Dynamics for Reaction of an Ion Pair in Aqueous Solution: Reactivity of Carboxylate Anions in Bimolecular Carbocation−Nucleophile Addition and Unimolecular Ion Pair Collapse
The sum of the rate constants for solvolysis and 18O-scrambling of 4-MeC6H4 13CH(Me)18OC(O)C6F5 in 50/50 (v/v) trifluoroethanol/water, k solv + k iso = 1.22 × 10-5 s-1, is larger than k solv = 1.06 × 10-5 s-1 for solvolysis of the unlabeled ester. This shows that the ion pair intermediate undergoes...
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| Veröffentlicht in: | Organic letters 2001-04, Vol.3 (8), p.1237-1240 |
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| creator | Tsuji, Yutaka Mori, Tetsuo Richard, John P Amyes, Tina L Fujio, Mizue Tsuno, Yuho |
| description | The sum of the rate constants for solvolysis and 18O-scrambling of 4-MeC6H4 13CH(Me)18OC(O)C6F5 in 50/50 (v/v) trifluoroethanol/water, k solv + k iso = 1.22 × 10-5 s-1, is larger than k solv = 1.06 × 10-5 s-1 for solvolysis of the unlabeled ester. This shows that the ion pair intermediate undergoes significant internal return. The data give k - 1 = 7 × 109 s-1 for internal return by unimolecular collapse of the ion pair, which is significantly larger than k Nu = 5 × 108 M-1 s-1 for bimolecular nucleophilic addition of carboxylate anions to 4-MeC6H4CH(Me)+. |
| doi_str_mv | 10.1021/ol015706s |
| format | Article |
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This shows that the ion pair intermediate undergoes significant internal return. The data give k - 1 = 7 × 109 s-1 for internal return by unimolecular collapse of the ion pair, which is significantly larger than k Nu = 5 × 108 M-1 s-1 for bimolecular nucleophilic addition of carboxylate anions to 4-MeC6H4CH(Me)+.</description><identifier>ISSN: 1523-7060</identifier><identifier>EISSN: 1523-7052</identifier><identifier>DOI: 10.1021/ol015706s</identifier><identifier>PMID: 11348203</identifier><language>eng</language><publisher>United States: American Chemical Society</publisher><subject>Anions ; Carbon - chemistry ; Chemistry, Organic - methods ; Esters - chemistry ; Ions ; Kinetics ; Polytetrafluoroethylene - chemistry</subject><ispartof>Organic letters, 2001-04, Vol.3 (8), p.1237-1240</ispartof><rights>Copyright © 2001 American Chemical Society</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-a311t-5b0ccf0aa7c065f3c064f38d937633c0e8cc3af79f941a21fa3fa8010758e8f43</citedby><cites>FETCH-LOGICAL-a311t-5b0ccf0aa7c065f3c064f38d937633c0e8cc3af79f941a21fa3fa8010758e8f43</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/ol015706s$$EPDF$$P50$$Gacs$$H</linktopdf><linktohtml>$$Uhttps://pubs.acs.org/doi/10.1021/ol015706s$$EHTML$$P50$$Gacs$$H</linktohtml><link.rule.ids>314,776,780,2751,27055,27903,27904,56716,56766</link.rule.ids><backlink>$$Uhttps://www.ncbi.nlm.nih.gov/pubmed/11348203$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink></links><search><creatorcontrib>Tsuji, Yutaka</creatorcontrib><creatorcontrib>Mori, Tetsuo</creatorcontrib><creatorcontrib>Richard, John P</creatorcontrib><creatorcontrib>Amyes, Tina L</creatorcontrib><creatorcontrib>Fujio, Mizue</creatorcontrib><creatorcontrib>Tsuno, Yuho</creatorcontrib><title>Dynamics for Reaction of an Ion Pair in Aqueous Solution: Reactivity of Carboxylate Anions in Bimolecular Carbocation−Nucleophile Addition and Unimolecular Ion Pair Collapse</title><title>Organic letters</title><addtitle>Org. Lett</addtitle><description>The sum of the rate constants for solvolysis and 18O-scrambling of 4-MeC6H4 13CH(Me)18OC(O)C6F5 in 50/50 (v/v) trifluoroethanol/water, k solv + k iso = 1.22 × 10-5 s-1, is larger than k solv = 1.06 × 10-5 s-1 for solvolysis of the unlabeled ester. This shows that the ion pair intermediate undergoes significant internal return. The data give k - 1 = 7 × 109 s-1 for internal return by unimolecular collapse of the ion pair, which is significantly larger than k Nu = 5 × 108 M-1 s-1 for bimolecular nucleophilic addition of carboxylate anions to 4-MeC6H4CH(Me)+.