Metamorphic meta isomer: carbon dioxide and ketenes are formed via retro-Diels–Alder reactions in the decomposition of meta-benzenediol

Literature Information

Publication Date 2019-08-21
DOI 10.1039/C9CP03519B
Impact Factor 3.676
Authors

Marius Gerlach, Andras Bodi, Patrick Hemberger


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Abstract

The deoxygenation reaction of m-benzenediol (resorcinol), an important lignin model compound, was studied in a hot microreactor. We revealed three decomposition channels by detecting elusive and reactive intermediates and product isomers selectively and found that resorcinol, similarly to catechol (o-benzenediol) and hydroquinone (p-benzenediol), (i) gets decarbonylated to yield hydroxycyclopentadiene. Additionally, (ii) decarboxylation (CO2 loss) yields C5H6 species in a retro-Diels–Alder reaction from a lactone species. Only acyclic products are detected at lower reactor temperatures and the most stable C5H6 isomer, cyclopentadiene (c-C5H6), is only observed at higher temperatures. Finally, (iii) two reactive ketene species, ethenone and buta-1,3-dienal, were observed in a third reaction channel. Both decarboxylation and ketene formation channels are unique among benzenediols for the meta-isomer, resorcinol. We have explored the resorcinol potential energy surface to rationalize the observed reactions. These findings may help to understand the source of ketenes in catalytic lignin depolymerization and give new insight into isomer-specific deoxygenation processes.

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Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
CiteScore: 5.5
Self-citation Rate: 10.3%
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Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.

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