Nucleophilicities of the Anions of Arylacetonitriles and Arylpropionitriles in Dimethyl Sulfoxide
The rates of the reactions of the colored para-substituted phenylacetonitrile anions 1a−c and the phenylpropionitrile anions 2a−c with Michael acceptors (3a−u) were determined by UV−vis spectroscopy in DMSO at 20 °C. The reactions follow second-order kinetics, and the corresponding rate constants k...
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| Veröffentlicht in: | Journal of organic chemistry 2009-01, Vol.74 (1), p.75-81 |
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| container_title | Journal of organic chemistry |
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| creator | Kaumanns, Oliver Appel, Roland Lemek, Tadeusz Seeliger, Florian Mayr, Herbert |
| description | The rates of the reactions of the colored para-substituted phenylacetonitrile anions 1a−c and the phenylpropionitrile anions 2a−c with Michael acceptors (3a−u) were determined by UV−vis spectroscopy in DMSO at 20 °C. The reactions follow second-order kinetics, and the corresponding rate constants k 2 obey the linear-free-energy relationship log k 2(20 °C) = s(N + E), from which the nucleophile-specific parameters N and s of the carbanions 1a−c and 2a−c have been derived. With nucleophilicity parameters from 19 < N < 29, they are among the most reactive nucleophiles which we have so far parametrized. In DMSO, the nucleophilicity of the tert-butoxide anion is comparable to that of the p-cyanophenylacetonitrile anion 1b. |
| doi_str_mv | 10.1021/jo802241x |
| format | Article |
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The reactions follow second-order kinetics, and the corresponding rate constants k 2 obey the linear-free-energy relationship log k 2(20 °C) = s(N + E), from which the nucleophile-specific parameters N and s of the carbanions 1a−c and 2a−c have been derived. With nucleophilicity parameters from 19 < N < 29, they are among the most reactive nucleophiles which we have so far parametrized. In DMSO, the nucleophilicity of the tert-butoxide anion is comparable to that of the p-cyanophenylacetonitrile anion 1b.</description><identifier>ISSN: 0022-3263</identifier><identifier>EISSN: 1520-6904</identifier><identifier>DOI: 10.1021/jo802241x</identifier><identifier>PMID: 19032115</identifier><identifier>CODEN: JOCEAH</identifier><language>eng</language><publisher>Washington, DC: American Chemical Society</publisher><subject>Acetonitriles - chemistry ; Anions - chemistry ; Chemical reactivity ; Chemistry ; Dimethyl Sulfoxide - chemistry ; Exact sciences and technology ; Indans - chemical synthesis ; Indans - chemistry ; Kinetics ; Kinetics and mechanisms ; Magnetic Resonance Spectroscopy ; Malonates - chemical synthesis ; Malonates - chemistry ; Molecular Structure ; Nitriles - chemistry ; Organic chemistry ; Quinones - chemical synthesis ; Quinones - chemistry ; Reactivity and mechanisms ; Spectrophotometry, Ultraviolet ; Stereoisomerism</subject><ispartof>Journal of organic chemistry, 2009-01, Vol.74 (1), p.75-81</ispartof><rights>Copyright © 2009 American Chemical Society</rights><rights>2009 INIST-CNRS</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-a409t-8c02eb13bf748641e6b91ae1eaf808d2d861fac2a9bb9f46ff731515778353c3</citedby><cites>FETCH-LOGICAL-a409t-8c02eb13bf748641e6b91ae1eaf808d2d861fac2a9bb9f46ff731515778353c3</cites></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><linktopdf>$$Uhttps://pubs.acs.org/doi/pdf/10.1021/jo802241x$$EPDF$$P50$$Gacs$$H</linktopdf><linktohtml>$$Uhttps://pubs.acs.org/doi/10.1021/jo802241x$$EHTML$$P50$$Gacs$$H</linktohtml><link.rule.ids>314,780,784,2765,27076,27924,27925,56738,56788</link.rule.ids><backlink>$$Uhttp://pascal-francis.inist.fr/vibad/index.php?action=getRecordDetail&idt=20993663$$DView