Sustainable synthesis of 1,2,3,4-cyclohexanetetracarboxylate from sugar-derived carboxylic acids

Article abstract of DOI:10.1039/d0cc02163f

Herein, we report a sustainable route for the synthesis of 1,2,3,4-cyclohexanetetracarboxylate from sugar-derived muconic acid and fumaric acid. The key Diels-Alder reaction constructed a cyclohexene framework substituted by four ester groups. The isolated yield of tetramethyl 5-cyclohexene-1,2,3,4-tetracarboxylate was up to 95.5percent without any catalyst used. And the hydrogenation reaction of the cycloadduct was catalyzed by commercial RANEY? Ni at room temperature and nearly 100percent yield of the cyclohexyl target products was obtained. This journal is

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Sustainable synthesis of 1,2,3,4-cyclohexanetetracarboxylate
from sugar-derived carboxylic acids
Rui Lu,a Huifang Jiang, a,b Xiaoqin Si, a,b Xiaolin Luo,a,b Fang Lu,*a and Jie Xu*a
Received 00th January 20xx,
Accepted 00th January 20xx
DOI: 10.1039/x0xx00000x
www.rsc.org/
Herein, we report a sustainable route for the synthesis of 1,2,3,4-
cyclohexanetetracarboxylate from sugar-derived muconic acid and
fumaric acid. The key Diels-Alder reaction constructed
cyclohexene framework substituted by four ester groups. The
isolated yield of tetramethyl 5-cyclohexene-1,2,3,4-
a
tetracarboxylate was up to 95.5% without any catalyst used. And
the hydrogenation reaction of cycloadduct was catalyzed by
commercial Raney Ni under room temperature and nearly 100%
yield of the cyclohexyl target products was obtained.
Scheme 1 Illustration of fossil-based route and proposed process
for the production of 1,2,3,4-cyclohexanetetracarboxylate
Aromatic monomers containing benzene ring constitute main
building block of the polymer materials.1 The traditional
engineering plastics and synthetic fibres are difficult to
degrade and would cause serious environmental problems and
threaten to human health.2 And seeking for suitable
alternative materials has become a research hot spot.3 In this
regards, the polyesters and plasticizers synthesized by
substituted cyclohexane oxygenates free of benzene ring
exhibit nontoxicity and specific performance, and have been
widely used in electric, electronic and optical materials,
biomedical devices, plasticizers fields, etc.4 It is followed that
the global market demand of cyclohexanecarboxylates is rising.
Eastman5 and BASF6 have realized the scale production of ten
thousand tons of 1,4- and 1,2-cyclohexanedicarboxylate,
respectively. The current production of these chemicals,
cyclohexanedicarboxylate and cyclohexanetetracarboxylate,
mainly relies on catalytic hydrogenation of petroleum-based
phthalate, terephthalate and pyromellitate under high
temperature and pressure conditions.7 Compared to common
aromatic products, the additional manufacturing process will
inevitably result in a sharp increase in cost which impedes the
further expansion of market space. Carbon neutral biomass
could offer a vast and natural resource to produce liquid fuels
and chemicals as a supplement to the petrochemical industry.8
However, methods for the efficient conversion of biomass-
derived feedstock into cyclohexanecarboxylate directly under
mild condition are scarce and urgent to be developed.
Diels-Alder reaction is one of the powerful tools to build six-
membered carbon rings. Following the [4+2] cycloaddition,
subsequent dehydro-aromatization or hydrogenation reaction
can generate the final products containing aryl or cyclohexyl
unit.9 The production of renewable aromatics based on the
controlled Diels-Alder cycloaddition of diverse dienes with
suitable dienophiles has attracted much attention.10 Our group
has applied esterification, Diels-Alder and subsequent
dehydrogenation reaction to produce diethyl terephthalate
from trans,trans-muconic acid (ttMA), ethanol and ethylene.11
If the cycloadduct undergo hydrogenation reaction instead of
dehydrogenation,
the
final
product
was
1,4-
cyclohexanedicarboxylate. Recently, we have also realized the
efficient synthesis of 1,2-cyclohexanedicarboxylate from
erythritol and fumarate via successive deoxydehydration,
Diels-Alder and hydrogenation reaction.12 Li and Zhang et al.
