Towards cleaner PolarClean: efficient synthesis and extended applications of the polar aprotic solvent methyl 5-(dimethylamino)-2-methyl-5-oxopentanoate
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,...
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| creator | Cseri, Levente Szekely, Gyorgy |
| description | 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 ( |
| doi_str_mv | 10.1039/c9gc01958h |
| format | Article |
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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 S
N
Ar 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.
Greener synthetic routes, physicalchemical properties, green metrics performance and applications for the eco-friendly polar aprotic solvent, methyl 5-dimethylamino-2-methyl-5-oxopentanoate (PolarClean).</description><identifier>ISSN: 1463-9262</identifier><identifier>EISSN: 1463-9270</identifier><identifier>DOI: 10.1039/c9gc01958h</identifier><language>eng</language><publisher>Cambridge: Royal Society of Chemistry</publisher><subject>Atom economy ; Brand names ; Catalysis ; Dielectric constant ; Dielectric properties ; Economic conditions ; Green chemistry ; Hazard assessment ; High-performance liquid chromatography ; Liquid chromatography ; Miscibility ; NMR ; Nuclear magnetic resonance ; Organic chemistry ; Solubility parameters ; Solvents ; Synthesis</subject><ispartof>Green chemistry : an international journal and green chemistry resource : GC, 2019, Vol.21 (15), p.4178-4188</ispartof><rights>Copyright Royal Society of Chemistry 2019</rights><lds50>peer_reviewed</lds50><oa>free_for_read</oa><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c354t-96bea439f3b4bab91f3d6d02a5ab504788bfd91d963b62461b35de3ff71b77353</citedby><cites>FETCH-LOGICAL-c354t-96bea439f3b4bab91f3d6d02a5ab504788bfd91d963b62461b35de3ff71b77353</cites><orcidid>0000-0002-3016-5477 ; 0000-0001-9658-2452</orcidid></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><link.rule.ids>314,780,784,4021,27921,27922,27923</link.rule.ids></links><search><creatorcontrib>Cseri, Levente</creatorcontrib><creatorcontrib>Szekely, Gyorgy</creatorcontrib><title>Towards cleaner PolarClean: efficient synthesis and extended applications of the polar aprotic solvent methyl 5-(dimethylamino)-2-methyl-5-oxopentanoate</title><title>Green chemistry : an international journal and green chemistry resource : GC</title><description>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 S
N
Ar 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.
Greener synthetic routes, physicalchemical properties, green metrics performance and applications for the eco-friendly polar aprotic solvent, methyl 5-dimethylamino-2-methyl-5-oxopentanoate (PolarClean).</description><subject>Atom economy</subject><subject>Brand names</subject><subject>Catalysis</subject><subject>Dielectric constant</subject><subject>Dielectric properties</subject><subject>Economic conditions</subject><subject>Green chemistry</subject><subject>Hazard assessment</subject><subject>High-performance liquid chromatography</subject><subject>Liquid chromatography</subject><subject>Miscibility</subject><subject>NMR</subject><subject>Nuclear magnetic resonance</subject><subject>Organic chemistry</subject><subject>Solubility parameters</subject><subject>Solvents</subject><subject>Synthesis</subject><issn>1463-9262</issn><issn>1463-9270</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2019</creationdate><recordtype>article</recordtype><recordid>eNpFkUtLxTAQhYso-Ny4FwJuVIgmTZM27qT4ggu60HXJ0xvpTWoS9d5_4s-114qu5gzzcWY4UxSHGJ1jRPiF4i8KYU6b-UaxgytGIC9rtPmnWbld7Kb0ihDGNat2iq-n8CmiTkD1RngTwWPoRWzXzSUw1jrljM8grXyem-QSEF4Ds8zGa6OBGIbeKZFd8AkEC0YGDGuDcRJDdgqk0H-sDRYmz1c9oPBEu0mLhfPhFJZwaiGFYRmGkRU-iGz2iy0r-mQOfute8Xxz_dTewdnD7X17NYOK0CpDzqQRFeGWyEoKybElmmlUCiokRVXdNNJqjjVnRLKyYlgSqg2xtsayrgkle8Xx5Dse_PZuUu5ew3v048quLBltUM2aeqTOJkrFkFI0thuiW4i46jDq1sl3Lb9tf5K_G-GjCY5J_XH_nyHf6DCDPg</recordid><startdate>2019</startdate><enddate>2019</enddate><creator>Cseri, Levente</creator><creator>Szekely, Gyorgy</creator><general>Royal