Facile synthesis and isolation of 5-hydroxymethylfurfural from diphenyl sulfoxide

Article abstract of DOI:10.1039/d1gc00302j

We report diphenyl sulfoxide (DPhSO) as an active, cheap and environmentally friendly solvent to facilely synthesize 5-hydroxymethylfurfural (HMF) from fructose. It acts as both the catalyst and solvent to afford nearly 100% conversion of fructose and 68.4% yield of HMF. In particular, HMF was easily extracted using water and DPhSO froze into an insoluble solid at low temperature. DPhSO was reused 6 times without significant loss of activity. The reaction mechanism of DPhSO-catalyzed HMF formation was analyzed by NMR and ESI-MS experiments and theoretical calculations.

Full text of DOI:10.1039/d1gc00302j

Showcasing research from Professor Jian Zhang's
laboratory, Ningbo Institute of Materials Technology &
Engineering Chinese Academy of Sciences, Ningbo, China.
As featured in:
Volume 23
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May 2021
Pages 3143-3488
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Facile synthesis and isolation of 5-hydroxymethylfurfural
from diphenyl sulfoxide.
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Cutting-edge research for
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An active, cheap and environmentally friendly DPhSO was
first employed to synthesize HMF from fructose as both
catalyst and solvent, realizing the easy isolation of HMF by
water due to the water-immiscible nature of DPhSO.
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James A. Dumesic et al.
Sustainable production of 5-hydroxymethyl furfural from
glucose for process integration with high fructose corn
syrup infrastructure
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Facile synthesis and isolation of
5
-hydroxymethylfurfural from diphenyl sulfoxide†
Cite this: Green Chem., 2021, 23,
241
3
a
a,b
a
a
a
Tongtong Zhang,‡ Yaoping Hu,‡ Liyuan Huai, * Zhijin Gao and Jian Zhang*
Received 27th January 2021,
Accepted 22nd March 2021
DOI: 10.1039/d1gc00302j
rsc.li/greenchem
We report diphenyl sulfoxide (DPhSO) as an active, cheap and to induce C–C bond scission. Ionic liquids and high-boiling
environmentally friendly solvent to facilely synthesize 5-hydroxy- organic solvents like dimethyl sulfoxide (DMSO) are the pre-
methylfurfural (HMF) from fructose. It acts as both the catalyst and ferred solvents to provide a high yield and selectivity of HMF
16–21
solvent to afford nearly 100% conversion of fructose and 68.4% (>90%) with the assistance of acid catalysts.
However,
yield of HMF. In particular, HMF was easily extracted using water product isolation could not be simply conducted due to either
and DPhSO froze into an insoluble solid at low temperature. the broad compatibility of ionic liquids with almost all sol-
DPhSO was reused 6 times without significant loss of activity. The vents or the difficulty in recycling DMSO with a high boiling
reaction mechanism of DPhSO-catalyzed HMF formation was ana- point. Deep eutectic solvents (DESs) are emerging as green sol-
lyzed by NMR and ESI-MS experiments and theoretical vents for HMF synthesis with good yields and recycling pro-
calculations.
perties, whereas these solvents require the aid of acid catalysts
2
2–24
and organic solvents for HMF separation.
A biphasic
As the only sustainable and abundant source of organic
carbon, biomass should be effectively converted into platform
chemicals
system allows HMF generation in the aqueous phase and con-
tinuous extraction into an organic solvent, well suppressing
for
building
useful
organic
products.
25,26
the unfavourable side reactions.
Nevertheless, these
5
-Hydroxymethylfurfural (HMF), being produced by the de-
technologies also face great difficulties in product isolation
and solvent refreshing. Therefore, proper selection of a “soft”
catalyst and green solvent to facilitate HMF separation and
hydration of pentoses or hexoses, is envisaged as a versatile
link between natural carbohydrates and new value-added
chemicals such as 2,5-dimethylfuran, 2,5-bis(hydroxymethyl)
furan, 5-hydroxymethyl-2-furancarboxylic acid, 2,5-diformyl-
furan and 2,5-furandicarboxylic acid for applications in clean
fuels and degradable polymers.
Over the past several decades, many efficient acid-catalyzed
methods to synthesize HMF have been reported,
27–29
stability and to refresh easily is still urgently needed.
Herein, we report for the first time the use of an in-
expensive industrial waste diphenyl sulfoxide (DPhSO) as a
separable solvent and catalyst for converting fructose to HMF.
The structure of DPhSO is similar to that of DMSO but their
physical properties are totally different. Thanks to the appro-
priate melting point (69–71 °C), DPhSO remains in a solid
phase before it liquefies at temperatures above ∼70 °C, thus
rendering itself a thermo-regulated phase-switchable solvent.