utilized the similar cyclizing strategy to synthesis 1,4-
cyclohexanedicarboxylic
acid
and
1,2-
a. State Key Laboratory of Catalysis, Dalian National Laboratory for Clean Energy,
Dalian Institute of Chemical Physics, Chinese Academy of Sciences,
Dalian 116023, P.R. China.
cyclohexanedicarboxylates through multi-step reaction.13
Multiple functional groups including a cyclohexane ring and
four carboxyl groups bring great challenge in the direct
synthesis of 1,2,3,4-cyclohexanetetracarboxylate. Although
Diels-Alder reaction is the effective strategy to construct
E-mail: xujie@dicp.ac.cn; lufang@dicp.ac.cn
b. University of Chinese Academy of Sciences, Beijing 100049, P.R. China.
†Electronic Supplementary Information (ESI) available: Experimental procedures;
additional figures; and GC-MS spectra (PDF).
See DOI: 10.1039/x0xx00000x
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cyclohexyl structure, the key point is that appropriate diene dimethyl trans,trans-muconate (ttDMM) instead of fumaric
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DOI: 10.1039/D0CC02163F
and dienophile with matched electron orbitals should be acid. And the major product of cycloaddition was tetramethyl
prepared and designed rationally. As an important new bio- 5-cyclohexene-1,2,3,4-tetracarboxylate and a small amount of
platform molecule, ttMA could be synthesized in high yield cycloadduct isomers was also detected by GC-MS (Fig. S1).
from glucose and mucic acid through enzymatic and chemical The Diels-Alder reactions of ttDMM with dimethyl fumarate
catalysis, respectively.14 Fumaric acid and its esters, which were conducted in air atomosphere at first (Fig. 1a). It was
could be used as a good candidate for dienophile, was found that the conversion of ttDMM was up to 63.8% after
o
obtained via the dehydration of malic acid under solvent free reacting for 0.5 h at 150 C. When the reaction time was
condition or the deoxydehydration of tartaric acid in our extended to 4 h, ttDMM was almost consumed completely and
previous works.12,15 Here, we propose a sustainable route for the yield of cycloadduct was only 12.8%. As depicted in Fig. 1b,
the production of 1,2,3,4-cyclohexanetetracarboxylate using argon was used to purge the vial instead of air. The conversion
sugar-derived ttMA and fumaric acid as starting materials. The of ttDMM had a decrease to 67.8% and the selectivity of
Diels-Alder reaction forms a substituted cyclohexene with four cycloadduct was improved to 97.4% significantly after reacting
ester groups and the hydrogenation of cycloadduct is for 4 h. Argon was chosen as the reaction atomosphere in the
conducted smoothly catalyzed by commercial Raney Ni under following experiment due to the excellent performance. The
room temperature (Scheme 1).
above-mentioned results showed that the performance of
ttMA possessing two electron-withdrawing carboxyl groups is cycloaddition between ttDMM and dimethyl fuamrate could
not a great candidate as diene in the normal-electron-demand greatly be affected by reaction atomosphere: it was much
Diels-Alder reaction. An efficient way is that ttMA undergoes better in argon than that in air. A visual reaction phenomenon
esterification to form muconate. Compared to the acid, was that the color of solution changed from colorless to brown
muconate is more reactive with ethylene in cycloaddition due after reacting in air while kept almost unchanged in argon (Fig.
to its altered electronic property and better solubility.11 To S5, a and b). It was speculated that some side reactions such as
build a substituted cyclohexene with four carboxyl groups, it oligomerization reaction of the substrates might exist in air
needs a dienophile such as fumaric acid to react with atomosphere which resulted in the poor selectivity of
muconate. To simplify the quantitative analysis process, cycloadduct. This was proved by LC-QTOF-MS analysis in which
dimethyl fumarate was selected as dienophile to react with some oligomers with higher molecular weight were detected
except unreacted substrates and cycloadduct (Fig. S6).
