Towards Improved Biorefinery Technologies: 5-Methylfurfural as a Versatile C6 Platform for Biofuels Development

Article abstract of DOI:10.1002/cssc.201802126

Low chemical stability and high oxygen content limit utilization of the bio-based platform chemical 5-(hydroxymethyl)furfural (HMF) in biofuels development. In this work, Lewis-acid-catalyzed conversion of renewable 6-deoxy sugars leading to formation of more stable 5-methylfurfural (MF) is carried out with high selectivity. Besides its higher stability, MF is a deoxygenated analogue of HMF with increased C/O ratio. A highly selective synthesis of the innovative liquid biofuel 2,5-dimethylfuran starting from MF under mild conditions is described. The superior synthetic utility of MF against HMF in benzoin and aldol condensation reactions leading to long-chain alkane precursors is demonstrated.

Full text of DOI:10.1002/cssc.201802126

Accepted Article
Title: Towards Improved Biorefinery Technologies: 5-Methylfurfural as
a Versatile C6-Platform for Biofuels Development
Authors: Konstantin Galkin and Valentine P. Ananikov
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10.1002/cssc.201802126
ChemSusChem
COMMUNICATION
Towards Improved Biorefinery Technologies: 5-Methylfurfural as
a Versatile C6-Platform for Biofuels Development
Konstantin I. Galkin and Valentine P. Ananikov*
Abstract: Low chemical stability and high oxygen content limits
utilization of bio-based platform chemical 5-(hydroxymethyl)furfural
(HMF) in biofuels development. In this work, Lewis-acid-catalyzed
conversion of renewable 6-deoxy sugars leading to formation of
more stable 5-methylfurfural (MF) is carried out with high selectivity.
Besides its higher stability, MF is a deoxygenated analogue of HMF
with increased C:O ratio. A highly selective synthesis of the
innovative liquid biofuel 2,5-dimethylfuran starting from MF under
mild conditions is described. Superior synthetic utility of MF against
HMF in benzoin and aldol condensation reactions leading to long-
chain alkane precursors is demonstrated.
synthesis from carbohydrates are associated with modification of
platform chemicals furfural and HMF using step-by-step or one-
pot procedures.[8] Direct synthesis of MF involving formation of
HMF from various hexoses followed by iodination and
hydrogenation processes was recently described,[8d] but direct
conversion of carbohydrates without formation of unstable HMF
as intermediate would be a more advantageous approach. In
this work, Lewis-acid-catalyzed dehydration of renewable 6-
deoxy hexoses into MF is implemented with high selectivity, and
the advantages of MF utilization against HMF for development of
liquid biofuels are illustrated.
Integration of renewable resources into sustainable energy cycle
is one of the key challenges of modern chemical science and
technology.[1] Conversion of lignocellulosic biomass to liquid
biofuels, fully compatible with petroleum-based fuels, provides
great opportunities to replace the fossil-derived energy with the
carbon neutral energy concept.[2] Direct utilization of plant
biomass as a source of alternative energy is inefficient due to
the high oxygen content and the low energy density of
carbohydrates.[3] A possible approach to increase the energy
characteristics is to carry out catalytic dehydration of
carbohydrates into platform chemical 5-(hydroxymethyl)furfural
(HMF), possessing many applications as a biofuel precursor.[4]
Direct utilization of HMF as a biofuel is limited by its high boiling
point, high oxygen content, relative chemical instability and
insolubility in hydrocarbons.[5] To access more suitable liquid
Scheme 1. Direct Lewis-acid-catalyzed conversion of 6-deoxy carbohydrates
into MF and the advantages of its utilization, in comparison to HMF, for
biofuels development are described in this work.
biofuels,
hydrodeoxygenation or other chemical modifications of HMF are
required. However, these approaches have number of
further
deoxygenation
by
direct
catalytic
Synthesis of MF from renewable feedstocks. We started
our investigations with MF synthesis by using the catalytic
dehydration of commercially available L-rhamnose (6-deoxy-L-
mannopyranose), which is abundant in plants and produced on
industrial scales.[9] Dehydration of carbohydrates into furanic
products is a well-studied process mediated mainly by BrØnsted
or Lewis acids.[2d, 4b, 10] Catalytic systems based on BrØnsted
acids are poorly adaptable to conversion of hexoses due to side
a
disadvantages associated with difficult hydrogenation of
hydroxyl groups in HMF (and related biofuel precursors)
resulting in harsh reaction conditions and low selectivity of
reduction.[6] In addition, chemical instability and high polarity of
HMF complicates its efficient preparation from renewable
7]
feedstocks.[5a-c,
In this regards, development of reliable
renewable chemical platforms for biofuels production is of
paramount importance.
