Exploring the role of solvent polarity in mechanochemical Knoevenagel condensation: in situ investigation and isolation of reaction intermediates
Mechanochemistry has proven to be a highly effective method for the synthesis of organic compounds. We studied the kinetics of the catalyst-free Knoevenagel reaction between 4-nitrobenzaldehyde and malononitrile, activated and driven by ball milling. The reaction was investigated in the absence of s...
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| Veröffentlicht in: | Physical chemistry chemical physics : PCCP 2023-09, Vol.25 (35), p.23637-23644 |
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| creator | Scheurrell, Kerstin B Martins, Inês C Murray, Claire Emmerling, Franziska |
| description | Mechanochemistry has proven to be a highly effective method for the synthesis of organic compounds. We studied the kinetics of the catalyst-free Knoevenagel reaction between 4-nitrobenzaldehyde and malononitrile, activated and driven by ball milling. The reaction was investigated in the absence of solvents (neat grinding) and in the presence of solvents with different polarities (liquid-assisted grinding). The reaction was monitored using time-resolved
Raman spectroscopy and powder X-ray diffraction (PXRD). Our results indicate a direct relationship between solvent polarity and reaction kinetics, with higher solvent polarity leading to faster product (2-(4-nitrobenzylidone)malononitrile) formation. For the first time, we were able to isolate and determine the structure of an intermediate 2-(hydroxy(4-nitrophenyl)methyl)malononitrile based on PXRD data. |
| doi_str_mv | 10.1039/d3cp02883f |
| format | Article |
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Raman spectroscopy and powder X-ray diffraction (PXRD). Our results indicate a direct relationship between solvent polarity and reaction kinetics, with higher solvent polarity leading to faster product (2-(4-nitrobenzylidone)malononitrile) formation. For the first time, we were able to isolate and determine the structure of an intermediate 2-(hydroxy(4-nitrophenyl)methyl)malononitrile based on PXRD data.</description><identifier>ISSN: 1463-9076</identifier><identifier>ISSN: 1463-9084</identifier><identifier>EISSN: 1463-9084</identifier><identifier>DOI: 10.1039/d3cp02883f</identifier><identifier>PMID: 37650575</identifier><language>eng</language><publisher>England: Royal Society of Chemistry</publisher><subject>Ball milling ; Comminution ; Condensates ; Grinding ; Malononitrile ; Organic compounds ; Raman spectroscopy ; Reaction intermediates ; Reaction kinetics ; Solvents ; X ray powder diffraction</subject><ispartof>Physical chemistry chemical physics : PCCP, 2023-09, Vol.25 (35), p.23637-23644</ispartof><rights>Copyright Royal Society of Chemistry 2023</rights><lds50>peer_reviewed</lds50><oa>free_for_read</oa><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c351t-5b9a3f4bf59828632cfa08a10be1b42590e38eaee87f71e29ec2a3d7104221653</citedby><cites>FETCH-LOGICAL-c351t-5b9a3f4bf59828632cfa08a10be1b42590e38eaee87f71e29ec2a3d7104221653</cites><orcidid>0000-0002-1639-7554 ; 0000-0001-8528-0301 ; 0000-0002-8306-3634</orcidid></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><link.rule.ids>314,776,780,27903,27904</link.rule.ids><backlink>$$Uhttps://www.ncbi.nlm.nih.gov/pubmed/37650575$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink></links><search><creatorcontrib>Scheurrell, Kerstin</creatorcontrib><creatorcontrib>B Martins, Inês C</creatorcontrib><creatorcontrib>Murray, Claire</creatorcontrib><creatorcontrib>Emmerling, Franziska</creatorcontrib><title>Exploring the role of solvent polarity in mechanochemical Knoevenagel condensation: in situ investigation and isolation of reaction intermediates</title><title>Physical chemistry chemical physics : PCCP</title><addtitle>Phys Chem Chem Phys</addtitle><description>Mechanochemistry has proven to be a highly effective method for the synthesis of organic compounds. We studied the kinetics of the catalyst-free Knoevenagel reaction between 4-nitrobenzaldehyde and malononitrile, activated and driven by ball milling. The reaction was investigated in the absence of solvents (neat grinding) and in the presence of solvents with different polarities (liquid-assisted grinding). The reaction was monitored using time-resolved
Raman spectroscopy and powder X-ray diffraction (PXRD). Our results indicate a direct relationship between solvent polarity and reaction kinetics, with higher solvent polarity leading to faster product (2-(4-nitrobenzylidone)malononitrile) formation. For the first time, we were able to isolate and determine the structure of an intermediate 2-(hydroxy(4-nitrophenyl)methyl)malononitrile based on PXRD data.