The sequential transfer hydrogenation/hydrogenolysis of furfural and 5-hydroxymethylfurfural to 2-methylfuran and 2,5-dimethylfuran was studied over in situ reduced, Fe2 O3 -supported Cu, Ni, and Pd catalysts, with 2-propanol as hydrogen donor. The remarkable activity of Pd/Fe2 O3 in both transfer hydrogenation/hydrogenolysis is attributed to a strong metal-support interaction. Selectivity towards hydrogenation, hydrogenolysis, decarbonylation, and ring-hydrogenation products is shown to strongly depend on the Pd loading. A significant enhancement in yield to 62%, of 2-methylfuran and 2-methyltetrahydrofuran was observed under continuous flow conditions.
Sequential butanediol lactonization and transfer hydrogenation/hydrogenolysis of furfural-derivatives offers new opportunities for reductive upgrading of biomass.
A highly intensified process for the selective conversion of hemicellulose to furfural is demonstrated which integrates a bifunctional catalytic system into a biphasic fixed-bed reactor operating in continuous mode.
The
development of a scalable telescoped continuous flow procedure
for the acetylation and nitration of 4-fluoro-2-methoxyaniline is
described. A subsequent batch deprotection then affords 4-fluoro-2-methoxy-5-nitroaniline,
a key building block in the synthesis of osimertinib, a third-generation
epidermal growth factor receptor tyrosine kinase inhibitor (EGFR-TKI)
that is used for the treatment of nonsmall-cell lung carcinomas carrying
EGFR-TKI sensitizing and EGFR T790M resistance mutations. The hazards
associated with nitration of organic compounds, such as thermal runaway
and explosivity of intermediates, make it difficult to scale up nitrations
to industrial quantities, particularly within large-scale batch reactors.
In this study, we investigated an acetic acid/aqueous nitric acid
mixture as a predominantly kinetically controlled nitration regime
and a water-free mixture of acetic acid, fuming nitric acid, and fuming
sulfuric acid (oleum) as a mass-transfer-limited nitration regime.
A modular microreactor platform with in-line temperature measurement
was utilized for the nitration. Furthermore, we identified that it
was necessary to protect the amine functionality through acetylation
to avoid side reactions. The process parameters and equipment configuration
were optimized at laboratory scale for the acetylation and nitration
to improve the product yield and purity. The two steps could be successfully
telescoped, and the laboratory-scale flow process was operated for
80 min to afford the target molecule in 82% isolated yield over two
steps, corresponding to a throughput of 25 mmol/h. The developed flow
process was then transferred to an industrial partner for commercial
implementation and scaled up by the use of higher flow rates and sizing-up
of the microreactor platform to pilot scale to afford the product
in 83% isolated yield, corresponding to a throughput of 2 mol/h (0.46
kg/h).
Functionalizing organic molecules is an important value-creating step throughout the entire chemical value-chain. Oxyfunctionalization of e.g. C-H or C=C bonds is one of the most important functionalization technologies used industrially. The major challenge in this field is the prevention of side reactions and/or the consecutive over-oxidation of the desired products. Despite its importance, a fundamental understanding of the intrinsic chemistry, and the subsequent design of a tailored engineering environment, is often missing. Industrial oxidation processes are indeed to a large extent based on empirical know-how. In this mini-review, we summarize some of our previous work to help to bridge this knowledge gap and elaborate on our ongoing research.
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