Synthesis of Renewable meta-Xylylenediamine from Biomass-Derived Furfural

Article abstract of DOI:10.1002/anie.201803828

We report the synthesis of biomass-derived functionalized aromatic chemicals from furfural, a building block nowadays available in large scale from low-cost biomass. The scientific strategy relies on a Diels–Alder/aromatization sequence. By controlling the rate of each step, it was possible to produce exclusively the meta aromatic isomer. In particular, through this route, we describe the synthesis of renewably sourced meta-xylylenediamine (MXD). Transposition of this work to other furfural-derived chemicals is also discussed and reveals that functionalized biomass-derived aromatics (benzaldehyde, benzylamine, etc.) can be potentially produced, according to this route.

Full text of DOI:10.1002/anie.201803828

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Accepted Article
Title: Synthesis of Renewable meta-Xylylenediamine from Biomass-
Derived Furfural
Authors: François Jérôme, Ivan Scodeller, Samir Mansouri, Didier
Morvan, Eric Muller, Karine De Oliveira Vigier, and Raphael
Wischert
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To be cited as: Angew. Chem. Int. Ed. 10.1002/anie.201803828
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10.1002/anie.201803828
Angewandte Chemie International Edition
COMMUNICATION
Synthesis of Renewable meta-xylylenediamine from Biomass-
Derived Furfural
Ivan Scodeller,[a] Samir Mansouri,[b] Didier Morvan,[b] Eric Muller,[b] Karine de Oliveira Vigier,[a] Raphael
Wischert,*[c] and François Jérôme*[a]
We report the synthesis of bio-based functionalized aromatic
chemicals from furfural, a building block nowadays available in large
scale from low-cost biomass. The scientific strategy relies on a Diels-
Alder / aromatization sequence. By controlling the rate of each step,
it was possible to produce exclusively the meta aromatic isomer. In
particular, through this route, we describe the synthesis of renewably-
sourced meta-xylylenediamine (MXD). Transposition of this work to
other furfural-derived chemicals is also discussed and reveals that
functionalized bio-based aromatics (benzaldehyde, benzylamine,
etc.) can be potentially produced, according to this route.
produced from 5-hydroxymethylfurfural (HMF) and ethylene,[28] in
particular for the synthesis of bio-based terephthalic acid.
Although aromatics were produced in good yields, the lack of
cost-competitive processing technologies to convert low cost
sugars to MF, DMF and HMF currently hampers the industrial
deployment of these routes.
Furfural is a cheap furanic derivative (1.0-1.2 €/kg) available in
large scale from biomass (>200 kT/year), making it an attractive
raw material for the production of bio-based aromatics.[29] In
previous strategies, furfural was decarbonylated in situ to furan
before the DA and aromatization reactions to yield BTX.[30] Mainly
for polymer synthesis, furfural was first converted to amines,[31]
acetals,[32] alcohols,[33] phenolic-type resins,[34] amides[35] or
hydrazones,[36] before DA reaction with alkenes. In these works,
the aromatization of cycloadducts was rarely attempted.
To date, the synthesis of functionalized and industrially relevant
aromatics from biomass such as benzaldehyde, benzonitrile or
benzylamine derivatives, remains scarcely explored.[15b, 28] Among
them, meta-xylylenediamine (MXD) is an important target. MXD
is widely used in the polymer industry as curing agent for epoxy
resins and coatings, and in the production of polyamide, and
polyurethane. Nowadays, MXD is produced at 100 kT/year scale
from fossil feedstocks (isophthalic acid) and is a growing market
(on average 3.45% per year), expected to reach 280 million € by
2021.[37]
Aromatics are an important class of chemicals, in particular for the
manufacture
of
polymers,
solvents,
pharmaceutical,
agrochemicals, and fragrances.[1] Aromatics are produced from
fossil carbon, either by catalytic reforming of naphta or steam
cracking of hydrocarbons.[2] With the exponential growth of the
world population and the resulting pressure on fossil resources,
the industrial production of aromatics will face difficulties to satisfy
the need of our society in a close future. The necessity to diversify
our resources and the general trend of reducing our CO2 footprint
have opened opportunities to produce aromatics from biomass.
Besides performance, profit, environmental and societal gains,
which remain the main criteria for success, utilization of biomass
for chemistry has the potential to develop chemical industries in
different countries, thus creating or relocating jobs.[3] Bio-based
aromatics are typically produced by catalytic fast pyrolysis of
Here, we report a 100% carbon economical bio-based route to
MXD from furfural and acrylonitrile, two abundant and cheap raw
materials. Driving the selectivity to the meta aromatic isomer is an
important scientific challenge, which we address in this work
(Scheme 1).
biomass,[4-11]
cyclotrimerization
of
bio-ethylene,[12]
depolymerization or cracking of lignin,[13] by conversion of
carbohydrates via the furanic platform,[14] or via the bio-based
pinacol platform.[15] In many cases, these processes aim at
producing benzene, toluene and xylene (BTX), which can be
further used without any modification of current downstream
processes and applications.
