Catalytic conversion of 5-hydroxymethylfurfural into 2,5-furandiamidine dihydrochloride

Article abstract of DOI:10.1039/c5gc01985k

Via implantation of nitrogen from aq. NH₃ into hydroxymethylfurfural (HMF), dimethyl furan-2,5-dicarboximidate was synthesized over a manganese oxide catalyst. It was realized by the ammoxidation of HMF followed by methanol addition under mild reaction conditions. The imidate prepared in situ was further transformed into 2,5-furandiamidine dihydrochloride by reaction with ammonium chloride.

Full text of DOI:10.1039/c5gc01985k

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Catalytic conversion of 5-hydroxymethylfurfural into 2,5-
furandiamidine dihydrochloride
Xiuquan Jia,a,b‡ Jiping Ma,a‡ Min Wang,a Hong Ma,a Chen Chena and Jie Xu*a
Received 00th January 20xx,
Accepted 00th January 20xx
DOI: 10.1039/x0xx00000x
www.rsc.org/
Via
implanting
of
nitrogen
from
aq.
NH3
into remains very challenging.13 As far as we know, there is no
hydroxymethylfurfural (HMF), dimethyl furan-2,5-dicarboximidate report about the catalytically synthetic strategy of HMF
was synthesized over manganese oxide catalyst. It was realized by processing with aq. NH3.
the ammoxidation of HMF followed by methanol addition under
mild reaction conditions. The imidate prepared in situ was further
transformed into 2,5-furandiamidine dihydrochloride by reaction
with ammonium chloride.
In the past decade, catalytic transformation of renewable Scheme
1 Catalytic transformation of 5-hydroxymethylfurfural to 2,5-
furandiamidine dihydrochloride.
biomass has received intense global attention, in the interest
of developing alternatives to fossil resources-derived
chemicals and fuels.1 Among the strategies for biomass
processing, the production of 5-hydroxymethylfurfural (HMF)
from hexoses is a typical example.2 HMF is widely viewed as a
versatile platform molecule. It can be selectively oxidized to
2,5-diformylfuran (DFF),3 2,5-furandicarboxylic acid4 and 5-
hydroxymethyl-2-furancarboxylic acid.5 It also can be
converted to 2,5-dimethylfuran, 2,5-dimethyltetrahydrofuran,
2,5-dihydroxymethylfuran and 2,5-dihydroxymethyltetra-
hydrofuran via selective hydrogenation.6 In addition, 5-
ethoxymethylfurfural7 and levulinic acid8 were obtained from
HMF via etherification and rehydration, respectively. These
kinds of work have been focused on the modulation of the
furan ring and adjacent hydroxymethyl/aldehyde group to
generate fine chemicals, liquid fuel additives, polymer
monomers, surfactants, etc..9
Aromatic diamidines, possessing homobifunctional amidine
groups, are of unique biological and pharmaceutical
significance.14 For example, pentamidine was used to treat
Pneumocystis-induced pneumonia whcih is the leading cause
of morbidity and mortality in AIDS patients.15 We present our
work on the conversion of HMF into unsubstituted
diarylamidines, via dimethyl furan-2,5-dicarboximidate
(Scheme 1). The conversion of imidate into amidine by the
reaction with ammonium chloride is well-established.16
A
major challenge needed in this reasearch is the transformation
of HMF into dimethyl furan-2,5-dicarboximidate. The common
procedure for imidate synthesis is the Pinner reaction of
nitriles with alcohols under anhydrous acidic conditions or
through a base-catalyzed process.16a, 17 The nitriles are either
prepared by the cyanation of halogenated compounds using
toxic cyanide,18 or by the ammoxidation of aldehydes or
alcohols.19 From the viewpoint of sustainable development
and green chemistry, it is desirable to directly convert readily
available aldehydes or alcohols, especially biomass-based
aldehydes or alcohols into imidates under mild conditions.
Catalytical implanting of nitrogen into HMF is another way
to the synthesis of value-added chemicals.10 Amines were
generally used as nitrogen sources as exampled in the
synthesis of aminomethylfurans11 and amide12 reported by
Stevens and Riisager’s group, respetively. Starting from aq.
NH3 to directly synthesize nitrogen-containing HMF derivatives
Herein, on continuance of our work on the oxidative
transformation of HMF,3a-b,
4a, 20
we demonstrate a novel
a.State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics,
Chinese Academy of Sciences, Dalian National Laboratory for Clean Energy,
Dalian 116023, P. R. China. E-mail: xujie@dicp.ac.cn.
b.University of the Chinese Academy of Sciences, Beijing 100049, P. R. China.
