imperative to develop sustainable routes
to produce renewable fuels
photocatalyzed coupling of isopropanol and acetone for the
[9]
synthesis of pinacol. This approach is efficient and feasible
because the hydrogen generated in the ABE fermentation step
and chemicals. Lignocellulosic
biomass is the most abundant
and carbon dioxide neutral
energy source that can be
used as an alternative to the
conventional fossil feedstocks
[
1]
for the production of fuels
[
2‒4]
and commodity chemicals
The past decade
wittnessed substantial
.
has
achievements in this area. An
elegant example is the
production of p-xylene from
biomass, involving
a Diels-
Alder (D-A) reaction and
dehydration
biomass-derived
cascade
of
2,5-
with
this
dimethylfuran (DMF)
Scheme 1. A comparison of fossil and bio routes to o-xylene (OX).
[
3]
ethylene.
Following
can be used to hydrogenate the acetone to isopropanol. Acrolein,
the simplest unsaturated aldehyde, can be efficiently formed by
the dehydration of glycerol, which is currently oversupplied as a
[
a]
b]
Dr. Y. Hu, Prof. N. Li, Prof. G. Li, Prof. A. Wang, Prof. Y. Cong, Prof.
X. Wang, Prof. T. Zhang
State Key Laboratory of Catalysis
[
10]
byproduct in the biodiesel production.
Thus, developing new
methods for the conversion of acrolein into bulk chemicals will
be of great significance in enhancing the biodiesel economy.
Herein, a two-step route for the synthesis of renewable OX was
first developed using biobased pinacol and acrolein as the
feedstocks (Scheme 1). In the first step, the dehydration of
pinacol selectively afforded 2,3-dimethylbutadiene. It is well-
known that this reaction is very challenging because of the
Dalian Institute of Chemical Physics, Chinese Academy of Sciences
457 Zhongshan Road, Dalian 116023, PR China
E-mail: taozhang@dicp.ac.cn; lining@dicp.ac.cn
Prof. N. Li, Prof. A. Wang, Prof. T. Zhang
iChEM (Collaborative Innovation Center of Chemistry for Energy
Materials)
[
Dalian Institute of Chemical Physics, Chinese Academy of Sciences
457 Zhongshan Road, Dalian 116023, PR China
[
11]
dominant pinacol rearrangement pathway. However, the high
diene selectivity was achieved in this work by employing
Supporting information for this article is given via a link at the end of
the document.
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ChemSusChem
10.1002/cssc.201700823
COMMUNICATION
2
[
(
Emim]Cl as the reaction medium and phosphotungstic acid
40, abbreviated as HPW) as the catalyst. Besides, the
selectivity, while the H-bond C ‒H···OH is not crucial for the
H
3
PW12
O
reaction. Besides the H-bonding interaction, the carbocation
good recyclability of the HPW/[Emim]Cl system can reduce the
waste output and production cost. In the second step, OX was
selectively produced by the D-A reaction of 2,3-
intermediate could also be stabilized by the surrounding anion
Cl , which also contributes to the high diene selectivity. In
contrast, the low selectivity of diene 2 in [Emim]BF , [Emim]NTf ,
4 2
-
dimethylbutadiene
with
acrolein
and
the
following
and [Emim]OAc can be explained by the weak interactions of the
decarbonylation/aromatization cascade in a one-pot fashion.
The acid-catalyzed dehydration of pinacol has two competitive
anions with the hydroxyl group. The sterically hindered butyl
group probably hampers the interaction between Cl and pinacol,
-
pathways: i) 1,2-elimination of H
2
O to diene 2; ii) pinacol
thus affording a low yield of diene 2 in [Bmim]Cl. Besides the
steric hindrance of hexyl group, the aggregation of [Hmim]Cl
may be another reason for its poor result. It has been reported
that with the increment of the alkyl chain length, IL prefers to
rearrangement to pinacolone 3. In most of the cases, this
reaction shows a preference on the pinacol rearrangement
pathway. In this regard, great efforts were devoted to increasing
the diene selectivity. Heteropolyacids (HPAs) have been
regarded as green and versatile solid acid catalysts in
[
15]
aggregate, which limits the transfer of electrons and protons.
