Synthesis of 1,4-Cyclohexanedimethanol, 1,4-Cyclohexanedicarboxylic Acid and 1,2-Cyclohexanedicarboxylates from Formaldehyde, Crotonaldehyde and Acrylate/Fumarate

Article abstract of DOI:10.1002/anie.201801287

Valuable polyester monomers and plasticizers—1,4-cyclohexanedimethanol (CHDM), 1,4-cyclohexanedicarboxylic acid (CHDA), and 1,2-cyclohexanedicarboxylates—have been prepared by a new strategy. The synthetic processes involve a proline-catalyzed formal [3+1+2] cycloaddition of formaldehyde, crotonaldehyde, and acrylate (or fumarate). CHDM is produced after a subsequent hydrogenation step over a commercially available Cu/Zn/Al catalyst and a one-pot hydrogenation/oxidation/hydrolysis process yields CHDA, whereas 1,2-cyclohexanedicarboxylate is obtained by a Pd/C-catalyzed tandem decarbonylation/hydrogenation step.

Full text of DOI:10.1002/anie.201801287

A Journal of the Gesellschaft Deutscher Chemiker
Angewandte
Chemie
International Edition
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Accepted Article
Title: Synthesis of 1,4-Cyclohexanedimethanol,
1,4-Cyclohexanedicarboxylic Acid and 1,2-
Cyclohexanedicarboxylates from Formaldehyde, Crotonaldehyde
and Acrylate
Authors: Yancheng Hu, Zhitong Zhao, Yanting Liu, Guangyi Li, Aiqin
Wang, Yu Cong, Tao Zhang, Feng Wang, and Ning Li
This manuscript has been accepted after peer review and appears as an
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To be cited as: Angew. Chem. Int. Ed. 10.1002/anie.201801287
Angew. Chem. 10.1002/ange.201801287
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10.1002/anie.201801287
Angewandte Chemie International Edition
COMMUNICATION
Synthesis of 1,4-Cyclohexanedimethanol, 1,4-Cyclohexane-
dicarboxylic Acid and 1,2-Cyclohexanedicarboxylates from
Formaldehyde, Crotonaldehyde and Acrylate
Yancheng Hu,‡,[a] Zhitong Zhao,‡,[a,b,c] Yanting Liu,[a] Guangyi Li,[a] Aiqin Wang,[a] Yu Cong,[a] Tao
Zhang,[a] Feng Wang,*[a] Ning Li*[a]
Dedication to the 70th anniversary of Dalian Institute of Chemical Physics, CAS.
Abstract:
1,4-Cyclohexanedimethanol
acid (CHDA),
(CHDM),
and
1,4-
1,2-
Therefore, the exploration of mild approaches for the production
of these cyclohexane oxygenates is in great demand.
cyclohexanedicarboxylic
cyclohexanedicarboxylates are valuable polyester monomers and
plasticizers. In this work, we propose a new strategy for the
synthesis of these compounds via a proline-catalyzed formal [3+1+2]
cycloaddition of formaldehyde, crotonaldehyde, and acrylate (or
fumarate), followed by a hydrogenation over commercially available
Formaldehyde is an essential C1 bulk chemical that can be
manufactured by the oxidation of methanol.[11, 12] Crotonaldehyde
is the self-aldol condensation product of acetaldehyde.[13] Ethyl
acrylate can be formed by the esterification/dehydration of lactic
acid.[14] All of these compounds can be derived from biomass.
Herein, we propose a two-step route for the synthesis of CHDM
and CHDA with formaldehyde, crotonaldehyde and ethyl
acrylate (Scheme 1). In the first step, proline-catalyzed formal
[3+1+2] cycloaddition of formaldehyde, crotonaldehyde, and
ethyl acrylate affords ethyl 4-formylcyclohex-3-enecarboxylate
(compound 1) via a domino Mannich condensation and Diels-
Alder (D-A) process. In the second step, a hydrogenation of
compound 1 over commercially available Cu/Zn/Al catalyst
results in CHDM (compound 2). As another option, CHDA
(compound 3) is synthesized by one-pot hydrogenation/air
oxidation/hydrolysis of compound 1. Fumarate is a derivative of
maleic anhydride (MA) from the oxidation of biobased furfural,[15]
Cu/Zn/Al catalyst,
a one-pot hydrogenation/oxidation/hydrolysis
process, or a Pd/C-catalyzed tandem decarbonylation/hydrogenation
step, respectively.