† Electronic Supplementary Information (ESI) available: See
DOI: 10.1039/x0xx00000x
strategy to implant nitrogen into HMF to construct diimidate
through one pot ammoxidation of HMF followed by methanol
addition over manganese oxide under mild conditions. By
reaction with ammonium chloride, the imidate prepared in situ
was
further
transformed
into
2,5-furandiamidine
‡These authors contributed equally.
dihydrochloride.
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2
(8%),
3
(11%), mononitrile imidate (
4
) (4%) and monoimidate
amide (
6
) (5%) (Table 1, entry 4). This partly because OMS-2 is
an efficient catalyst for oxidation of the hydroxymethyl group
of HMF (Table S1, Entry 4). Subsequently, at increased
temperature of 60 oC, the yield of
meanwhile 12% yield of
the side-products
5
decreased to 29%,
formed (Table 1, entry 5). In addition,
of 2,5-furandiamide, and 2,5-
6
Scheme 2 Products of 5-hydroxymethylfurfural transformation.
furandicarboxylic acid were identified by high performance
liquid chromatography. And a decreased catalyst loading of
0.05 g gave 73% yield of
(Table 1, entry 6) due to the formation of oligomers. An 88%
yield of was formed upon prolonging reaction time to 30 h
5, as well as a decreased total yield
The oxidative synthesis of dimethyl furan-2,5-
dicarboximidate (5) from HMF, methanol and aq. NH3 was
5
conducted in an autoclave reactor with oxygen pressure up to
0.5 MPa and the products were shown in Scheme 2. Initially, a
range of catalysts were explored (Fig. S5). Among the various
catalysts examined, only manganese dioxides offered the
target product with a complete conversion of HMF and the
detailed results were presented in Table 1.
(Table 1, entry 7). To show the practical value of the present
procedure, a gram-scale transformation of HMF (40-fold scale)
was carried out. Subsequent purification gave
5 as white
crystalline solid (74% isolated yield, Fig. S6). While only trace
aldimine was detected when the reaction was conducted
under N2 atmosphere.
After the reaction was completed, OMS-2 was easily
retrieved from the reaction mixture by simple centrifugation.
The recovered OMS-2 catalyst could be reused at least five
times without obvious loss of its catalytic performance (Fig.
S7). There was no remarkable difference in X-ray powder
diffraction patterns between the fresh OMS-2 and the
recovered OMS-2 after the sixth use, showing the crystal
structure of OMS-2 was preserved in the reaction conditions
(Fig. S4). Inductively coupled plasma atomic-emission
spectroscopy analysis revealed that no Mn species were
detected in the reaction mixture, indicating the heterogeneous
catalytic nature of OMS-2.
Table 1 Catalytic conversion of 5-hydroxymethylfurfural to dimethyl
furan-2,5-dicarboximidate over different manganese oxides.a
Entry Catalyst
Conversion Yield (%)
(%)
2
26
-
3
4
16
7
6
4
-
5
6
-
1
β-MnO2
δ-MnO2
γ-MnO2
OMS-2
OMS-2
OMS-2
OMS-2
>99%
>99%
>99%
>99%
>99%
>99%
>99%
4
21
14
54
71
29
73
88
2
36
9
-
3
-
-
4
8
-
11
-
5
12
-
5b
6c
7d
-
1
2
-
-
5
6
aReaction conditions: 0.25 mmol HMF, 0.1 g MnO2, 120 μL aq. NH3 (6
equiv.),
mL MeOH, 0.5 MPa O2, 30 oC, 12 h. b60 oC, 2,5-
5
furandiamide and 2,5-furandicarboxylic acid were identified by
Fig.1 Time course of catalytic conversion of 5-hydroxymethylfurfural to
dimethyl furan-2,5-dicarboximidate over OMS-2 (■ = conversion of 1, ● =
yield of 2, ▲ = yield of 3, ▼ = yield of 4, ◄ = yield of 5, ► = yield of 6).
Reaction conditions: 1.5 mmol HMF, 0.6 g OMS-2, 720 μL aq. NH3 (6 equiv.),
30 mL MeOH, 0.5 MPa O2, 30 oC.
HPLC. c0.05 g OMS-2, oligomers were detected by MALDI-TOF. d30 h.
In the case of β-MnO2 and δ-MnO2, 5-hydroxymethyl-
furonitrile
(2) and 5-hydroxymethylfurancarboximidate (3)
were the main products, respectively, indicating a low activity
of hydroxymethyl group transformation (Table 1, entries 1-2).