[a]
Table 1. Effects of solvent on the HPW-catalyzed pinacol dehydration.
[
12]
replacement to the conventional mineral acids. Therefore, we
chose Keggin HPA phosphotungstic acid (HPW) as the catalyst
to test the solvent effects on the dehydration of pinacol (Table 1).
[11]
Just like many previous works, the dehydration of pinacol in
non-polar solvent (e.g. toluene) favored the rearrangement
pathway (Entry 1). However, it is surprising to find that the
dehydration of pinacol in strong polar solvents (such as dimethyl
sulfoxide (DMSO) and N-methyl pyrrolidone (NMP)) gave diene
N [b]
T
[c]
[c]
Entry
Solvent
E
Yield of 2 / %
Yield of 3 / %
1
2
3
4
Toluene
DMSO
NMP
0.099
0.444
0.355
‒
0
93
13
8
38
17
88
2
as the main product albeit with low yields (Entries 2, 3). These
results indicate that the polarity of the solvent seriously affects
[Emim]Cl
5
[
13]
the dehydration patterns of pinacol.
In view of the fact that
[Emim]Cl
without HPW)
5
‒
N.R.
N.R.
(
ionic liquids (ILs) are endowed with strong electrostatic force
6
7
8
9
‒
‒
0.676
0.710
‒
0
0
79
71
93
N.R.
7
[
14]
and H-bonding interaction, we surmised that the dehydration
in ILs could possibly give a significant increase in the diene
selectivity. As we expected, when the reaction was conducted in
[Emim]NTf
[Emim]BF
2
4
6
[Emim]OAc
[Emmim]Cl
[Pmim]Cl
[Bmim]Cl
[Hmim]Cl
N.R.
83
63
46
N.R.
[
Emim]Cl, diene 2 was obtained in 88% yield and only trace
10
‒
amount of pinacolone 3 was detected (Entry 4). From the blank
experiments using [Emim]Cl or HPW alone (Entries 5, 6), no
diene 2 was observed, indicating that the synergism effect of
11
‒
4
1
2
3
0.614
0.562
2
1
N.R.
[
Emim]Cl and HPW is essential for the high diene selectivity.
The influences of the anion and cation in the imidazolium-based
-
ILs on the reaction were also investigated. When Cl was
-
-
changed to the larger anions such as NTf2 and BF , the main
4
product switched from diene to pinacolone (Entries 7, 8).
Furthermore, the dehydration did not occur in [Emim]OAc (Entry
9
). Interestingly, changing the solvent to [Emmim]Cl, which
2
bears a methyl group at the C position of the ring, afforded
diene 2 in a good yield (Entry 10). By varying the alkyl chain
length on the cation of ILs, we found that longer alkyl substituent
resulted in a decreased diene yield (Entries 11‒13). These
results reveal that the chemoselectivity of diene 2 is strongly
dependent on the chemical structure of ILs.
o
[
a] Reaction conditions: pinacol (1.0 g), HPW (100 mg), solvent (4.0 g), 130 C,
N
16 h. [b] E
T
scale was used to indicate the polarity of organic solvents and
room-temperature ionic liquids. The values were obtained from ref 13. [c] Yields
of 2 and 3 were detected by GC using tridecane as the internal standard. DMSO
=
Dimethyl sulfoxide. NMP = N-Methyl pyrrolidone. N.R. = No Reaction.
According to the reported works, there are different H-bonding
[
14]
interactions between the cation and anion in neat ILs.
In
To further demonstrate the H-bonding interaction of pinacol and
IL, additional NMR experiments were conducted. From the results
shown in Table 1, we can see that the C shift of C1 atom of
pinacol in the mixture of [Emim]Cl and pinacol moves upfield
2
particular, the proton at the C -position is more acidic than other
hydrogens, which leads to the formation of a stronger H-bond
with the anion (C ‒H···X). However, after submitting pinacol to
1
3
2
the ILs, the cation and anion of ILs also compete to interact with
4
(74.82 ppm, Δδ = 0.36 ppm), while [Emim]BF exerts no influence
the hydroxyl group of pinacol through hydrogen bond
on the chemical shift of pinacol. This phenomenon confirms that
-
2
(
C ‒H···OH, X···HO), which might account for the increase of
there exits H-bond between Cl and the hydroxyl group of pinacol
+
-
diene selectivity. According to the results we obtained, both
Emim]Cl and [Emmim]Cl have good performances for the
(Cim Cl ···HO). Besides, the mixture of [Bmim]Cl and pinacol also
gave a decrease in the shift of C1 atom (74.96 ppm, Δδ = 0.22
ppm), but its shift value was lower than that in [Emim]Cl. It is
[
dehydration of pinacol to diene 2. These results suggest that the
-
interaction between Cl and the hydroxyl group of pinacol
because that the bulky butyl group on the ring weakens the H-
bond Cl ···HO, which led to a low diene yield in [Bmim]Cl.