The stability tests of each substrate were also conducted to
further clarify the effect of reaction conditions (Fig. 2). ttDMM
and dimethyl fumarate were put into the reactor and heated
under air and argon, respectively. The stability was measured
by the recovery of the substrate. After heated in air for 4 h
with 1,4-dioxane as solvent, the recovery of dimethyl fumarate
was only 8.4% and ttDMM could almost not be detected.
When the operation was conducted in argon, the recoveries of
dimethyl fumarate and ttDMM had a sharp increase to 82.6%
and 96.8%, respectively. Therefore, it might be proposed that
the Diels-Alder reaction was competed with oligomerization of
the substrates; and the oligomerization was mainly occurred in
air while the Diels-Alder reaction could run smoothly in argon
Fig. 1 Time course of the Diels-Alder reaction of dimethyl
trans,trans-muconate (ttDMM) and dimethyl fumarate in air (
a)
Fig.
2 Stability tests of dimethyl fumarate and dimethyl
and argon ( ) atomosphere. Reaction conditions: ttDMM (0.05
b
trans,trans-muconate (ttDMM) under different conditions.
Reaction conditions: ttDMM (0.05 mmol) or dimethyl fumarate
mmol), dimethyl fumarate (0.15 mmol), 1,4-dioxane (0.5 mL), 150
oC, 4 h. The selectivity of cycloadduct was calculated based on the
molar amount of ttDMM input.
o
(0.15 mmol), solvent (0.5 mL), 150 C, 4 h.
2 | J. Name., 2020, 00, 1-3
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to form cycloadduct. Besides, n-octane was also used as
solvent instead of 1,4-dioxane in the tests and the recovery of
dimethyl fumarate further increased to 97.3% and 98.2%
recovery of ttDMM was achieved. The cause of this association
was not known warranting further investigation.
View Article Online
DOI: 10.1039/D0CC02163F
Result optimization experiments were also studied. The feed
ratio of substrates had an important influence on the reaction
results (Table 1, entries 1-4). With the input of dimethyl
fumarate increased, the conversion of ttDMM was improved
as well as the yield of cycloadduct. And the molar ratio of
dimethyl fumarate to ttDMM was enhanced from 3/1 to 4/1,
the conversion of ttDMM and the yield of cycloadduct had no
remarkable increase (Table 1, entries 3 and 4). Therefore, the
feed ratio of 3/1 was chosen in the following test. ttDMM
almost converted completely as the temperature was elevated
Scheme 2 Complete synthetic process of tetramethyl 1,2,3,4-
cyclohexanetetracarboxylate
from
dimethyl
trans,trans-
muconate and dimethyl fumarate
were all high value-added chemicals and could be widely used
in polymer field. With Pd/C as catalyst, 39.6% and 10.6% yield
of hydrogenated and aromatic products were obtained under
inert atomosphere, respectively. Besides, 8.5% yield of
trimethyl
trimellitate
was
formed
through
the
o
to 180 C and the yield of cycloadduct was risen to 96.9%
dealkoxycarbonylation process. To acquire the substituted
cyclohexane products, the hydrogenation reaction of
cycloadduct was conducted with commercial Raney Ni as
(entry 5). And using n-octane as solvent resulted a slight
increase of yield to 97.4% (Table 1, entry 6). To amplify the
cycloaddition reaction, 1.0 mmol of ttDMM and 3.0 mmol of
dimethyl fumarate were charged and the reaction was
conducted at 180 oC for 4 h in n-octane under argon
atomosphere. The products were isolated by column
chromatography and a 95.5% yield of tetramethyl 5-
cyclohexene-1,2,3,4-tetracarboxylate (about 300 milligrams)
was obtained. The unreacted dimethyl fumarate could be
recycled for next batch of experiment.