Following the evolution of the time course, different
compounds were detected, and Fig. 1 shows the kinetic
Target product
5 was effectively formed with 54% yield in the
curves. Initially, HMF was rapidly converted to
2 with a
presence of γ-MnO2 (Table 1, entry 3). Manganese oxide based
octahedral molecular sieves (KMn8O16; OMS-2) gave the best
maximum of ca. 66% yield after 1 h. DFF was not detected.
This behavior indicates the high activity of ammoxidation of
result with 71% yield of 5, as well as a small amount of product
2 | J. Name., 2012, 00, 1-3
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aldehyde group over OMS-2. And it is essential on the occasion
of DFF ammoxidation (Scheme S1), which largely circumvents
the polymerization of DFF with NH3 by forming
methanediamines,21 with
a characteristic absorption of
aldimine group at 1636 cm-1 (Fig. S8-9). Instead of
polymerization, ammoxidation product 2,5-dicyanofuran was
detected at 0.5 h and 72% yield of
5 was obtained after 12 h
(Fig. S10; Table S2, entry 4). In the case of β-MnO2, δ-MnO2
and γ-MnO2, the polymerization reaction of DFF with NH3 was
obviously detected by real-time in-situ react Fourier transform
infrared (React FT-IR, Fig. S11-13), and only trace
5 was
detected (Table S2, entries 1-3). It may be attributed to
relatively lower activity of ammoxidation of aldehyde group
over other manganese oxides.
As the reaction prolonged,
by the increase of target product 5. At the same time
amount of and also appeared. They first increased and
then decreased with reaction proceeding. This indicates and
were reaction intermediates. It is possible that was first
converted to via methanol addition to the cyano group.
Further ammoxidation of hydroxymethyl group of led to the
formation of appeared after 5 h as a by-product, and kept
at low concentration as reaction proceeding. was stable
under the reaction conditions, without forming amide
(Scheme S2). It is probable that was generated from the 4 via Fig. S25). Through React FT-IR spectral measurements the
2
was decreased accompanied
,
minor
3
4
Fig.2 Time course of catalytic conversion of HMF characterized by real-time
in situ React FT-IR. Reaction conditions: 1.25 mmol HMF, 10 mL MeOH, 30 oC,
then 600 μL aq. NH3 (6 equiv.) added at 0.5 h, 0.5 g OMS-2 and 0.5 MPa O2
charged at 1.5 h.
3
4
2
3
3
4. 6
5
In essence, the ammoxidation of aldehyde group to cyano
group proceeded via aldimine group as the intermediate (see
6
6
hydrolysis of cyano group. Indeed, the cyano group could be dynamic behavior of the aldimine group was clearly observed
hydrolyzed to acyl group under the reaction condition (Table (Fig. 2 and Fig. S14-15). Initially, the intensity of typical band at
S3, entry 5). The hydrolysis product of intermediate
detected. We presume the different reactivity of compound
and
might be a result of different activation capability on the aq. NH3. Meanwhile the band at 1633 cm-1 associated with
2
was not 1677 cm-1 associated with C=O stretching vibration of
aldehyde group of HMF significantly decreased upon adding
4
2
cyano group by electron-withdrawing imidate and C=N stretching vibration of aldimine appeared, and increased
hydroxymethyl group, respectively. The cyano group of its intensity to an equilibrium in 1 h. Afterwards, OMS-2 and O2
product
imidate group. In comparison, the electron-withdrawing effect rapidly decreased. Meanwhile, the bands at 1234 and 1197
of hydroxymethyl group of intermediate
might be too weak cm-1 associated with C-O stretching vibration of imidate were
4
is activated by the strong electron-withdrawing were charged, and the intensity of the band at 1633 cm-1
2
to activate the cyano group hydrolysis at the mild reaction simultaneously observed.
condition of 30 oC. The above results show the transformation
of HMF to
5 involved the oxidation of hydroxymethyl group to
aldehyde group, the ammoxidation of aldehyde group to cyano
group and the methanol addition to cyano group.
Fig.3 Relationship of peak height at 1677 cm-1ascribed to C=O stretching
vibration of the aldehyde group in HMF and reaction time (t) of HMF
condensation with aq. NH3. Reaction conditions: (a): 1.25 mmol HMF,0.5 g
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OMS-2, 10 mL MeOH, 600 μL aq. NH3 (6 equiv.), 30 oC; (b) is the same as (a)
except no OMS-2 was added.
reaction.
to the cyano group. The ammoxidation of
converted to smoothly via addition with methanol, as well as
trace through hydration.