The catalytic conversion of renewable, cheap, and abundant
lignocellulose to fuels[1] and commodity chemicals[2‒6] has drawn
tremendous
Cyclohexanedimethanol
attention
over
the past
(CHDM)
decade.
and
1,4-
1,4-
cyclohexanedicarboxylic acid (CHDA), introduced by Eastman
Chemical Company, are valuable monomers for aliphatic
polyesters
cyclohexanedicarboxylate) (PCCD)), and copolyesters (e.g.,
poly(ethylene terephthalateco-1,4-cylclohexylenedimethylene
(e.g.,
poly(1,4-cyclohexylenedimethylene-1,4-
5-hydroxylmethylfurfural (HMF)[16] or levulinic acid (LA)[17]
.
Meanwhile, we also develop a two-step route for the synthesis of
1,2-cyclohexanedicarboxylates by a proline-catalyzed formal
[3+1+2] cycloaddition of fumarate, formaldehyde, and
terephthalate) (PETG)).[7] Compared to the traditional
polyethylene terephthalate (PET), the polyesters containing
CHDM or CHDA unit have higher biodegradability, glass
transition temperature, thermal stability, weather resistance, and
mechanical strength.[8] Notably, their properties can also be
altered by varying the cis/trans ratio of the ring.[8] 1,2-
Cyclohexanedicarboxylates, another important family of
cyclohexane oxygenates, have been used as environmentally
benign plasticizers to replace the traditional phthalates that often
leach out into the environment with time and cause health
crotonaldehyde, followed by
a
Pd/C-catalyzed tandem
decarbonylation/hydrogenation step (Scheme 1).
Firstly, we investigated the catalytic performances of a variety
of amines for the formal [3+1+2] cycloaddition of formaldehyde,
crotonaldehyde and ethyl acrylate (Table 1, entries 1‒8). The
not branched amines such as nPrNH2, ethanolamine, and iPr2NH
showed low activity for this reaction, which was attributed to the
unstability of the iminium intermediate. Likewise, the cyclic and
tertiary amines (such as pyrrolidine, Et3N and DABCO) also
gave poor yields of compound 1. Interestingly, a combination of
acetic acid and pyrrolidine gave a better result, which can be
rationalized because the acid/base co-catalyst enables the
formation of a more stable iminium salt intermediate.[18] Inspired
by this result, we studied the catalytic activity of proline, which
is a natural and non-toxic amino acid containing both pyrrolidine
motif and acid functionality. As we expected, proline was a
good catalyst for the reaction, giving compound 1 in 47% yield.
A survey of the reaction temperature indicates that the best
result was obtained at 130 °C, while a higher temperature led to
an inferior result (Entries 9, 10). The initial molar ratio of the
reactants also exerted an impact on the reaction (Entries 9, 11,
12). With an increase in the initial amount of formaldehyde and
crotonaldehyde, the yield of compound 1 was improved. 91%
yield of 1 was achieved when 2.0 equivalents of formaldehyde
hazards.[9]
Currently,
CHDM,
CHDA
and
1,2-
cyclohexanedicarboxylates are industrially prepared by the
oxidation of petroleum-derived xylenes and subsequent
hydrogenation of phthalic acids. In these processes, high
pressures and temperatures are often involved (Scheme 1).[10]
[a] Dr. Y. Hu, Z. Zhao, Dr. Y. Liu, Prof. G. Li, Prof. A. Wang, Prof. Y. Cong,
Prof. T. Zhang, Prof. F. Wang, Prof. N. Li
Dalian Institute of Chemical Physics, Chinese Academy of Sciences, 457
Zhongshan Road, Dalian 116023, China
[b] Z. Zhao
University of Chinese Academy of Sciences, Beijing 100049, China
[c] Z. Zhao
State Key Laboratory of Fine Chemicals, College of Chemistry, Faculty of
Chemical Environmental and Biological Science and Technology, Dalian
University of Technology, Dalian 116024, China
*E-mail: wangfeng@dicp.ac.cn; lining@dicp.ac.cn
‡These authors contributed equally.
and
crotonaldehyde
were
employed
(Entry
12).