Dehydro-aromatization of cyclohexene or substituted
cyclohexene has been studied extensively as a kind of
foundational model reactions.16 The hydrogen generated from
dehydrogenation reaction could be added to C=C bond of the
substrate again. Theoretically, it need remove four hydrogen
atoms of cyclohexene to form benzene ring. If the reaction
reaches equilibrium, the final molar ratio of hydrogenation
products and aromatization product was 2/1 without additive
hydrogen acceptor or operation for hydrogen removal. Thus,
to take full advantage of the active hydrogen, a strategy for
catalyst under mild condition. The main product was
1 which
could be identified by GC and NMR method (Fig. S11 and S12-
S17). Although they could not be distinguished by routine
chromatographic column, it was predicted that a small amount
of stereoisomers
2 and 3 might be also formed via the serial
isomerization and hydrogenation reaction of cycloadduct. All
of the three products could be used as cyclohexyl monomers
and nearly 100% total yield was obtained after reaction for 24
h at room temperature (Scheme 2).
Conclusions
In summary, a sustainable route for the production of
cyclohexanetetracarboxylate using sugar-derived carboxylic
acid as starting materials was developed. The Diels-Alder
reaction of dimethyl trans,trans-muconate and dimethyl
fumarate could be efficiently conducted under optimized
reaction condition without any catalyst used and the
maximum isolated yield of cycloadduct was up to 95.5%. A
strategy for simultaneous synthesis of benzene and
cyclohexane with four ester groups was also proposed to make
the best of the formed hydrogen. With extra hydrogen
resource introduced, nearly 100% yield of tetramethyl 1,2,3,4-
cyclohexanetetracarboxylates was obtained. This work
expands the way of employing Diels-Alder reaction to
synthesize green monomer and also provides a novel strategy
for utilizing the by-product hydrogen.
simultaneous
synthesis
of
tetramethyl
1,2,3,4-
cyclohexanetetracarboxylate
and tetramethyl 1,2,3,4-
prehnitate was proposed (Fig. S9 and S10). The two products
Table 1 The optimization for Diels-Alder reaction of dimethyl
trans,trans-muconate (ttDMM) and dimethyl fumaratea
Yield of
Conversion Selectivity of
of ttDMM
Dienophile/Diene
(mol/mol)
cycloadductb
Entry
cycloadductb
(%)
(%)
(%)
1
2
3
4
5c
6c,d
1/1
2/1
3/1
4/1
3/1
3/1
28.0
45.3
67.8
71.8
>99.9
>99.9
96.1
97.3
97.4
98.0
96.9
97.4
26.9
44.1
66.1
70.4
96.9
97.4
The authors are grateful to the National Key R&D Program of
China (2018YFB1501601), the National Natural Science
Foundation of China (No. 21908218 and 21872139), and the
Strategic Priority Research Program of the Chinese Academy of
Sciences (XDB17020300) for providing financial support to do
this scientific research.
a
Reaction condition: ttDMM (0.05 mmol), 1,4-dioxane (0.5 mL),
150 oC, 4 h, argon atomosphere. bThe selectivity of cycloadduct
was calculated according to the input amount of ttDMM and the
yield of cycloadduct was based on the molar ratio of the detected
Conflicts of interest
amount to the theoretical value. c ttDMM (0.1 mmol), 180 C. d n-
o
Octane (0.5 mL).
There are no conflicts to declare
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Pang, M. Zheng, A. Wang and T. Zhang, Joule, 2V0ie1w9A,rt3ic,le1O9n3li7ne-
Notes and references
DOI: 10.1039/D0CC02163F
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DOI: 10.1039/D0CC02163F
Table of contents
A sustainable route for the production of 1,2,3,4-cyclohexanetetracarboxylate from sugar-derived
carboxylic acids is presented.