As the sulfoxide group could act as the catalytically active
center for fructose dehydration, no additional catalyst is
required in this system. Easy product separation was per-
formed by water extraction of HMF from DPhSO due to the
high partition coefficient of HMF in water/DPhSO biphasic
media, where HMF is soluble in water while DPhSO is slightly
1
–7
8
–13
while
their industrialization process is strictly hindered by the unre-
solved technological problems, particularly product stabiliz-
ation and isolation. First, HMF is poorly stable in aqueous
media and easily rehydrates to levulinic acid (LA) and formic
1
4,15
acid (FA).
Brønsted acid catalysts always present consider-
able activity but simultaneously drive the rehydration reaction
a
Key Laboratory of Bio-based Polymeric Materials Technology and Application of
Zhejiang Province, Ningbo Institute of Materials Technology & Engineering, Chinese
Academy of Sciences, Ningbo 315201, P. R. China. E-mail: huailiyuan@nimte.ac.cn,
jzhang@nimte.ac.cn
−
1
soluble in water with a measured solubility of 1.2 g L
.
Notably, DPhSO is thermally and chemically stable after being
used multiple times, which paves the way for the future mass
production of HMF. The reaction mechanism was also investi-
gated to gain a clear comprehension of the catalytic nature of
DPhSO.
b
School of Materials Science and Chemical Engineering, Ningbo University, Ningbo
315211, P. R. China
†
Electronic supplementary information (ESI) available. See DOI: 10.1039/
d1gc00302j
These two authors contributed equally.
‡
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The catalytic performances of several active solvents for ing DPhSO and formed humins. The HMF aqueous solution
fructose dehydration were first compared without the addition was easily collected for further reaction. It is noted that DMSO,
of other catalysts, including DMSO, DPhSO and three ionic having a much lower melting point (18.5 °C), is mutually
liquids (EMImBr, BMImBr and BMImCl) as shown in Fig. 1a. soluble with many kinds of common solvents.
With the increase of reaction time, DMSO was the best aprotic
Both fructose conversion and HMF formation in DPhSO
solvent to provide the highest yield of HMF, and the yield in were significantly improved by raising the reaction tempera-
DPhSO approached almost the same value lately. Both solvents ture from 100 to 140 °C (Fig. S1c and d†), reaching the highest
are obviously superior to the three commercial ionic liquids HMF yield of 68.4% at 11 h. LA and FA were also quantified
but are quite different in product isolation. Experiments at with low yields of 1.38% and 4.63%, respectively. However, as
higher fructose concentrations were further conducted and the temperature was continuously elevated to 160 °C, the yield
compared with those reported in the literature under the same first increased and then decreased to give a maximum of only
conditions (Table S1†). The results indicated that the HMF 55.4% at 1.5 h, which could be attributed to the deterioration
yield is comparable with that in DMSO, confirming that and/or polymerization of HMF.
DPhSO is a potential solvent. Fig. 1b illustrates the whole de-
The structural stability and recyclability of the solvent is
hydration process of fructose in DPhSO and the subsequent vital for a new liquid-phase catalysis technology. Fig. 1c shows
HMF separation procedure. Initially, fructose and DPhSO were the reuse performance of DPhSO without removing humins
simultaneously put into a glass bottle with a sealed cap. They after each run. The added fructose was almost completely con-
were quickly melted to liquid form at the preheated target verted, while the HMF yield slightly dropped from 68.4% to
temperature. With increasing reaction time, the mixture first 61.2% after six cycles. Such a decline could be related to the
turned from colourless to yellow and then dark brown, being accumulation of humins that either affected the fructose solu-
typically related to the formation of HMF and humins. The bility in successive cycles or physically blocked the interaction
reaction was terminated by quickly cooling the bottle and between the reactant and active solvent. The characteristics of
adding pure water. Owing to the water-immiscible nature of the hydrogen species in DPhSO showed no obvious change
1
DPhSO and the high partition coefficient of HMF in the after the reaction and refreshing as indicated by the H NMR
1
DPhSO/water biphasic media, pure water serves as a wonderful spectra (Fig. 1d). The magnified H NMR spectra of DPhSO in
solvent to extract HMF from DPhSO. Meanwhile, the liquid Fig. S2† after heating and reaction also proved its stability, and
3
0
DPhSO at the bottom solidified into a brown mixture contain- several additional peaks can be assigned to humins. The
Fig. 1 (a) The comparison of HMF yield in DPhSO and other active solvents at 120 °C. Initial conditions: fructose, 0.05 g; DPhSO, 1.0 g; DMSO,
1
.0 mL; and ionic liquids, 1.0 g. (b) The whole reaction and separation process of HMF formation from fructose in DPhSO. (c) Cyclic utilization of
1
DPhSO at 140 °C, cycle R means that the used DPhSO has been refreshed. (d) The H NMR spectra of DPhSO before reaction, after reaction and
after refreshing. (e) The used DPhSO before and after refreshing. H , 30 wt%, 5.0 mL; NaOH, 1 M, 5.0 mL; and time, 30 min.