-
(
Cl···HO) plays
a
dominant role in controlling the diene
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ChemSusChem
10.1002/cssc.201700823
COMMUNICATION
1
00
To fulfill the need of real application, the reusability of the
HPW/[Emim]Cl system for the pinacol dehydration was checked.
After each usage, the mixture spontaneously separated into two
phases. The upper layer (i.e. diene 2, GC purity > 94%) was
isolated by decantation. The lower layer (i.e. [Emim]Cl, HPW,
and the byproduct water) was recovered by desiccation and
reused in subsequent runs. From the result shown in Figure 3,
the HPW/[Emim]Cl system can be reused for at least four times
without significant loss in the acitivity.
Yield of 2
Yield of 3
8
6
4
2
0
0
0
0
0
100
Yield of 2
Yield of 3
80
HPMo
HSiW
HPW
H WO
2 4
60
40
20
0
Figure 1. Yields of 2 and 3 over different acid catalysts. Reaction conditions:
pinacol (1.0 g), catalyst (100 mg), [Emim]Cl (4.0 g), 130 C, 16 h.
o
Subsequently, the catalytic performances of other HPAs and
tungstic acid were examined. As shown in Figure 1, other
commonly used Keggin-type HPAs such as phosphomolybdic
acid (H
3
PMo12
O40, abbreviated as HPMo) and tungstosilicic acid
0
1
2
3
4
(
H
3
SiW12
O40, abbreviated as HSiW) were also found to be active
Number of recycling tests
for the reaction. The activity sequence for the investigated HPAs
is HPW > HSiW > HPMo, which is consistent with the acid
strength sequence of these HPAs. Tungstic acid can promote
the dehydration as well but gave an inferior result.
Figure 3. Yields of 2 and 3 over HPW as a function of number of recycling
tests. Reaction conditions: pinacol (1.0 g), HPW (100 mg), [Emim]Cl (4.0 g),
[
16]
o
130 C, 16 h.
100
Yield of 2
Yield of 3
Having established the efficient synthesis of diene 2 from the
selective dehydration of pinacol, we then directed our attention
toward the solvent-free D-A reaction of diene 2 and acrolein into
3-cyclohexenecarbaldehyde 5, which was a potential precursor
for the production of o-xylene (OX) by decarbonylation and
aromatization (or dehydrogenation) reactions. According to our
observation, the D-A reaction of diene 2 and acrolein can
proceed spontaneously in the absence of solvent or catalyst.
After being stirred at 100 C for 2 h, diene 2 and acrolein were
almost quantitatively converted to compound 5 (Figures S5, S19,
and S20).
As the final aim of this work, we studied the production of
renewable OX by the decarbonylation/aromatization cascade of
80
60
40
20
0
o
1
20
130
140
150
160
o
T / C
3
-cyclohexenecarbaldehyde 5. As we know, Pd/C is a highly
[
4e‒g,17]
Figure 2. Yields of
2
and 3 over HPW as
a
function of the reaction
active
dehydrogenation
catalyst
for
both
decarbonylation
and
[
2h,18]
temperature. Reaction conditions: pinacol (1.0 g), HPW (100 mg), [Emim]Cl
. Due to this reason, we surmised that
(4.0 g), 16 h.