Previously, bio-based furanic derivatives such as 2-methylfuran
(MF) and 2,5-dimethylfuran (DMF) have been successfully
converted
to
BTX,
through
sequential
Diels-Alder
(DA)/aromatization reactions with ethylene over acid catalysts.[16-
Scheme 1. Pathway to meta-xylylenediamine (MXD) from furfural and
acrylonitrile.
27]
Using the same strategy, renewable aromatics were also
The direct DA reaction of furfural with acrylonitrile failed. Density
functional theory calculations (DFT)[38] at the M06-HF/cc-pVTZ
level[39] (for details and discussion see ESI) indeed confirmed that
[a]
Ivan Scodeller, Dr. Karine de Oliveira Vigier, Dr. François Jérôme
Institut de Chimie des Milieux et matériaux de Poitiers, CNRS,
Université de Poitiers, 1 rue Marcel Doré, 86073 Poitiers (FRANCE)
E-mail: francois.jerome@univ-poitiers.fr
Samir Mansouri, Dr. Didier Morvan, Dr. Eric Muller
Centre de Recherche SOLVAY, 85 Avenue des Frères Perret,
69190 Saint-Fons (FRANCE)
the reaction was thermodynamically unfavorable, with
a
[b]
[c]
substantially positive free energy of reaction (ΔG = +24 kJ mol−1
at 60°C) and an associated barrier of ΔG‡ = 124 kJ mol−1 (Table
S1, entry 1), consistent with the previously observed low reactivity
of furfural in DA reactions. Attempts to use other dienophiles such
as 2-pentenenitrile, acrolein, allyl alcohol or maleic anhydride also
Dr. Raphael Wischert
Eco-Efficient Products and Processes Laboratory, UMI 3464
CNRS/Solvay, 3966 Jin Du Road, Shanghai 201108 (CHINA)
E-mail: raphael.wischert@solvay.com
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10.1002/anie.201803828
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COMMUNICATION
failed. Even in the presence of an acid catalyst or extended
reaction time (up to 4 days), furfural remained unaltered, in line
with calculations (Table S1, entries 2−5). The reactivity of diene
and dienophile in a Diels-Alder reaction is inversely proportional
to the difference in energy of the highest occupied molecular
orbital (HOMO) and the lowest unoccupied molecular orbital
(LUMO) of diene and dienophile, respectively.[40] Electron-
withdrawing substituents stabilize the HOMO of the diene,
resulting in a larger HOMO-LUMO gap and lower reactivity. In the
present case, the electron-withdrawing formyl group in furfural
stabilizes the HOMO by 0.5 eV, compared to furan, which is
known to readily undergo DA reactions (Table S2, entries 1-2).
Therefore, decreasing the electron-withdrawing character of the
aldehyde group should result in a higher reactivity. Among
different strategies, derivatization of furfural by acetalization[32]
with ethylene glycol (also industrially available from biomass) to
2-(furan-2-yl)-1,3-dioxolane destabilizes the HOMO by 0.6 eV
(Table S2, entry 3), resulting in a thermodynamically favorable
reaction with acrylonitrile (ΔG = -2 kJ mol−1 at 60 °C) and an
associated barrier of ΔG‡ = 113 kJ mol−1 (Table S1, entry 6).
Compared to furfural, the reaction is more favorable by 26 kJ
mol−1 and the barrier is reduced by 11 kJ mol−1. As predicted by
the calculation, the reaction was successful: 51% of 2-(furan-2-
yl)-1,3-dioxolane was selectively converted to the corresponding
DA cycloadduct (48% yield) at 60°C (Table 1, entry 1). The ortho
and meta cycloadducts were produced in a 52:48 ratio, with the
endo form being dominant. Time to reach equilibrium (DA vs retro-
DA reaction) was 120 h, affording cycloadducts in 76% yield
(Table 1, entry 2). As expected, when the temperature was
increased to 100°C, conversion and yield dropped dramatically
because the retro DA reaction became dominant (Table 1, entry
3). Further, the ortho to meta ratio changed to 40:60, in excellent
agreement with the thermodynamic isomer ratio of 39:61
calculated by DFT (ESI).
When the temperature was reduced to 40 °C, the yield dropped
significantly and at 25 °C no conversion was observed (Table 1,
entries 4-5), indicating that the activation barrier of the reaction
could not be overcome, in line with calculations (Table S3 and
discussion in the SI). Hence, 60 °C was selected as a compromise.