11]
processes involving oligomerization and decomposition,[5c,
whereas Lewis acids show superior efficiency for dehydration of
aldohexoses.[2d, 4b, 12] We conducted conversion of L-rhamnose
using various Lewis acid catalysts in a biphasic system 1-butyl-
In the present work, we demonstrate that deoxygenated
analogue of HMF, 5-methylfurfural (MF), is a promising platform
for biofuels development (Scheme 1). MF is an industrially
available product that can be considered as a perspective
biofuel candidate due to its reduced oxygen content, chemical
stability, high energy density, low volatility and solubility in
hydrocarbons (Scheme 1).[8] The existing methods of MF
3-methylimidazolium
chloride/methyl
isobutyl
ketone
([BMIM]Cl/MIBK) according to the general methods of high-
yielding dehydration of aldohexoses (Table 1).[12b, 13] Catalysis by
Lewis acids demonstrated full conversion of the initial 6-deoxy
carbohydrate, and the maximal yield of MF was obtained by
using chromium chlorides (Table 1, Entries 1-8). The influence
of reaction conditions such as reaction temperature, type of
catalyst and reaction time was also investigated (see the Table 1,
Entries 1-13 and the Supporting Information for details). Under
the optimized reaction conditions, (Table 1, Entry 8) formation of
[*]
Dr. K. I. Galkin, Prof. Dr. V. P. Ananikov
Zelinsky Institute of Organic Chemistry
Russian Academy of Sciences
Leninsky Prospekt, 47, Moscow, 119991 (Russia)
E-mail: val@ioc.ac.ru
1
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10.1002/cssc.201802126
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COMMUNICATION
MF was conducted with a good yield of 61%. Isolation of MF
was performed by extraction from ionic liquid with MIBK during
the reaction, followed by distillation leading to the desired
product as a colorless oil of more than 99% purity. Only traces of
MF were detected after the conversion process with BrØnsted
acids as catalysts (Table 1, Entries 11-13). Conversion of other
commercially available 6-deoxy sugars L-fucose (6-deoxy L-
galactose) and D-quinovose (6-deoxy D-glucose) was also
studied. Under the same reaction conditions as had been used
for L-rhamnose dehydration, MF was obtained with 12% and
unless the high cost purification is performed). In our previous
work it has been found that oily HMF undergoes rapid
decomposition in the presence of acidic impurities (traces of acid
catalysts), and these processes complicate many applications of
HMF in organic synthesis.[5c] We compared stabilities of
synthesized MF and oily HMF, both obtained by the CrCl2
catalyzed dehydration of L-rhamnose and D-glucose,
respectively, in [BMIM]Cl medium. The samples of ~99% purity
were stored at room temperature for 1 week, and their
composition was monitored by NMR. After 7 days of storage, the
60% yields from L-fucose and D-quinovose, respectively (Table 1, color of the HMF sample changed from light yellow to dark
Entries 14, 15). The absence of the reactive hydroxymethyl
group in C(6) position in the starting materials (6-deoxy
carbohydrates) provided the higher selectivity of conversion as
compared to D-glucose dehydration into HMF proceeded with
only 48% yield at the same reaction conditions (Table 1, Entry
16). A significant decrease in the selectivity of L-fucose
conversion is consistent with a cyclic reaction pathway (see
Scheme S1 for the reaction mechanism in Supplementary
Information).
brown (Figure 1a) and approximately 20 % of by-products
insoluble in chloroform were formed. In contrast, the sample of
MF maintained its light yellow color without significant changes
in purity and solubility in n-hexane (Figure 1b).
Table 1. Catalytic conversion of 6-deoxy hexoses [a]
.