Pd/C may promote the production of OX by the
decarbonylation/aromatization cascade of compound 5. Just as
o
we anticipated, this reaction can take place at 260 C under
solvent-free conditions, although the OX yield was not very high
We further studied the influence of the temperature on the
HPW-catalyzed pinacol dehydration. According to Figure 2, a
(
(
Table 2, entry 1). It is interesting that the utilization of toluene
or THF) as solvent significantly improved the OX yield (Table 2,
high yield of diene 2 (88%) was achieved when the reaction was
o
carried out at 130 C for 16 h. With the increment of the
entries 2 and 3). Gratifyingly, 97% yield of OX was achieved
when the reaction was conducted in ethyl acetate (Table 2, entry
o
o
temperature to 140 C or 150 C, the yield of diene 2 remained
comparable. However, after further increasing the temperature
4
),
esterification of biomass-derived ethanol and acetic acid. In
contrast, the attempt of using H O as a green reaction medium
a renewable solvent that can be produced by the
o
to 160 C, a slight decrease in the yield of 2 was observed. This
can be rationalized because too high temperature resulted in the
self D-A reaction of diene 2 (Figures S2, S17, and S18).
2
failed (Table 2, entry 5). The temperature also exerts a great
influence on the OX yield over the Pd/C catalyst. With the
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ChemSusChem
10.1002/cssc.201700823
COMMUNICATION
o
o
decrease of the temperature to 240 C (or 220 C), a lower OX
yield was obtained (Table 2, entries 6, 7).
The catalytic activity of other metals for this cascade process
was further assessed. Besides Pd/C, Pt/C and Raney Ni were
also found to be active for the process although their activity was
lower than that of Pd/C (Table 2, entries 8 and 12). In contrast,
the Ru/C, Ir/C, and Ni/C catalysts were totally inactive under the
investigated conditions (Table 2, entries 9‒11).
Table 2. Screening reaction conditions for the transformation of compound 5
[
a]
into o-xylene 6 via decarbonylation/aromatization cascade.
Scheme 2. Possible reaction pathway for the conversion of compound 5 to OX.
[
b]
o
[c]
We also tried to combine the D-A reaction and the following
decarbonylation/aromatization cascade into a one-pot fashion
Entry
Catalyst
Solvent
T / C
Yield of 6 / %
1
2
3
4
5
6
7
8
9
Pd/C
Pd/C
Pd/C
Pd/C
Pd/C
Pd/C
Pd/C
Pt/C
Ru/C
Ir/C
-
260
260
260
260
260
240
220
260
260
260
260
260
48
88
(
Scheme 3). To do this, a mixture of 2,3-dimethylbutadiene and
Toluene
THF
o
acrolein was first stirred at 100 C for 2 h. After that, ethyl
acetate and Pd/C were added in sequence and the system was
stirred at 260 C for 12 h. As we expected, a high yield (90%) of
87
EA
97
o
H
2
O
0
OX was achieved by this method. In real application, this is
advantageous because the isolation of compound 5 can be
avoided, which will further improve the efficiency and economy
of the process. Taking into account of the optimum diene yield in
the first step, the renewable OX was produced in 79% overall
yield from pinacol and acrolein via such a two-step route.
Crotonaldehyde is another commonly used unsaturated
aldehyde that can be prepared by the self-aldol condensation of
biomass-derived acetaldehyde. 1,2,4-Trimethylbenzene (TMB)
is a bulk chemical that is widely used as a gasoline additive and
EA
EA
EA
EA
EA
EA
EA
69
31
78
N.R.
N.R.
N.R.
39
10
11
Ni/C
12
Raney Ni
[
a] Reaction conditions: compound 5 (0.28 g, 2.0 mmol), catalyst (28 mg),
solvent (0 or 20 mL), argon atmosphere, 600 rpm, 12 h. [b] The catalysts were
obtained from commercial sources and the metal content of the supported
catalysts was 5% by weight. [c] Yields were detected by GC using tridecane
as the internal standard. THF = Tetrahydrofuran. EA = Ethyl acetate. N.R. =
No Reaction.
a
precursor to trimellitic anhydride for the production of
plasticizers for PVC products (such as tri(2-ethylhexyl)
trimellitate, TOTM) and polyester resins. Analogously, a two-
step route for the production of renewable 1,2,4-
trimethylbenzene from pinacol and crotonaldehyde was also
proposed (Scheme 3). The detailed information was given in the
supporting information (Figures S11 and S12). A high overall
yield of 1,2,4-trimethylbenzene (83%) was achieved through this
sustainable process.