</description><subject>Ball milling</subject><subject>Comminution</subject><subject>Condensates</subject><subject>Grinding</subject><subject>Malononitrile</subject><subject>Organic compounds</subject><subject>Raman spectroscopy</subject><subject>Reaction intermediates</subject><subject>Reaction kinetics</subject><subject>Solvents</subject><subject>X ray powder diffraction</subject><issn>1463-9076</issn><issn>1463-9084</issn><issn>1463-9084</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2023</creationdate><recordtype>article</recordtype><recordid>eNpdkctO3DAUhi0EYihlwwNUlthUlQZ8iROHHZrOtBVIdAHryHFOZowcO9gOKo_BG9fM0Fl0dS769J_Lj9A5JZeU8Pqq43okTEreH6ATWpR8XhNZHO7zqpyhTzE-EUKooPwYzXhVCiIqcYLeln9G64Nxa5w2gIO3gH2Po7cv4BIevVXBpFdsHB5Ab5TzegOD0criW-chQ2oNFmvvOnBRJePd9TscTZpyfIGYzHrbxsp12GThXZWHBFB6mxuXIAzQGZUgfkZHvbIRzj7iKXpcLR8WP-d39z9-LW7u5poLmuairRXvi7YXtWSy5Ez3ikhFSQu0LZioCXAJCkBWfUWB1aCZ4l1FScEYLQU_RV93umPwz1PesxlM1GCtcuCn2DAp6jK_lRQZvfgPffJTcHm7TJVFkT8pWKa-7SgdfIwB-mYMZlDhtaGkeTeq-c4Xv7dGrTL85UNyavPle_SfM_wvyv6Q1Q</recordid><startdate>20230913</startdate><enddate>20230913</enddate><creator>Scheurrell, Kerstin</creator><creator>B Martins, Inês C</creator><creator>Murray, Claire</creator><creator>Emmerling, Franziska</creator><general>Royal Society of Chemistry</general><scope>NPM</scope><scope>AAYXX</scope><scope>CITATION</scope><scope>7SR</scope><scope>7U5</scope><scope>8BQ</scope><scope>8FD</scope><scope>JG9</scope><scope>L7M</scope><scope>7X8</scope><orcidid>https://orcid.org/0000-0002-1639-7554</orcidid><orcidid>https://orcid.org/0000-0001-8528-0301</orcidid><orcidid>https://orcid.org/0000-0002-8306-3634</orcidid></search><sort><creationdate>20230913</creationdate><title>Exploring the role of solvent polarity in mechanochemical Knoevenagel condensation: in situ investigation and isolation of reaction intermediates</title><author>Scheurrell, Kerstin ; B Martins, Inês C ; Murray, Claire ; Emmerling, Franziska</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c351t-5b9a3f4bf59828632cfa08a10be1b42590e38eaee87f71e29ec2a3d7104221653</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2023</creationdate><topic>Ball milling</topic><topic>Comminution</topic><topic>Condensates</topic><topic>Grinding</topic><topic>Malononitrile</topic><topic>Organic compounds</topic><topic>Raman spectroscopy</topic><topic>Reaction intermediates</topic><topic>Reaction kinetics</topic><topic>Solvents</topic><topic>X ray powder diffraction</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Scheurrell, Kerstin</creatorcontrib><creatorcontrib>B Martins, Inês C</creatorcontrib><creatorcontrib>Murray, Claire</creatorcontrib><creatorcontrib>Emmerling, Franziska</creatorcontrib><collection>PubMed</collection><collection>CrossRef</collection><collection>Engineered Materials Abstracts</collection><collection>Solid State and Superconductivity Abstracts</collection><collection>METADEX</collection><collection>Technology Research Database</collection><collection>Materials Research Database</collection><collection>Advanced Technologies Database with Aerospace</collection><collection>MEDLINE - Academic</collection><jtitle>Physical chemistry chemical physics : PCCP</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Scheurrell, Kerstin</au><au>B Martins, Inês C</au><au>Murray, Claire</au><au>Emmerling, Franziska</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Exploring the role of solvent polarity in mechanochemical Knoevenagel condensation: in situ investigation and isolation of reaction intermediates</atitle><jtitle>Physical chemistry chemical physics : PCCP</jtitle><addtitle>Phys Chem Chem Phys</addtitle><date>2023-09-13</date><risdate>2023</risdate><volume>25</volume><issue>35</issue><spage>23637</spage><epage>23644</epage><pages>23637-23644</pages><issn>1463-9076</issn><issn>1463-9084</issn><eissn>1463-9084</eissn><abstract>Mechanochemistry has proven to be a highly effective method for the synthesis of organic compounds. We studied the kinetics of the catalyst-free Knoevenagel reaction between 4-nitrobenzaldehyde and malononitrile, activated and driven by ball milling. The reaction was investigated in the absence of solvents (neat grinding) and in the presence of solvents with different polarities (liquid-assisted grinding). The reaction was monitored using time-resolved
Raman spectroscopy and powder X-ray diffraction (PXRD). Our results indicate a direct relationship between solvent polarity and reaction kinetics, with higher solvent polarity leading to faster product (2-(4-nitrobenzylidone)malononitrile) formation. For the first time, we were able to isolate and determine the structure of an intermediate 2-(hydroxy(4-nitrophenyl)methyl)malononitrile based on PXRD data.</abstract><cop>England</cop><pub>Royal Society of Chemistry</pub><pmid>37650575</pmid><doi>10.1039/d3cp02883f</doi><tpages>8</tpages><orcidid>https://orcid.org/0000-0002-1639-7554</orcidid><orcidid>https://orcid.org/0000-0001-8528-0301</orcidid><orcidid>https://orcid.org/0000-0002-8306-3634</orcidid><oa>free_for_read</oa></addata></record> |
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| identifier | ISSN: 1463-9076 |
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| source | Royal Society Of Chemistry Journals 2008-; Alma/SFX Local Collection |
| subjects | Ball milling Comminution Condensates Grinding Malononitrile Organic compounds Raman spectroscopy Reaction intermediates Reaction kinetics Solvents X ray powder diffraction |
| title | Exploring the role of solvent polarity in mechanochemical Knoevenagel condensation: in situ investigation and isolation of reaction intermediates |
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