2
was further converted into
3
via methanol addition
3
gave 4, which was
5
6
The effect of OMS-2 on the rate of condensation of the
aldehyde group with NH3 can be seen from the results given in
Fig. 3. The intensity of peak at 1677 cm-1 ascribed to C=O
stretching vibration of the aldehyde group in HMF decreased
slightly in the absence of OMS-2 (Fig. 3b). While it decreased
sharply with the addition of OMS-2 (Fig. 3a). This
demonstrated that OMS-2 played an active role in promoting
the condensation of aldehyde group of HMF with aq. NH3.
The rate-limiting step was further investigated. As seen
Scheme
4 One pot transformation of 5-hydroxymethylfurfural to 2,5-
furandiamidine dihydrochloride.
from Fig. 1, the enrichment of
2 in the initial stage suggested
In order to examine the reactivity of furan imidate to
amidine, 2,5-furandiamidine dihydrochloride was prepared by
that the oxidation of the hydroxymethyl group into aldehyde,
or the addition of the cyano group with methanol to imidate
was the controlling step. If the latter was the controlling step,
2,5-dicyanofuran accumulation should occur during the further
reaction of the methanolic solution of
5 prepared in situ with
two equivalent of ammonium chloride to the total imidate
groups present. The generated diamidine salts was
recrystallized from alcohol-petroleum ether mixture giving
yellow powder in 71% yield (Fig. S29-30).
conversion of 2, which was not detected. On the other hand,
OMS-2 played no effect on the addition of 2,5-dicyanofuran
with methanol (Fig. S16-18). In fact, the addition of 2,5-
dicyanofuran with methanol proceeded smoothly over various
manganese oxides, even in the absence of manganese oxide
(Table S3). This might be a result of activation on the cyano
group by another electron-withdrawing cyano or imidate
Conclusions
In summary, we reported a novel method of catalytic
group.16a In addition, the compounds
2 and 3 coexisted in the
synthesis of imidate
5 via implanting of nitrogen from aq. NH3
into HMF over manganese oxide under mild conditions. OMS-2
is an efficient catalyst that favours the 1) oxidation of the
hydroxymethyl group to aldehyde, 2) condensation of
aldehyde with ammonia to aldimine, and 3) oxidation of
aldimine to nitrile. The conversions of aldehyde, aldimine and
nitrile groups all preferentially proceed rather than the
oxidation of hydroxymethyl group. By reaction with
reaction mixture as shown in Fig. 1. All these results
demonstrate that the oxidation of the hydroxymethyl group
into aldehyde was the rate-limiting step.
ammonium chloride, the imidate
5
prepared in situ was further
dihydrochloride
transformed into 2,5-furandiamidine
expediently. This work provides a new and unique strategy to
obtain valuable nitrogen-implanted chemicals from biomass
resources.
Acknowledgements
This work was supported by the National Natural Science
Foundation of China (projects 21233008 and 21303183) and
the “Strategic Priority Research Program-Climate Change:
Carbon Budget and Related Issues” of the Chinese Academy of
Sciences (XDA05010203).
Scheme 3 Proposed reaction pathway of catalytic transformation of 5-
hydroxymethylfurfural to dimethyl furan-2,5-dicarboximidate over OMS-2.
Notes and references
Taking into account the kinetic behaviour of the different
compounds above-mentioned, a reaction network is presented
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Green Chemistry
Page 6 of 7
View Article Online
DOI: 10.1039/C5GC01985K
Catalytic conversion of 5-hydroxymethylfurfural into
2,5-furandiamidine dihydrochloride
Xiuquan Jia,a,b‡ Jiping Ma,a‡ Min Wang,a Hong Ma,a Chen Chena and Jie Xu*a
aState Key Laboratory of Catalysis, Dalian Institute of Chemical Physics,
Chinese Academy of Sciences, Dalian National Laboratory for Clean Energy,
Dalian 116023, P. R. China. E-mail: xujie@dicp.ac.cn.
bUniversity of the Chinese Academy of Sciences, Beijing 100049, P. R. China.
‡ These authors contributed equally.
2,5-Furandiamidine
dihydrochloride
was
firstly
synthsized
from
5-hydroxymethylfurfural by reaction of dimethyl furan-2,5-dicarboximidate prepared
in situ with ammonium chloride.

Page 7 of 7
Green Chemistry
View Article Online
DOI: 10.1039/C5GC01985K