To figure out the reaction pathway, we performed the
decarbonylation/aromatization cascade of compound 5 over
Pd/C catalyst at 220 C. From Figure S7, the decrease of
reaction temperature led to a low OX yield and the appearance
o
of 1,2-dimethylcyclohex-1-ene 7 in the products. On the contrary,
3,4-dimethylbenzaldehyde 8 was not identified in the mixture.
This phenomenon indicates that the reaction first undergoes
decarbonylation, followed by aromatization to generate OX
(
Scheme 2). To further confirm this pathway, we conducted the
o
reaction at 260 C for 4 h and detected 1,2-dimethylcyclohex-1-
ene 7 in the mixture as well (Figure S8). From the results, we
can also see that the aromatization of 7 is the rate determining
step in the process.
Scheme 3. A sustainable two-step route for the production of renewable o-
xylene and 1,2,4-trimethylbenzene.
In summary, we have developed an efficient and sustainable
two-step route for the production of OX from biomass-derived
pinacol and acrolein. In the first step, the HPW-catalyzed pinacol
dehydration
in
[Emim]Cl
selectively
afforded
2,3-
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ChemSusChem
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COMMUNICATION
dimethylbutadiene. The utilization of [Emim]Cl as solvent
significantly improved the 2,3-dimethylbutadiene selectivity
which can be ascribed to the H-bonding interaction between Cl
Wan, Nat. Commun. 2013, 4, 2141; g) X. Li, D. Wu, T. Lu, G. Yi, H. Su,
Y. Zhang, Angew. Chem. Int. Ed. 2014, 53, 4200; Angew. Chem. 2014,
126, 4284; h) R. Lu, F. Lu, J. Chen, W. Yu, Q. Huang, J. Zhang, J. Xu,
Angew. Chem. Int. Ed. 2016, 55, 249; Angew. Chem. 2016, 128, 257.
a) C. L. Williams, C. C. Chang, P. Do, N. Nikbin, S. Caratzoulas, D. G.
Vlachos, R. F. Lobo, W. Fan, P. J. Dauenhauer, ACS Catal. 2012, 2,
-
and the hydroxyl group of pinacol. Besides, the stabilization of
[
3]
-
the carbocation intermediate by the surrounding anion Cl may
be another reason for the high selectivity. Notably, the good
reusability of the HPW/[Emim]Cl system can reduce the waste
output and production cost. In the second step, D-A reaction of
935; b) P. T. M. Do, J. R. McAtee, D. A. Watson, R. F. Lobo, ACS Catal.
2013, 3, 41; c) C. C. Chang, S. K. Green, C. L. Williams, P. J.
Dauenhauer, W. Fan, Green Chem. 2014, 16, 585; d) C. C. Chang, H.
J. Cho, J. Y. Yu, R. J. Gorte, J. Gulbinski, P. Dauenhauer, W. Fan,
Green Chem. 2016, 18, 1368; e) H. J. Cho, L. Ren, V. Vattipalli, Y.-H.
Yeh, N. Gould, B. Xu, R. J. Gorte, R. Lobo, P. J. Dauenhauer, M.
Tsapatsis, W. Fan, ChemCatChem 2017, 9, 398.
2,3-dimethylbutadiene with acrolein and the following Pd/C-
catalyzed decarbonylation/aromatization cascade were
successfully combined into a one-pot fashion. The intensified
two-step process could efficiently produce renewable OX in 79%
overall yield. Analogously, biomass-derived crotonaldehyde and
pinacol can also serve as the feedstocks for the production of
[
4]
a) M. Shiramizu, F. D. Toste, Chem.‒Eur. J. 2011, 17, 12452; b) Y.-T.
Cheng, G. W. Huber, Green Chem. 2012, 14, 3114; c) J. J. Pacheco, M.