</description><subject>Anions</subject><subject>Carbon - chemistry</subject><subject>Chemistry, Organic - methods</subject><subject>Esters - chemistry</subject><subject>Ions</subject><subject>Kinetics</subject><subject>Polytetrafluoroethylene - chemistry</subject><issn>1523-7060</issn><issn>1523-7052</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2001</creationdate><recordtype>article</recordtype><sourceid>EIF</sourceid><recordid>eNptkc1OGzEUha2KqoHAghdA3lCJRej1OJOZdJeGv0hRi1qyHt14bNWRxw72DCI7lrDlUXikPAmeJkq76Ma-tr5zfK8PIccMzhkk7IszwNIMBuED2WdpwnsZpMnerh5AhxyEsABg8Wb4iXQY4_08Ab5P3i5WFistAlXO058SRa2dpU5RtHQSq1vUnmpLR_eNdE2gv5xpWuTr-ullyz_oetUqxujn7nFlsJZ0ZCMTWuE3XTkjRWPQbwiBrX79_Pq9EUa65W9tIl-W-s_LaEs6s_9odk2MnTG4DPKQfFRogjza7l0yu7q8G9_0pj-uJ-PRtIecsbqXzkEIBYiZgEGqeFz7iuflkGcDHk8yF4KjyoZq2GeYMIVcYQ4MsjSXuerzLvm88V16F4cPdVHpIGRswrY_UWSQp8CSLIJnG1B4F4KXqlh6XaFfFQyKNqBiF1BkT7amzbyS5V9ym0gETjcAilAsXONtnPE_Ru8e1JxJ</recordid><startdate>20010419</startdate><enddate>20010419</enddate><creator>Tsuji, Yutaka</creator><creator>Mori, Tetsuo</creator><creator>Richard, John P</creator><creator>Amyes, Tina L</creator><creator>Fujio, Mizue</creator><creator>Tsuno, Yuho</creator><general>American Chemical Society</general><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>20010419</creationdate><title>Dynamics for Reaction of an Ion Pair in Aqueous Solution: Reactivity of Carboxylate Anions in Bimolecular Carbocation−Nucleophile Addition and Unimolecular Ion Pair Collapse</title><author>Tsuji, Yutaka ; Mori, Tetsuo ; Richard, John P ; Amyes, Tina L ; Fujio, Mizue ; Tsuno, Yuho</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-a311t-5b0ccf0aa7c065f3c064f38d937633c0e8cc3af79f941a21fa3fa8010758e8f43</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2001</creationdate><topic>Anions</topic><topic>Carbon - chemistry</topic><topic>Chemistry, Organic - methods</topic><topic>Esters - chemistry</topic><topic>Ions</topic><topic>Kinetics</topic><topic>Polytetrafluoroethylene - chemistry</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Tsuji, Yutaka</creatorcontrib><creatorcontrib>Mori, Tetsuo</creatorcontrib><creatorcontrib>Richard, John P</creatorcontrib><creatorcontrib>Amyes, Tina L</creatorcontrib><creatorcontrib>Fujio, Mizue</creatorcontrib><creatorcontrib>Tsuno, Yuho</creatorcontrib><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>Organic letters</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Tsuji, Yutaka</au><au>Mori, Tetsuo</au><au>Richard, John P</au><au>Amyes, Tina L</au><au>Fujio, Mizue</au><au>Tsuno, Yuho</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Dynamics for Reaction of an Ion Pair in Aqueous Solution: Reactivity of Carboxylate Anions in Bimolecular Carbocation−Nucleophile Addition and Unimolecular Ion Pair Collapse</atitle><jtitle>Organic letters</jtitle><addtitle>Org. 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| language | eng |
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| source | ACS Publications; MEDLINE |
| subjects | Anions Carbon - chemistry Chemistry, Organic - methods Esters - chemistry Ions Kinetics Polytetrafluoroethylene - chemistry |
| title | Dynamics for Reaction of an Ion Pair in Aqueous Solution: Reactivity of Carboxylate Anions in Bimolecular Carbocation−Nucleophile Addition and Unimolecular Ion Pair Collapse |
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