Society of Chemistry</general><scope>AAYXX</scope><scope>CITATION</scope><scope>7SR</scope><scope>7ST</scope><scope>7U6</scope><scope>8BQ</scope><scope>8FD</scope><scope>C1K</scope><scope>JG9</scope><orcidid>https://orcid.org/0000-0002-3016-5477</orcidid><orcidid>https://orcid.org/0000-0001-9658-2452</orcidid></search><sort><creationdate>2019</creationdate><title>Towards cleaner PolarClean: efficient synthesis and extended applications of the polar aprotic solvent methyl 5-(dimethylamino)-2-methyl-5-oxopentanoate</title><author>Cseri, Levente ; Szekely, Gyorgy</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c354t-96bea439f3b4bab91f3d6d02a5ab504788bfd91d963b62461b35de3ff71b77353</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2019</creationdate><topic>Atom economy</topic><topic>Brand names</topic><topic>Catalysis</topic><topic>Dielectric constant</topic><topic>Dielectric properties</topic><topic>Economic conditions</topic><topic>Green chemistry</topic><topic>Hazard assessment</topic><topic>High-performance liquid chromatography</topic><topic>Liquid chromatography</topic><topic>Miscibility</topic><topic>NMR</topic><topic>Nuclear magnetic resonance</topic><topic>Organic chemistry</topic><topic>Solubility parameters</topic><topic>Solvents</topic><topic>Synthesis</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Cseri, Levente</creatorcontrib><creatorcontrib>Szekely, Gyorgy</creatorcontrib><collection>CrossRef</collection><collection>Engineered Materials Abstracts</collection><collection>Environment Abstracts</collection><collection>Sustainability Science Abstracts</collection><collection>METADEX</collection><collection>Technology Research Database</collection><collection>Environmental Sciences and Pollution Management</collection><collection>Materials Research Database</collection><jtitle>Green chemistry : an international journal and green chemistry resource : GC</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Cseri, Levente</au><au>Szekely, Gyorgy</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Towards cleaner PolarClean: efficient synthesis and extended applications of the polar aprotic solvent methyl 5-(dimethylamino)-2-methyl-5-oxopentanoate</atitle><jtitle>Green chemistry : an international journal and green chemistry resource : GC</jtitle><date>2019</date><risdate>2019</risdate><volume>21</volume><issue>15</issue><spage>4178</spage><epage>4188</epage><pages>4178-4188</pages><issn>1463-9262</issn><eissn>1463-9270</eissn><abstract>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 S
N
Ar 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.
Greener synthetic routes, physicalchemical properties, green metrics performance and applications for the eco-friendly polar aprotic solvent, methyl 5-dimethylamino-2-methyl-5-oxopentanoate (PolarClean).</abstract><cop>Cambridge</cop><pub>Royal Society of Chemistry</pub><doi>10.1039/c9gc01958h</doi><tpages>11</tpages><orcidid>https://orcid.org/0000-0002-3016-5477</orcidid><orcidid>https://orcid.org/0000-0001-9658-2452</orcidid><oa>free_for_read</oa></addata></record> |
| fulltext | fulltext |
| identifier | ISSN: 1463-9262 |
| ispartof | Green chemistry : an international journal and green chemistry resource : GC, 2019, Vol.21 (15), p.4178-4188 |
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| language | eng |
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| source | Royal Society Of Chemistry Journals 2008-; Alma/SFX Local Collection |
| subjects | Atom economy Brand names Catalysis Dielectric constant Dielectric properties Economic conditions Green chemistry Hazard assessment High-performance liquid chromatography Liquid chromatography Miscibility NMR Nuclear magnetic resonance Organic chemistry Solubility parameters Solvents Synthesis |
| title | Towards cleaner PolarClean: efficient synthesis and extended applications of the polar aprotic solvent methyl 5-(dimethylamino)-2-methyl-5-oxopentanoate |
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