E. Davis, Proc. Natl. Acad. Sci. USA 2014, 111, 8363; d) E. Mahmoud,
J. Y. Yu, R. J. Gorte, R. F. Lobo, ACS Catal. 2015, 5, 6946; e) S.
Thiyagarajan, H. C. Genuino, M. Sliwa, J. C. van der Waal, E. de Jong,
J. van Haveren, B. M. Weckhuysen, P. C. A. Bruijnincx, D. S. van Es,
ChemSusChem 2015, 8, 3052; f) S. Thiyagarajan, H. C. Genuino, J. C.
van der Waal, E. de Jong, B. M. Weckhuysen, J. van Haveren, P. C. A.
Bruijnincx, D. S. van Es, Angew. Chem. Int. Ed. 2016, 55, 1368; Angew.
Chem. 2016, 128, 1390; g) H. C. Genuino, S. Thiyagarajan, J. C. van
der Waal, E. de Jong, J. van Haveren, D. S. van Es, B. M. Weckhuysen,
P. C. A. Bruijnincx, ChemSusChem 2017, 10, 277; h) S. K. Green, R. E.
Patet, N. Nikbin, C. L. Williams, C. C. Chang, J. Y. Yu, R. J. Gorte, S.
Caratzoulas, W. Fan, D. G. Vlachos, P. J. Dauenhauer, Appl. Catal. B-
Environ. 2016, 180, 487; i) M. Koehle, E. Saraçi, P. Dauenhauer, R. F.
Lobo, ChemSusChem 2017, 10, 91.
1,2,4-trimethylbenzene.
Acknowledgements
This work was supported by the National Natural Science
Foundation of China (no. 21690082; 21506213; 21476229),
Dalian Science Foundation for Distinguished Young Scholars
(
no. 2015R005), the Strategic Priority Research Program of the
Chinese Academy of Sciences (XDB17020100), Department of
Science and Technology of Liaoning Province (under contract of
2
015020086-101) and 100-talent project of Dalian Institute of
[
5]
A. M. Niziolek, O. Onel, C. A. Floudas, AIChE J. 2016, 62, 1531.
a) E. J. Corey, R. L. Danheiser, S. Chandrasekaran, J. Org. Chem.
1976, 41, 260; b) J. L. Namy, J. Souppe, H. B. Kagan, Tetrahedron Lett.
Chemical Physics (DICP). Dr. Hu appreciates the Postdoctoral
Science Foundation of China (2015M581365) and the dedicated
grant for methanol conversion from DICP for funding this work.
[6]
1983, 24, 765.
[
[
7]
8]
a) O. C. Slotterbeck, Trans. Electrochem. Soc. 1947, 92, 377; b) F. D.
Popp, H. P. Schultz, Chem. Rev. 1962, 62, 19.
Keywords: Biomass • o-Xylene • Pinacol dehydration • acrolein
a) B. G. Harvey, H. A. Meylemans, J. Chem. Technol. Biotechnol. 2011,
•
decarbonylation and aromatization
86, 2-9; b) H. Luo, L. Ge, J. Zhang, J. Ding, R. Chen, Z. Shi, Bioresour.
Technol. 2016, 200, 111-120.
[
1]
a) G. W. Huber, J. N. Chheda, C. J. Barrett, J. A. Dumesic, Science
[9]
B. Cao, J. Zhang, J. Zhao, Z. Wang, P. Yang, H. Zhang, L. Li, Z. Zhu,
ChemCatChem 2014, 6, 1673.
2
005, 308, 1446; b) G. W. Huber, S. Iborra, A. Corma, Chem. Rev.
006, 106, 4044; c) J. Q. Bond, D. M. Alonso, D. Wang, R. M. West, J.
2
[10] L. Liu, X. P. Ye, J. J. Bozell, ChemSusChem 2012, 5, 1162.
[11] a) I. Bucsi, A. Molnar, M. Bartok, G. A. Olah, Tetrahedron 1994, 50,
8195; b) A. C. Cole, J. L. Jensen, I. Ntai, K. L. T. Tran, K. J. Weaver, D.
C. Forbes, J. H. Davis, J. Am. Chem. Soc. 2002, 124, 5962; c) M. A.
Nikitina, I. I. Ivanova, ChemCatChem 2016, 8, 1346.
A. Dumesic, Science 2010, 327, 1110; d) P. Anbarasan, Z. C. Baer, S.
Sreekumar, E. Gross, J. B. Binder, H. W. Blanch, D. S. Clark, F. D.
