Towards cleaner PolarClean: efficient synthesis and extended applications of the polar aprotic solvent methyl 5-(dimethylamino)-2-methyl-5-oxopentanoate
Type
ArticleAuthors
Cseri, LeventeSzekely, Gyorgy

KAUST Department
Advanced Membranes & Porous Materials CenterAdvanced Membranes and Porous Materials Research Center
Chemical Engineering Program
Chemical and Biological Engineering
Physical Science and Engineering (PSE) Division
Date
2019Permanent link to this record
http://hdl.handle.net/10754/656254
Metadata
Show full item recordAbstract
As a result of recent efforts in green solvent selection, methyl 5-(dimethylamino)-2-methyl-5-oxopentanoate, sold under the brand name Rhodiasolv PolarClean, has received considerable scientific and industrial attention as a possible non-toxic replacement for common polar aprotic solvents. However, the multicomponent nature and multi-step synthesis of this solvent remains an obstacle for its more widespread use and niche applications. In this work, a retrosynthetic approach was taken to identify novel shorter synthetic routes in alignment with green chemistry principles. High purity methyl 5-(dimethylamino)-2-methyl-5-oxopentanoate was obtained in novel single-step reactions via two different base-catalysed Michael additions from readily available building blocks. The more advanced synthetic route shows great potential owing to the swift (30 min), solvent-free reaction and catalytic amounts of base (<6.5 mol%). Green metrics analysis, including Atom Economy, Complete E factor, Carbon Intensity and hazard analysis found the new synthesis to be more sustainable than the patented routes. Application of this green solvent was demonstrated for the first time for O- and N-arylation in SNAr reaction with solvent recovery with similar or superior yields compared to other green solvents. Moreover, broad opportunities for this green solvent in membrane science were identified, where the use of conventional, toxic polar aprotic solvents in large quantities is unavoidable. Important practical solvent properties and parameters such as dielectric constant, solubility parameters, solvent miscibility and NMR residual shifts have been determined to facilitate the uptake of methyl 5-(dimethylamino)-2-methyl-5-oxopentanoate as a green solvent.Citation
Cseri, L., & Szekely, G. (2019). Towards cleaner PolarClean: efficient synthesis and extended applications of the polar aprotic solvent methyl 5-(dimethylamino)-2-methyl-5-oxopentanoate. Green Chemistry, 21(15), 4178–4188. doi:10.1039/c9gc01958hSponsors
The authors are thankful to Ms Hai Anh Le Phuong and Mr Fan Fei (both from The University of Manchester) for their assistance with UV-Vis spectroscopy and capacitance measurements, respectively.Publisher
Royal Society of Chemistry (RSC)Journal
Green ChemistryAdditional Links
http://xlink.rsc.org/?DOI=C9GC01958Hae974a485f413a2113503eed53cd6c53
10.1039/c9gc01958h