Entry
Substrate
Catalyst
Temp. (°C)
Yield of MF (%)
1
L-rhamnose
L-rhamnose
L-rhamnose
L-rhamnose
L-rhamnose
L-rhamnose
L-rhamnose
L-rhamnose
L-rhamnose
L-rhamnose
L-rhamnose
L-rhamnose
L-rhamnose
L-fucose
AlCl3
100
100
100
110
120
130
100
110
120
130
100
100
100
110
110
110
8
2
FeCl3
10
3
CrCl3·6H2O
CrCl3·6H2O
CrCl3·6H2O
CrCl3·6H2O
CrCl2
22
4
31
5
52
6
29
7
37
Figure 1. a) Samples of pure MF and HMF (0 day) and after 7 days of
storage; b) 1H NMR spectra of aged HMF (top spectrum, no signals, insoluble)
and aged MF (bottom spectrum, signals clearly visible, soluble); samples in n-
hexane for solubility assessment.
8
CrCl2
61
9
CrCl2
48
Selective reduction of C6-furfurals, mostly HMF, is a
general approach used for the synthesis of the innovative liquid
biofuel 2,5-dimethylfuran (DMF) with combustion properties and
physical characteristics comparable to gasoline.[14] Formation of
10
11
12
13
14
15
16
CrCl2
36
HCl
0
H2SO4
traces
traces
12
DMF by hydrodeoxygenation of HMF usually proceeds via MF or
15]
methylfurfuryl alcohol (MFA) as intermediates.[6b,
For this
Amberlyst®
CrCl2
reason, milder and more selective formation of DMF was
observed when MF or MFA instead of HMF were used as
starting substrates.[6a-c, 16] However, direct hydrodeoxygenation
of hydroxymethyl or carbonyl moieties in furan-containing
precursors is generally difficult and low selective, and occurs at
high temperatures of around 100-250 °C.[6, 15-17] To facilitate the
suitability of this process, a substitution of oxygen-containing
D-quinovose
D-glucose
CrCl2
60
CrCl2
48[b]
[a] Reaction conditions: 6-deoxy carbohydrate, catalyst (0.1 eq),
[BMIM]Cl/MIBK, 2h; [b] yield of HMF.
functional groups at the furan ring with more flexible substituents
18]
was performed, followed by a reduction stage.[15e,
We
evaluated the convenient methodology of DMF synthesis by
focusing on the mildest reaction conditions using the transfer
hydrogenation of 5-methylfurfuryl acetate (MFAc) (Scheme 2).
Comparison of chemical properties of MF and HMF.
Generally, direct conversion of carbohydrates provides
a
pathway to rough HMF as an oil (usually of 80-90% purity,
2
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10.1002/cssc.201802126
ChemSusChem
COMMUNICATION
2-
7
8
13, 91
14, 81
pentanone
15,
16,
MIBK
94/94[c]
96/42[c]
cyclo-
hexanone
9
17, 56
18, 59
Scheme 2. Selective synthesis of DMF from MF under mild conditions using
the Ni-mediated transfer hydrogenation. Reaction conditions: (i) NaBH4, MeOH,
0 °C; (ii) Ac2O, Et3N, DMAP; (iii) NiCl2, NaBH4, MeOH, 0 °C. For comparison,
the transformation of HMF is also shown (for the reaction conditions see
Supporting Information).
cyclo-
pentanone
10
11
19, 86
21, 42
20, traces
22, 14
mesityl
oxide
MFAc was synthesized using a two-stage methodology
involving only renewable carbon sources: MF was treated with
sodium borohydride to obtain MFA, followed by acetylation
process (Scheme 2 and Supporting Information for details).
Deoxygenation of MFAc was carried out using nickel boride[19]
prepared in situ from NiCl2 and sodium borohydride in methanol.
Reduction process was conducted at 0 °C for 3 hours and
proceeded with 99 % conversion and 95 % yield of DMF (91 %
overall yield starting from MF). Under the same reaction
conditions, only 86 % conversion and 67 % yield of DMF was
detected after deoxygenation of 2,5-bis(acetoxymethyl)furan
(BAcMF) obtained from HMF[20] (Scheme 2). It is important to
point out, that the studied MF to DMF transformation is based on
renewable, easy separable or recyclable reagents.
[a] Reaction conditions: furanic substrate, [BMIM]Cl, DBU (0.1 eq), 80 °C, 2 h;
[b] Reaction conditions: NaOH, MeOH or MeOH/H2O 1:1, RT, 12 h; [c] Substrate
aged for 7 days was used
Under the similar reaction conditions, the yield of the furoin
1 obtained by self-condensation of MF was significantly higher
than the yield of product 2 obtained from HMF (60 % and 19 %,
respectively). In addition, isolation of the highly hydrophilic
compound 1 by extraction from water was unsuccessful, and the
resulting product was purified by column chromatography of the
crude reaction mixture. In contrast, the more hydrophobic
compound 2 was easily separated from the reaction mixture by
extraction with ethyl acetate followed by flash chromatography
on silica gel (see Supporting Information for details).