Supporting information for this article is given via a link at the end of the
document.
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10.1002/anie.201801287
Angewandte Chemie International Edition
COMMUNICATION
Scheme 1. A comparison of petroleum- and bio-based routes to cyclohexane oxygenates.
group and C5 atom of the product originate from crotonaldehyde
and formaldehyde, respectively. On the basis of this result, a
plausible mechanism is proposed in Scheme 3. A nucleophilic
addition of proline onto the carbonyl group of crotonaldehyde
and the following dehydration generate the iminium salt
intermediate I, which is prone to isomerization through the
deprotonation of β-CH, resulting in the formation of enamine II.
Likewise, formaldehyde can be activated by proline as well,
providing iminium species III that is further attacked by the α-
carbon atom of enamine II to afford intermediate IV. A
subsequent elimination of proline gives Mannich-type product
V,[19] which easily reacts with acrylate to deliver D-A product VI.
A final hydrolysis of iminium motif produces the compound 1 and
regenerates the catalyst.
Table 1. Yield of compound 1 from the formal [3+1+2] cycloaddition of
formaldehyde, crotonaldehyde, and ethyl acrylate.[a]
Entry
Catalyst
T [°C ]
Initial molar ratio[b]
Yield of 1 [%][c]
1
2
3
4
5
6
nPrNH2
ethanolamine
iPr2NH
100
100
100
100
100
100
1 : 1 : 1
1 : 1 : 1
1 : 1 : 1
1 : 1 : 1
1 : 1 : 1
1 : 1 : 1
7
12
10
23
10
17
Et3N
DABCO
pyrrolidine
pyrrolidine +
HOAc
7
100
1 : 1 : 1
39
8
9
10
11
12
proline
proline
proline
proline
proline
100
130
160
130
130
1 : 1 : 1
1 : 1 : 1
1 : 1 : 1
1.5 : 1.5 : 1
2 : 2 : 1
47
58
39
69
91
[a] Reaction conditions: crotonaldehyde (10.0 mmol, 0.85 mL), 37% HCHO
aqueous solution (10.0 mmol, 1.0 mL), ethyl acrylate (10.0 mmol, 1.0 mL),
catalyst (10 mol%, based on the amount of acrylate), 12 h. [b] The initial molar
ratio of feedstocks was given as n(crotonaldehyde) : n(formaldehyde) : n(acrylate). [c] Yield
of 1 was detected by GC using tridecane as the internal standard and
Scheme 2. Isotopic labeling experiment.
calculated based on the initial amount of acrylate. DABCO
diazabicyclo[2.2.2]octane.
= 1,4-
To understand the reaction pathway, an isotopic labeling
experiment was performed (Scheme 2). It turned out that the
deuterium atoms were distributed onto 5 position of the ring
(Supplementary Figures S1‒S4), illustrating that the formyl
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10.1002/anie.201801287
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COMMUNICATION
1,4-cyclohexanedicarboxylic acid (CHDA) (Scheme 4). Notably,
the three distinct reactions can be combined into a one-pot
sequence. To do this, a mixture of compound 1, Pd/C and THF
was first stirred at 40 °C in H2 (2.0 MPa) for 8 h. Then H2 was
released, and the mixture was stirred at 80 °C in air for 5 h.
Eventually, an aqueous solution of NaOH was introduced, and
the system was further stirred at 80 °C for 6 h. Through this
sequential operation, CHDA was isolated in 86% yield (Scheme
4). As a result, using formaldehyde, crotonaldehyde, and ethyl
acrylate as the feedstocks, CHDA was produced in two steps
with an overall yield of 78%.
Scheme
5.