Among different tested acid catalysts, only anhydrous ZnI2 and
ZnCl2 significantly decreased the time to reach the chemical
equilibrium, with ortho/meta and endo/exo ratios almost identical
to those obtained without catalyst (Table S4). For instance, the
conversion of 2-(furan-2-yl)-1,3-dioxolane reached 78% and 87%
after 25 h of reaction, in the presence of ZnCl2 and ZnI2,
respectively (Table 1, entries 6, 7). The selectivity was however
slightly lower with Zn-based catalysts, due to the partial
deprotection of the starting 2-(furan-2-yl)-1,3-dioxolane (~10%),
water being used as a stabilizer of acrylonitrile (0.2-0.5 wt%).
Aromatization of DA cycloadducts is usually carried out in the
presence of acid catalysts such as H2SO4,[24, 41] H-Y zeolites,[24] Hf,
Zr and Sn beta zeolites,[42] silica-supported Lewis acids,[43] or
mixed sulfonic carboxylic anhydrides in methane sulfonic acid.[44]
Unfortunately, this reaction often competes with the retro DA
reaction, due to the high temperature required. In line with these
reports, in the presence of H2SO4, Aquivion PFSA PW65S or
zeolite HY, at 100°C, both under solvent-free conditions or in
dimethylsulfoxide (DMSO), no aromatization took place and only
the retro-DA reaction was observed.
The presence of an acidic proton in the cycloadducts (-CH-CN
group) prompted us to investigate aromatization under basic
conditions, initially unsuccessful under commonly used
deprotonation conditions (ESI). From the chemical shift of this
acidic proton (2.75-3.30 ppm), we concluded that a superbase
would be required for deprotonation. DMSO has the ability to
generate such species with a pKa value of about 30-32, by
solvation of counter-cations such as K+ or Na+.[45] Pleasingly,
aromatization of the DA cycloadducts (meta/ortho ratio of 1) with
20 mol% of CH3ONa in DMSO resulted in 86% yield to aromatics
after only 1 h at 30 °C, with a meta/ortho ratio of 1.8 (Table 2,
entry 1), indicating faster reaction of the meta isomer. Other bases
Table 1. DA reaction between 2-(furan-2-yl)-1,3-dioxolane and
acrylonitrile.[a]
Table 2. Deprotonation of the DA adducts obtained from 2-(furan-2-yl)-1,3-
dioxolane and acrylonitrile.[a]
Entry
T
(°C)
Cat.
Time
(h)
Conv
(%)
Yield
(%)
ortho
(%)[b]
meta
(%)[c]
1
2
3
4
5
6
7
60
60
-
48
120
7.5
48
51
82
21
10
0
48
76
19
9
52
48
40
51
0
48
52
60
49
0
Time
(h)
Total Yield to
aromatics (%)
Entry
Catalyst
meta:ortho ratio
-
100
40
-
1
2
3
4
5
CH3ONa
tBuONa
KOH
1
1
1
1
7
86
84
80
74
38
1.8:1
1.5:1
1.7:1
2.3:1
3.4:1
-
-
25
48
0
60
ZnCl2
ZnI2
25
78
87
68
75
53
53
47
47
NaOH
A26
60
25
[a] 5 eq. acrylonitrile; [b] endo/exo = 7/3; [c] endo/exo = 6/4.
[a] cycloadduct ortho:meta ratio of 1:1
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10.1002/anie.201803828
Angewandte Chemie International Edition
COMMUNICATION
such as tBuONa, KOH, and NaOH led to similar yields and ratios
(Table 2, entries 2-4). To facilitate the work-up, an insoluble
strongly basic anion exchange resin (Amberlyst-26, OH– form)
was tested. Despite being less active, aromatics were selectively
produced in 38% yield in 7 h (Table 2, entry 5). In all cases, almost
quantitative yields could be reached by extending the reaction
time to 3 h, except for Amberlyst-26, which required 3 days. Note
that, without any base, the aromatization did not proceed in
DMSO. Consistent with the results presented in Table 2, the
kinetic profile of the aromatization reaction revealed that the meta
cycloadduct was more reactive than the ortho isomer. In particular,
the aromatic ortho started to be produced only after the meta DA
adduct was almost completely converted (Fig. 1). Calculations
indeed support a higher acidity of the meta, compared to the
ortho-CH-CN protons (by ~2 pKa units, see ESI). This difference
is of strong interest since it allows the meta and the ortho aromatic
isomers to be produced consecutively, but separately.
that the reaction can be easily quenched by filtration of the base,
thus making product separation from DMSO unnecessary.
Deprotection of the meta isomer in THF in the presence of a
catalytic
amount
of
aqueous
HCl
afforded
meta-
cyanobenzaldehyde in quantitative yield, and ethylene glycol,
which can be recycled for protection of furfural. Reductive
amination of the aldehyde (80 °C, 30 bar of H2, in the presence of
Raney Co and ammonia) afforded MXD with 70% yield (results
not optimized, Fig. 3).