2
O
2
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result demonstrated the robust stability and reuse perform- reaction pathways were compared and the most favourable one
ance of DPhSO to catalyse HMF formation even in the pres- is shown in Fig. 2a, and others are displayed in Fig. S3.† The
3
1
ence of tremendous amount of humins. The accumulated fructose first undergoes isomerization as reported in DMSO
humins in DPhSO could be effectively removed by simple oxi- and is slightly endothermic by 1.12 kcal mol− , indicating that
1
dation by adding 30 wt% H O and 1 M NaOH at 50 °C isomerization occurs easily. The isomer then undergoes direct
2
2
(Fig. 1e). The refreshed DPhSO with a white colour gave a HMF dehydration via two adjacent hydroxyl groups. In the second
yield of 66.5%, being close to that of the first run. In a scale- step, the SvO group of DPhSO attacks the hydroxyl group at
up experiment with the optimal ratio of fructose and DPhSO, 3-C of β-D fructose through hydrogen bond interactions, fol-
an increased fructose (1.5 g) and DPhSO (30 g) system achieved lowed by attacking the hydroxyl at 4-C. The hydrogen bond
a HMF yield of 60.1% at 130 °C after optimizing several temp- between SvO of DPhSO and the hydroxyl exists in all inter-
eratures of 120 °C, 130 °C and 140 °C with small LA and FA mediates and transition states and thus could promote de-
yields of 1.39% and 5.35%. Besides, the DPhSO was found to hydration and stabilize the intermediates. The calculated
−
1
weigh 28.2 g after refreshing. Considering the factors of energy barriers were 43.87, 54.47, and 59.37 kcal mol for
solvent loss and wall hanging in the process of regeneration, these three elementary steps and the reaction energies were
4.75, 1.91 and −13.73 kcal mol− , respectively. Clearly, the rate-
1
there was no obvious solvent degradation during the reaction.
The reaction mechanism of DPhSO-promoted dehydration determining step is the third step, and the energy barrier is
from fructose to HMF was then investigated through theore- similar to that in the recently reported fructose dehydration
−
1 32
tical and experimental studies. The theoretical calculations catalysed by DMSO (48.57 kcal mol
)
and BMImBr
−1 33
were first performed to demonstrate the intrinsic catalytic pro- (57.35 kcal mol ), indicating that DPhSO can act as a cata-
perties of DPhSO. The activation energies of all the possible lyst for the conversion of fructose to HMF.
Fig. 2 (a) Geometric structures of the dehydration intermediates and relative Gibbs free energies for the conversion of fructose to HMF catalyzed
13
by DPhSO at 120 °C. The energies are relative to the isolated β-D fructose and DPhSO. (b) The 2- C NMR spectra for the reaction of fructose with
DPhSO at 100 °C; the cooled solution was dissolved in DMSO and the spectra were obtained at room temperature. (c) The ESI-MS spectra for the
reaction of fructose with DPhSO at 100 °C; the solution was dissolved in methanol and the spectra were obtained at room temperature.
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The reaction intermediates were characterized by NMR and fructose are the key to promote the reaction. Our work pro-
1
3
13
the no. 2 carbon labelled C (2- C) of fructose was used to vides a convenient way for HMF formation and separation and
assign the chemical shifts of intermediates. The cyclic fructose paves the way for further improvement of HMF productivity via
(β-pyranose, α-furanose, and β-furanose) was first confirmed in the modification of the solvent structure or the design of high-
the initial spectrum (t = 0 min) as shown in Fig. S4.† When the performance heterogeneous catalysts.
reaction proceeded for 30 minutes (Fig. 2b), a new resonance
peak at 152.3 ppm of HMF appeared, while the other new peaks
were attributed to the reaction intermediates and byproducts. Conflicts of interest
31
Based on the proposed reaction mechanism in DMSO, fruc-
tose first isomerized and the isomer appeared at 109 ppm. The
The authors declare no conflict of interest.
1
3
2
- C of the first dehydration intermediate IM1 was similar to
that of the isomer and can be assigned to 111.5 ppm. As the
reaction proceeds for 5 hours, the second dehydration inter-
mediate IM2 was obvious as indicated by the 157 ppm peak,
which agrees with the result in DMSO solvent. Besides, the
main intermediates were also verified by H NMR spectroscopy
as shown in Fig. S5 and Table S2†, combined with experimental
Acknowledgements
The authors acknowledge the programs supported by the
Chinese Academy of Sciences (QYZDB-SSW-JSC037) and the
Ningbo Science and Technology Bureau (2018B10056 and
1
2019B10096).
characterization and DFT calculations. By comparing the NMR
13
spectra of labeled and unlabeled C, it is found that the main
byproducts formed in this system are located around 176 and
Notes and references
9
5–105 ppm. The peak at 176 ppm can be assigned to LA due to
31
the HMF hydrolysis in water after the reaction. The peaks
around 95–105 ppm are the difructose dianhydrides (DFAs) as
indicated in DMSO, which can further form HMF with enough
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−
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