Authors:	Beck, Alexander D. Schäffer, Lukas Haufe, Stefan Waldvogel, Siegfried R.
Title:	Assessment of the electrochemical synthesis route to silicones starting from slica as feedstock
Online publication date:	16-Feb-2024
Year of first publication:	2022
Language:	english
Abstract:	We successfully achieved methylation of various SiO2 sources to cyclic methylsiloxanes via electroreduction reaction. Contrary to previous assumptions, the reaction does not start from methanol as methyl radical source, that results in methoxylation of the electrolyte solvent. Methylammonium cations were found to enable the direct conversion, strongly dependent on the radical intermediate stabilization by the electrolyte. THF/Bu4NCF3SO3 is the sole applicable system with yields below 14 % referred to the methylammonium cations for the highest amount of product obtained so far. Mechanistic insights show that methylation does not occur via the supposed hydrolysis of dimethoxydimethylsilane intermediate, but via a direct conversion reaction, as comparative studies of a Fenton-type procedure clearly indicate. Further, cyclic methylsiloxane products are prone to subsequent electrochemical equilibration, strongly directed by the electrolyte solvent.
DDC:	540 Chemie 540 Chemistry and allied sciences
Institution:	Johannes Gutenberg-Universität Mainz
Department:	FB 09 Chemie, Pharmazie u. Geowissensch.
Place:	Mainz
ROR:	https://ror.org/023b0x485
DOI:	http://doi.org/10.25358/openscience-10097
Version:	Published version
Publication type:	Zeitschriftenaufsatz
Document type specification:	Scientific article
License:	CC BY-NC-ND
Information on rights of use:	https://creativecommons.org/licenses/by-nc-nd/4.0/
Journal:	European journal of organic chemistry 2022 47
Pages or article number:	202201253
Publisher:	Wiley
Publisher place:	Weinheim
Issue date:	2022
ISSN:	1099-0690
Publisher DOI:	10.1002/ejoc.202201253
Appears in collections:	DFG-491381577-H