Toste, Nature 2012, 491, 235; e) M. Mascal, S. Dutta, I. Gandarias,
Angew. Chem. Int. Ed. 2014, 53, 1854; Angew. Chem. 2014, 126,
1
885; f) S. Sankaranarayanapillai, S. Sreekumar, J. Gomes, A. Grippo,
[12] S. S. Wang, G. Y. Yang, Chem. Rev. 2015, 115, 4893.
[13] a) C. Reichardt, Chem. Rev. 1994, 94, 2319; b) C. Reichardt, Green
Chem. 2005, 7, 339.
G. E. Arab, M. Head-Gordon, F. D. Toste, A. T. Bell, Angew. Chem. Int.
Ed. 2015, 54, 4673; Angew. Chem. 2015, 127, 4756; g) Q. Xia, Z. Chen,
Y. Shao, X. Gong, H. Wang, X. Liu, S. F. Parker, X. Han, S. Yang, Y.
Wang, Nat. Commun. 2016, 7, 11162.
[14] a) K. Dong, S. J. Zhang, Chem.‒Eur. J. 2012, 18, 2748; b) K. Dong, S.
Zhang, J. Wang, Chem. Commun. 2016, 52, 6744.
[
2]
a) M. Besson, P. Gallezot, C. Pinel, Chem. Rev. 2014, 114, 1827; b) A.
Fukuoka, P. L. Dhepe, Angew. Chem. Int. Ed. 2006, 45, 5161; Angew.
Chem. 2006, 118, 5285; c) N. Ji, T. Zhang, M. Y. Zheng, A. Q. Wang, H.
Wang, X. D. Wang, J. G. G. Chen, Angew. Chem. Int. Ed. 2008, 47,
[15] a) J. J. Wang, H. Y. Wang, S. L. Zhang, H. H. Zhang, Y. Zhao, J. Phys.
Chem. B 2007, 111, 6181; b) C. Y. Shi, Y. L. Zhao, J. Y. Xin, J. Q.
Wang, X. M. Lu, X. P. Zhang, S. J. Zhang, Chem. Commun. 2012, 48,
4103.
8
510; Angew. Chem. 2008, 120, 8638; d) T. Buntara, S. Noel, P. H.
[16] I. V. Kozhevnikov, K. I. Matveev, Appl. Catal. 1983, 5, 135.
[17] a) P. Lejemble, A. Gaset, P. Kalck, Biomass 1984, 4, 263; b) J. Mitra, X.
Y. Zhou, T. Rauchfuss, Green Chem. 2015, 17, 307.
Phua, I. Melián-Cabrera, J. G. de Vries, H. J. Heeres, Angew. Chem.
Int. Ed. 2011, 50, 7083; Angew. Chem. 2011, 123, 7221; e) Y. Liu, C.
Luo, H. C. Liu, Angew. Chem. Int. Ed. 2012, 51, 3249; Angew. Chem.
[18]
M. C. Yin, R. H. Natelson, A. A. Campos, P. Kolar, W. L. Roberts, Fuel
2013, 103, 408.
2012, 124, 3303; f) Y. L. Wang, W. P. Deng, B. J. Wang, Q. H. Zhang,
X. Y. Wan, Z. C. Tang, Y. Wang, C. Zhu, Z. X. Cao, G. C. Wang, H. L.
This article is protected by copyright. All rights reserved.

ChemSusChem
10.1002/cssc.201700823
COMMUNICATION
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COMMUNICATION
Herein we develop an efficient and
sustainable two-step route for the
production of o-xylene from biomass-
Yancheng Hu, Ning Li*, Guangyi Li,
Aiqin Wang, Yu Cong, Xiaodong Wang,
Tao Zhang*
derived
pinacol
and
acrolein.
Noteworthy features of this route
include a recyclable HPW/[Emim]Cl
system for the selective pinacol
dehydration to 2,3-dimethylbutadiene,
Page No. – Page No.
Sustainable Production of o-Xylene
from Biomass-Derived Pinacol and
Acrolein
and
a
one-pot process for the
production of OX by the D-A reaction
of 2,3-dimethylbutadiene with acrolein
and
the
following
decarbonylation/aromatization
cascade.
This article is protected by copyright. All rights reserved.