Proposed
pathway
for
the
production
of
1,2-
Scheme 3. Plausible mechanism for the proline-catalyzed formal [3+1+2]
cyclohexanedicarboxylate from formaldehyde, crotonaldehyde, and fumarate.
cycloaddition of formaldehyde, crotonaldehyde, and ethyl acrylate.
Fumarates can participate in the proline-catalyzed formal
[3+1+2] cycloaddition as well, affording 4-formylcyclohex-4-ene-
1,2-dicarboxylates (compound 5) as the products (Scheme 5).
For example, the utilization of diethyl fumarate as the reactant
Subsequently, we studied the synthesis of CHDM and CHDA
from compound 1. Cu-based catalysts have been widely used
for the hydrogenation of esters to alcohols.[20] We found that
compound
1
can
be
hydrogenated
to
1,
4-
gave
diethyl
4-formylcyclohex-4-ene-1,2-dicarboxylate
cyclohexanedimethanol (CHDM) over commercially available
Cu/Zn/Al catalyst. Under the optimized reaction conditions
(240 °C, 4.0 MPa of H2, 12 h), a high yield (84%) of CHDM was
achieved (Supplementary Figure S5). Taking into account the
optimized yield of compound 1 (91%) in the first step, the overall
yield of CHDM starting from formaldehyde, crotonaldehyde, and
ethyl acrylate could reach 76% (Scheme 4).
(compound 5a) in 83% yield. A subsequent decarbonylation and
hydrogenation would produce 1,2-cyclohexanedicarboxylates
(compound 6) (Scheme 5), which are used as safe plasticizers
for those PVC products with close contact, such as toys,
childcare articles, cling film, cosmetics, intravenous bags and
medical tubing. An investigation of different metal catalysts
shows that Pd/C exhibited the highest activity for the
decarbonylation of 5a (Supplementary Table S2). At the
optimized reaction temperature (160 °C), 100% conversion of 5a
and 96% yield of INT-5a were achieved over Pd/C catalyst
(Supplementary Figure S6).
We also attempted the direct synthesis of diethyl 1,2-
cyclohexanedicarboxylate (compound 6a) with 5a by a Pd/C-
catalyzed tandem decarbonylation/hydrogenation process. To
do this, a mixture of 5a, Pd/C and ethyl acetate was first stirred
in a batch reactor at 160 °C in argon atmosphere for 10 h. Then
2.0 MPa of H2 was charged into the reactor, and the mixture was
stirred at 100 °C for 4 h. As anticipated, 6a was obtained in a
high isolated yield (95%) without the separation of INT-5a
(Scheme 6). Consequently, the synthesis of 6a from
formaldehyde, crotonaldehyde, and diethyl fumarate was
accomplished in two steps with an overall yield of 79%.
Other biomass-derived fumarates bearing longer alkyl group
were also examined. When dibutyl fumarate (an ester of bio-
butanol with MA) was used as the feedstock, 77% overall yield
of dibutyl 1,2-cyclohexanedicarboxylate (compound 6b) was
achieved (Scheme 6). 2-Ethylhexanol is produced by sequential
aldol condensation and hydrogenation of biomass-derived n-
butyraldehyde.[21] Its esterification product di(2-ethylhexyl)
fumarate was smoothly transformed into di(2-ethylhexyl) 1,2-
cyclohexanedicarboxylate (DEHCH, compound 6c) in 72%
Scheme 4. Reaction pathways for the production of CHDM and CHDA using
compound 1 as the feedstock.
As another option, the C=C bond of compound 1 could be
hydrogenated over Pd/C in H2 (2.0 MPa) at 40 °C, giving ethyl 4-
formylcyclohexanecarboxylate (INT-2) as the sole product. In the
absence of any catalyst, INT-2 was easily oxidized into
carboxylic acid (INT-3) by air at 80 °C. A final hydrolysis yielded
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10.1002/anie.201801287
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COMMUNICATION
overall yield (Scheme 6), which can serve as a replacement for
Acknowledgements
a widespread plasticizer di(2-ethylhexyl) phthalate (DEHP)[22]
.