Figure 3. Catalytic conversion of 3-(1,3-dioxolan-4-yl)benzonitrile to MXD.
50
45
40
35
30
25
20
15
10
5
Guided by DFT calculations, which predicted destabilization of the
HOMO vs. furfural (Table S2, entries 3−6) and conversion to
products (ΔG = 3 to 9 kJ mol-1, ΔG‡ = 111–112 kJ mol–1, Table S1,
entries 7-9), alternative pathways to benzonitrile derivatives were
explored, starting from other furfural-derived chemicals
(ethylfurfuryl ether, furfuryl alcohol, 2-methylfuran and furfuryl
amine). Except from furfuryl amine, these attempts were again
successful, leading to the corresponding cycloadducts in 54% to
73% yield (Table 4). Different ortho/meta ratio were obtained,
because (i) the DA reaction had not reached equilibrium and (ii)
slightly different electronic and steric effects. At equilibrium (after
few days of reaction), the ortho/meta ratio was close to 1 in all
cases. Aromatization (30°C in DMSO, 20 mol% of tBuONa)
afforded the corresponding aromatics in high yield (> 80%),
except for furfuryl alcohol (Table 4, entry 3). For furfuryl alcohol
and ethylfurfuryl ether, the corresponding meta cycloadduct was
0
0
20
40
60
80
100
Conv. (%)
Figure. 1. Yield of ortho and meta isomers as a function of the conversion.
With this result in hands, the possibility to enrich aromatic
products into the meta isomer was then checked (Fig. 2). At 50%
conversion, the aromatization was quenched by dilution in water
and the aromatic meta product and the unreacted ortho
cycloadduct were both recovered by extraction with ethyl acetate.
Next, these two products were heated at 120°C under vacuum to
induce the quick retro-DA of the remaining ortho cycloadduct back
to acrylonitrile and 2-(furan-2-yl)-1,3-dioxolane, leaving the meta
aromatic unaltered. After completion of the retro-DA, distilled
acrylonitrile was re-introduced into the reactor and re-submitted
to DA and aromatization reactions. After these two repeated
cycles, the meta aromatic isomer was thus produced with an
overall yield of 75%. The process can be then repeated up to the
nearly exclusive formation of the meta isomer (Fig. 2). Using the
solid base Amberlyst-26 instead of CH3ONa has the advantage
Table 4. Scope of the reaction.
Yield to
cycloadduct (%)
Yield to aromatics
(%)[a]/[b]
Entry
R
meta
18
13
26
-
Ortho
36
Total
66/96
53/80
9/32
-
meta[c]
88/100
29/62
12/42
-
ortho[c]
1
2
3
4
-CH2OEt
-CH3
62/94
72/97
5/21
-
53
-CH2OH
47
(b]
-CH2NH2
-
[a] after 10 min; [b] after 60 min; [c] yield relative to the corresponding ortho or
meta DA cycloadduct; [b] from furfuryl amine, a complex mixture of compounds
was obtained due to parasite Michael addition of furfuryl amine to acrylonitrile.
Figure. 2. Reaction sequence for enriching the meta aromatic isomer.
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10.1002/anie.201803828
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COMMUNICATION
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selectivity to the meta aromatic can be kinetically controlled, as
discussed above. Reversely, from 2-methyl furan, the ortho
cycloadduct was more reactive (Table 4, entry 2).
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In conclusion, we report here that industrially relevant aromatic
chemicals, such as MXD, can be selectively synthesized from
furfural and acrylonitrile through a 100% carbon-economical route.
The pathway involves a Diels-Alder/aromatization sequence as a
key step. Importantly, we showed that (1) the aromatization step
could be catalyzed at low temperature by bases instead of acids,
thus avoiding the usually observed retro-Diels-Alder reaction, and
(2), by playing with the rate of the reactions, it was possible to
selectively drive the reaction to the meta aromatics. One should
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Entry for the Table of Contents
COMMUNICATION
Renewable meta-xylylenediamine was
produced at low temperatures from
bio-based furfural and acrylonitrile by
using sequential Diels-Alder/base-
catalyzed aromatization reactions. A
kinetic control of the aromatization
step permitted the selective formation
of the meta isomer.
Ivan Scodeller, Samir Mansouri, Didier
Morvan, Eric Muller, Karine de Oliveira
Vigier, Raphael Wischert,* and François
Jérôme *
Base-catalyzed aromatization
Page No. – Page No.
Synthesis of Renewable meta-
xylylenediamine from Biomass-
Derived Furfural
+
Bio-based
Meta-xylylenediamine
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