Comparative study of suitability of MF and HMF for the
preparation of diverse long-chain alkane precursors.
Condensation of HMF and its derivatives with highly accessible
carbonyl compounds followed by complete hydrodeoxygenation
Evaluation of synthetic potential of MF and HMF in the
base-catalyzed aldol condensation leading to a number of
known and new compounds 3-22 was conducted using highly
accessible bio-derived acyclic and cyclic ketones under green
is a promising route to alkanes with high carbon chain lengths,
23]
conditions (Table 2).[3,
Product 4 obtained by di-aldol
21]
highly suitable as a drop-in diesel and jet biofuels.[4e,
We
condensation of HMF with acetone was isolated in a low yield
(42 %) due to its decomposition in solution during the reaction
and isolation processes. In contrast, the deoxygenated
derivative 3 was stable and obtained with a high selectivity
(Table 2, Entry 2). Products 5-10 of di-aldol condensation of
furfurals with butanone and cyclic ketones (Table 2, Entries 3-5),
as well as mono-aldol adducts 11-18 (Table 2, Entries 6-9) were
obtained in similar yields from both MF and HMF. In contrast,
the mono-aldol condensation with cyclopentanone and mesityl
oxide leading to products 19-22 showed much higher selectivity
when using MF as a starting substrate (Table 2, Entries 9, 11).
Synthetic utility of aged MF and HMF for the synthesis of
alkane precursors formed from cyclopentanone and MIBK was
also studied. Approximately a two-fold decrease in yield and
complications of the isolation process were observed for adducts
8 and 16 obtained from HMF, while utilization of aged MF did not
lead to any significant decrease in the selectivity of
condensation process (Table 2, Entries 4, 7). Therefore, MF will
be much more tolerant to conventional logistics of transportation
to fuel-producing plants, while transportation of HMF would
require special considerations to avoid further obstacles (re-
purification, drop in yield, etc.).
compared the synthetic potential of MF and HMF in the benzoin
and aldol condensation reactions with ketones for the
preparation of long-chain (C9-C18) alkane precursors. Benzoin
condensation of MF and HMF with formation of n-dodecane
precursors 1 and 2, respectively, was conducted by the
organocatalytic approach[7c, 22] using common imidazolium salt
[BMIM]Cl in presence of DBU (Table 2, Entry 1).
Table 2. Comparison of synthetic potentials of MF and HMF in benzoin[a] and
aldol[b] condensation reactions.
Product,
yield (%)
from MF
(R=CH3)
Product,
yield (%)
from HMF
(R=CH2OH)
Initial
ketone
Entry
1
Product
-
1, 60
2, 19
2
3
acetone
3, 87
5, 81
4, 42
6, 83
butanone
In conclusion, a selective model synthesis of the promising
biofuel candidate MF directly from renewable feedstocks by the
Lewis-acid-catalyzed dehydration of 6-deoxy carbohydrates was
carried out. Under the optimized reaction conditions, MF was
obtained in good yields by using an easily accessible catalytic
system. The advantageous higher stability of MF allows its
integration into a biofuel production cycle after synthesis/storage
cyclo-
pentanone
7,
8,
4
5
6
97/96[c]
91/44[c]
cyclo-
hexanone
9, 94
10, 89
12, 89
acetone
11, 91
3
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This study was supported by the Russian Science Foundation
(Grant RSF 17-13-01176).
Keywords: plant biomass • deoxy carbohydrates • biofuels • 5-
(hydroxymethyl)furfural
dimethylfuran
• 5-methylfurfural • alkanes • 2,5-
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COMMUNICATION
Biofuels from renewables:
Konstantin I. Galkin and Valentine P.
Development of renewable sources
for biofuels production is a critical task
for carbon neutral economy.
Ananikov*
Page No. – Page No.
Comparison of the synthetic utility of
bio-based platform chemical HMF and
deoxygenated analogue MF (obtained
by Lewis-acid-catalyzed dehydration
of renewable 6-deoxy hexoses)
showed much higher utility of MF in
biofuels development.
Towards Improved Biorefinery
Technologies: 5-Methylfurfural as a
Versatile C6-Platform for Biofuels
Development
6
This article is protected by copyright. All rights reserved.