10.1002/cssc.201800646
ChemSusChem
COMMUNICATION
for the target products of phthalic anhydride and dibutyl
phthalate (Figure S9). We turned to the derivative of
tetrahydrophthalic anhydride or the cycloadduct of 1,3-butadiene
and dibutyl maleate, dibutyl cis-cyclohexane-1,2-dicarboxylate.
A 68.2% yield of dibutyl phthalate was obtained after the
could be formed at mild condition via the hydrogenation of
cycloadduct. The results demonstrate that in-situ generation of
1,3-butadiene could effectively reduce self-Diels-Alder reaction
and auto-polymerization of reactants. In addition, experimental
and computational results reveal that fumaric acid and fumarate
with trans-configuration are better candidates served as
dienophiles than maleic acid and maleate with cis-configuration.
Thus, the Diels-Alder reaction of fumarate derived from malic
acid with erythritol which could in-situ generate 1,3-butadiene via
DODH was run in high efficiency. This work provides the
guidance in the design of new route based on Diels-Alder
reaction, and opens up the opportunities for the production of
new environmental friendly plastic materials from plant.
o
dehydrogenation was run 6 h at 220 C in nitrogen. When the
reaction was conducted in air atomosphere in which O2 was
acted as an additional hydrogen acceptor, the yield of dibutyl
phthalate improved to 86.7% (Figure S10).
Dibutyl trans-cyclohexane-1,2-dicarboxylate is the cycloadduct
prepared from the multi-step reaction. And the final
aromatization step should be performed on the trans-isomer.
However, dibutyl phthalate from the dehydrogenation of trans-
isomer presented a quite low yield (17.1 %) in autoclave (entry 6
in Table S3). During the dehydrogenation process, the
hydrogenation and dehydrogenation are competing reaction.
And removing the formed hydrogen is the key to improve the
selectivity of dehydrogenated product. Therefore, the
dehydrogenation was conducted in a glass flask with flow of
Acknowledgements
This work was financially supported by the National Natural
Science Foundation of China (No. 91545102, 21473188 and
21790331), the Key Research Program of the Chinese Academy
of Sciences (Grant No.ZDRW-CN-2016-1), the Strategic Priority
Research Program of the Chinese Academy of Sciences
(XDB17020300), and Dalian Science Foundation for
Distinguished Young Scholars (No. 2016RJO8) for scientific
research.
nitrogen instead of
a sealed autoclave (Table 2). Using
tetraglyme as the solvent, a 65.2% yield of dibutyl phthalate was
obtained. As introduced K3PO4 to the reaction system, the yield
could further increase to 77.8%. This could be explained by that
the additive weakened the hydrogenated performance of Pd/C
catalyst so as to enhance the selectivity of dehydrogenated
product. And the selectivity of dibutyl phthalate increased from
68.1% to 77.8%.
Cyclohexane-1,2-dicarboxylate could be easily formed by
hydrogenating 4-cyclohexene-1,2-dicarboxylate at mild condition
(Table S4). The catalyst of Pd/C gave an excellent performance
of near 100% yield of trans-cyclohexane-1,2-dicarboxylate. At
lower temperature, Ni/C catalyst presented the weaker activity,
and raising the reaction temperature to 120 oC could also obtain
100% yield of hydrogenated product.
Keywords: aromatic • biomass • catalysis • Diels-Alder • plastics
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Scheme 2. Process for the production of trans-4-cyclohexene-1,2-
dicarboxylate followed by dehydrogenation or hydrogenation to phthalate or
trans-cyclohexane-1,2-dicarboxylate from malic acid and erythritol.
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palladium-catalyzed dehydrogenation reaction of cycloadduct
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