record in Pascal Francis$$Hfree_for_read</backlink><backlink>$$Uhttps://www.ncbi.nlm.nih.gov/pubmed/19032115$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink></links><search><creatorcontrib>Kaumanns, Oliver</creatorcontrib><creatorcontrib>Appel, Roland</creatorcontrib><creatorcontrib>Lemek, Tadeusz</creatorcontrib><creatorcontrib>Seeliger, Florian</creatorcontrib><creatorcontrib>Mayr, Herbert</creatorcontrib><title>Nucleophilicities of the Anions of Arylacetonitriles and Arylpropionitriles in Dimethyl Sulfoxide</title><title>Journal of organic chemistry</title><addtitle>J. Org. Chem</addtitle><description>The rates of the reactions of the colored para-substituted phenylacetonitrile anions 1a−c and the phenylpropionitrile anions 2a−c with Michael acceptors (3a−u) were determined by UV−vis spectroscopy in DMSO at 20 °C. The reactions follow second-order kinetics, and the corresponding rate constants k 2 obey the linear-free-energy relationship log k 2(20 °C) = s(N + E), from which the nucleophile-specific parameters N and s of the carbanions 1a−c and 2a−c have been derived. With nucleophilicity parameters from 19 < N < 29, they are among the most reactive nucleophiles which we have so far parametrized. In DMSO, the nucleophilicity of the tert-butoxide anion is comparable to that of the p-cyanophenylacetonitrile anion 1b.</description><subject>Acetonitriles - chemistry</subject><subject>Anions - chemistry</subject><subject>Chemical reactivity</subject><subject>Chemistry</subject><subject>Dimethyl Sulfoxide - chemistry</subject><subject>Exact sciences and technology</subject><subject>Indans - chemical synthesis</subject><subject>Indans - chemistry</subject><subject>Kinetics</subject><subject>Kinetics and mechanisms</subject><subject>Magnetic Resonance Spectroscopy</subject><subject>Malonates - chemical synthesis</subject><subject>Malonates - chemistry</subject><subject>Molecular Structure</subject><subject>Nitriles - chemistry</subject><subject>Organic chemistry</subject><subject>Quinones - chemical synthesis</subject><subject>Quinones - chemistry</subject><subject>Reactivity and mechanisms</subject><subject>Spectrophotometry, Ultraviolet</subject><subject>Stereoisomerism</subject><issn>0022-3263</issn><issn>1520-6904</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2009</creationdate><recordtype>article</recordtype><sourceid>EIF</sourceid><recordid>eNpt0E1LwzAYB_AgipvTg19AelHwUM1Lk7bHMV9h6MHdS5omLCNNZtLC9u3NtrJdzCXkz48nD38AbhF8QhCj55UrIMYZ2pyBMaIYpqyE2TkYw5imBDMyAlchrGA8lNJLMEIlJBghOgb8qxdGuvVSGy10p2VInEq6pUymVju7f0391nAhO2d157WJhNtmn669W-tTrG3yolvZLbcm-emNchvdyGtwobgJ8ma4J2Dx9rqYfaTz7_fP2XSe8gyWXVoIiGWNSK3yrGAZkqwuEZdIclXAosFNwZDiAvOyrkuVMaVygiiieV4QSgSZgIfD2LjTby9DV7U6CGkMt9L1oWJsB3Mc4eMBCu9C8FJVa69b7rcVgtWuzupYZ7R3w9C-bmVzkkN_EdwPgAfBjfLcCh2ODsOyJIyRk-MixPm9t7GKfz78A_rsimw</recordid><startdate>20090102</startdate><enddate>20090102</enddate><creator>Kaumanns, Oliver</creator><creator>Appel, Roland</creator><creator>Lemek, Tadeusz</creator><creator>Seeliger, Florian</creator><creator>Mayr, Herbert</creator><general>American Chemical Society</general><scope>IQODW</scope><scope>CGR</scope><scope>CUY</scope><scope>CVF</scope><scope>ECM</scope><scope>EIF</scope><scope>NPM</scope><scope>AAYXX</scope><scope>CITATION</scope><scope>7X8</scope></search><sort><creationdate>20090102</creationdate><title>Nucleophilicities of the Anions of Arylacetonitriles and Arylpropionitriles in Dimethyl