The metabolism of styrene was studied in the rat after intraperitoneal administration of the cold and the 14C-labeled compound. In addition to phenylethylene glycol, mandelic acid, benzoic acid and hippuric acid, phenolic metabolites, namely, 4-vinylphenol, p-hydroxymandelic acid, p-hydroxybenzoic acid, and p-hydroxyhippuric acid, were identified in the urine of the treated animals. These biotransformation products were characterized by mass spectrometry and by comparative thin layer chromatography with standard compounds. Results of covalent binding studies of 14C-phenylethylene glycol to rat liver microsomal proteins suggest that these phenolic compounds may be formed as a result of chemical rearrangements of unstable arene oxides, reactive intermediates possibly implicated in styrene toxicity.
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Chemistry
January 2025
Institute of Science Tokyo, Department of Chemical Science and Engineering, O-okayama, 152-8552, Meguro-ku, JAPAN.
Switching the location of metal atoms or ions in a molecule has been of great interest as a behavior of molecular machines. We describe herein that the reversible metal translocation can be coupled with the ligand-binding/release of organometallic complexes. The two rhodium moieties sandwiched between arylpolyene ligands exhibit metal-assembly and disassembly through reversible migration between the arene site and the olefin site, in response to the association and dissociation of additional ligands.
View Article and Find Full Text PDFJ Org Chem
January 2025
Department of Chemistry, University of Michigan, 930 North University Avenue, Ann Arbor, Michigan 48109, United States.
This report describes the design, development, and optimization of an electrochemical deoxyfluorination of arenes using a tetrafluoropyridine-derived leaving group. NEt·3HF serves as the fluoride source, and the reactions are conducted using either constant potential or constant current electrolysis in an undivided electrochemical cell. Mechanistic studies support a net oxidative pathway, in which initial single-electron oxidation generates a radical cation intermediate that is trapped by fluoride.
View Article and Find Full Text PDFThe selective amination of aromatic C-H bonds is a powerful strategy to access aryl amines, functionalities found in many pharmaceuticals and agrochemicals. Despite advances in the field, a platform for the direct, selective C-H amination of electronically diverse (hetero)arenes, particularly electron-deficient (hetero)arenes, remains an unaddressed fundamental challenge. In addition, many (hetero)arenes present difficulty in common selective pre-functionalization reactions, such as halogenation, or metal-catalyzed borylation and silylation.
View Article and Find Full Text PDFChemistry
January 2025
TU Chemnitz: Technische Universitat Chemnitz, Insitut für Chemie, Straße der Nationen 62, 09111, Chemnitz, GERMANY.
The intramolecular migration of three hydrogen atoms from one moiety of a gaseous radical cation to the other prior to fragmentation is an extremely rare type of redox reaction. Within the scope of this investigation, this scenario requires an ionized but electron-rich arene acceptor bearing a para-(3-hydroxyalkyl) residue. The precise mechanism of such unidirectional 3H transfer processes, including the order of the individual H transfer steps, has remained unclear in spite of previous isotope labelling and recent infrared ion spectroscopy (IRIS) studies.
View Article and Find Full Text PDFACS Catal
January 2025
Department of Pure and Applied Chemistry, University of Strathclyde, 295 Cathedral Street, Glasgow G1 1XL, United Kingdom.
An aryl radical assay is used to provide information about the formation of aryl radicals from aryl halides in coupling reactions to arenes in the presence of palladium sources and under LED irradiation (λ = 456 nm). The assay uses 2-halo--xylenes as substrates. Aryl radical formation is indicated both by a defined product composition and by signature deuterium isotope effects.
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