This work was supported by the National Natural Science
Foundation of China (no. 21721004; 21690080; 21690082;
21776273), the Strategic Priority Research Program of the
Chinese Academy of Sciences (XDB17020100), the National
Key Projects for Fundamental Research and Development of
China (2016YFA0202801), Department of Science and
Technology of Liaoning Province (under contract of
2015020086-101)，Dalian Science Foundation for Distinguished
Young Scholars (no. 2015R005). Y. Hu appreciates the
Postdoctoral Science Foundation of China (2015M581365) and
the dedicated grant for methanol conversion from DICP for
funding this work.
Scheme 6. Yields of different products from the two-step route toward 1,2-
cyclohexanedicarboxylates. Reaction conditions for the first step: proline (10
mol%, 115 mg), crotonaldehyde (20.0 mmol, 1.7 mL), 37% HCHO aqueous
solution (20.0 mmol, 2.0 mL), fumarate (10.0 mmol), 130 °C for 18 h. Reaction
conditions for the second step: compound 5 (10 mmol), Pd/C (10 wt%), ethyl
acetate (20 mL), Ar (1.0 atm), 160 °C for 10 h; then H2 (2.0 MPa) was charged,
100 °C for 4 h.
Conflict of interest
The authors declare no conflict of interest.
Keywords: formaldehyde • crotonaldehyde • CHDM • CHDA •
To evaluate the environmental footprint of our approaches, E-
factor analysis[23] was conducted and the details were provided
in the Supplementary Tables S3‒S8. Based on our calculation,
the E-factors for CHDM, CHDA, and diethyl 1,2-
cyclohexanedicarboxylate were determined as 4.474 kg/kg,
4.823 kg/kg, and 2.325 kg/kg, respectively, which is in
accordance with Sheldon’s analysis of bulk chemicals that have
an E-factor of 1‒5 (Table S9).[23] Besides, life cycle assessments
(LCA)[24] of biomass- and fossil-routes toward above-mentioned
three compounds were also performed (Supplementary Tables
S10‒S12 and Figures S7‒S10). As shown in Figure S9, the
greenhouse gas (GHG) emissions released during the CHDM
(compound 2) synthesis via bio-pathway is 13.14% less than the
one generated by fossil pathway. In constrast, bio-route toward
CHDA (compound 3) releases more GHGs than fossil pathway.
For diethyl 1,2-cyclohexanedicarboxylate (compound 6a), the
GHGs from the fossil- and bio-routes are close. Based on the
contributions to life cycle GHGs of the three bio-routes
(Supplementary Figure S10), we think that further optimization of
feedstock productions and reducing the dosage of NaOH and
HCl are the two most effective ways to decrease GHGs
(Supplementary Table S13 and Figures S11).
1,2-cyclohexanedicarboxylate
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cyclohexanedicarboxylic
acid
(CHDA)
and
1,2-
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10.1002/anie.201801287
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10.1002/anie.201801287
Angewandte Chemie International Edition
COMMUNICATION
Entry for the Table of Contents
COMMUNICATION
Yancheng Hu, Zhitong Zhao, Yanting
Liu, Guangyi Li, Aiqin Wang, Yu Cong,
Tao Zhang, Feng Wang,* Ning Li*
Page No. – Page No.
Synthesis
Cyclohexanedimethanol,
of
1,4-
1,4-
Cyclohexanedicarboxylic Acid and
1,2-Cyclohexanedicarboxylates from
Formaldehyde, Crotonaldehyde and
Acrylate
CHDM, CHDA and 1,2-cyclohexanedicarboxylates, valuable polyester monomers
and plasticizers in industry, are produced from biomass derivates by two-step
routes which feature a sustainable proline-catalyzed formal [3+1+2] cycloaddition of
formaldehyde, crotonaldehyde, and acrylate (or fumarate), followed by
hydrogenation over commercially available Cu/Zn/Al catalyst, one-pot
Pd/C-catalyzed tandem
a
a
hydrogenation/oxidation/hydrolysis process, or
decarbonylation/hydrogenation step, respectively.
a
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