Sulfoxide</title><author>Kaumanns, Oliver ; Appel, Roland ; Lemek, Tadeusz ; Seeliger, Florian ; Mayr, Herbert</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-a409t-8c02eb13bf748641e6b91ae1eaf808d2d861fac2a9bb9f46ff731515778353c3</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2009</creationdate><topic>Acetonitriles - chemistry</topic><topic>Anions - chemistry</topic><topic>Chemical reactivity</topic><topic>Chemistry</topic><topic>Dimethyl Sulfoxide - chemistry</topic><topic>Exact sciences and technology</topic><topic>Indans - chemical synthesis</topic><topic>Indans - chemistry</topic><topic>Kinetics</topic><topic>Kinetics and mechanisms</topic><topic>Magnetic Resonance Spectroscopy</topic><topic>Malonates - chemical synthesis</topic><topic>Malonates - chemistry</topic><topic>Molecular Structure</topic><topic>Nitriles - chemistry</topic><topic>Organic chemistry</topic><topic>Quinones - chemical synthesis</topic><topic>Quinones - chemistry</topic><topic>Reactivity and mechanisms</topic><topic>Spectrophotometry, Ultraviolet</topic><topic>Stereoisomerism</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Kaumanns, Oliver</creatorcontrib><creatorcontrib>Appel, Roland</creatorcontrib><creatorcontrib>Lemek, Tadeusz</creatorcontrib><creatorcontrib>Seeliger, Florian</creatorcontrib><creatorcontrib>Mayr, Herbert</creatorcontrib><collection>Pascal-Francis</collection><collection>Medline</collection><collection>MEDLINE</collection><collection>MEDLINE (Ovid)</collection><collection>MEDLINE</collection><collection>MEDLINE</collection><collection>PubMed</collection><collection>CrossRef</collection><collection>MEDLINE - Academic</collection><jtitle>Journal of organic chemistry</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Kaumanns, Oliver</au><au>Appel, Roland</au><au>Lemek, Tadeusz</au><au>Seeliger, Florian</au><au>Mayr, Herbert</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Nucleophilicities of the Anions of Arylacetonitriles and Arylpropionitriles in Dimethyl Sulfoxide</atitle><jtitle>Journal of organic chemistry</jtitle><addtitle>J. Org. Chem</addtitle><date>2009-01-02</date><risdate>2009</risdate><volume>74</volume><issue>1</issue><spage>75</spage><epage>81</epage><pages>75-81</pages><issn>0022-3263</issn><eissn>1520-6904</eissn><coden>JOCEAH</coden><abstract>The rates of the reactions of the colored para-substituted phenylacetonitrile anions 1a−c and the phenylpropionitrile anions 2a−c with Michael acceptors (3a−u) were determined by UV−vis spectroscopy in DMSO at 20 °C. The reactions follow second-order kinetics, and the corresponding rate constants k 2 obey the linear-free-energy relationship log k 2(20 °C) = s(N + E), from which the nucleophile-specific parameters N and s of the carbanions 1a−c and 2a−c have been derived. With nucleophilicity parameters from 19 < N < 29, they are among the most reactive nucleophiles which we have so far parametrized. 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| subjects | Acetonitriles - chemistry Anions - chemistry Chemical reactivity Chemistry Dimethyl Sulfoxide - chemistry Exact sciences and technology Indans - chemical synthesis Indans - chemistry Kinetics Kinetics and mechanisms Magnetic Resonance Spectroscopy Malonates - chemical synthesis Malonates - chemistry Molecular Structure Nitriles - chemistry Organic chemistry Quinones - chemical synthesis Quinones - chemistry Reactivity and mechanisms Spectrophotometry, Ultraviolet Stereoisomerism |
| title | Nucleophilicities of the Anions of Arylacetonitriles and Arylpropionitriles in Dimethyl Sulfoxide |
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