Kinetics and mechanism of unimolecular heterolysis of cage-like compounds: XXI. Solvent effect on the realtive rate of heterolysis of 2-methyland 2-phenyl-2-haloadamantanes. Role of activation parameters

Kinetics and mechanism of unimolecular heterolysis of cage-like compounds: XXI. Solvent effect on the realtive rate of heterolysis of 2-methyland 2-phenyl-2-haloadamantanes. Role of activation parameters

The kinetics of heterolysis of 2-chloro-2-methyladamantane, 2-bromo-2-methyladamantane, 2-chloro-2-phenyladamantane, and 2-bromo-2-phenyladamantane in isopropyl alcohol, tert-butyl alcohol, acetonitrile, nitromethane, cyclohexanone, and γ-butyrolactone were studied using the verdazyl technique. The...

Ausführliche Beschreibung

Gespeichert in:
Bibliographische Detailangaben
Veröffentlicht in:Russian journal of organic chemistry 2009-09, Vol.45 (9), p.1336-1343
Hauptverfasser: Dvorko, G. F, Vasil'kevich, A. I, Koshchii, I. V, Mikhal'chuk, K. V
Format: Artikel
Sprache:eng
Schlagworte:
Chemistry
Chemistry and Materials Science
Organic Chemistry
Online-Zugang:Volltext
Tags: Tag hinzufügen
Keine Tags, Fügen Sie den ersten Tag hinzu!
container_end_page 1343
container_issue 9
container_start_page 1336
container_title Russian journal of organic chemistry
container_volume 45
creator Dvorko, G. F
Vasil'kevich, A. I
Koshchii, I. V
Mikhal'chuk, K. V
description The kinetics of heterolysis of 2-chloro-2-methyladamantane, 2-bromo-2-methyladamantane, 2-chloro-2-phenyladamantane, and 2-bromo-2-phenyladamantane in isopropyl alcohol, tert-butyl alcohol, acetonitrile, nitromethane, cyclohexanone, and γ-butyrolactone were studied using the verdazyl technique. The rate constant ratio k Ph/k Me decreases from three orders of magnitude to unity in the solvent series BuOH > i-PrOH > t-BuOH > MeCN > PhNO₂ > cyclohexanone > γ-butyrolactone > sulfolane, which results from weakening of conjugation between the phenyl group and emerging carbocationic center. The effect of solvent on the entropy and enthalpy of heterolysis in going from 2-methyl-substituted 2-haloadamantanes to their 2-phenyl analogs is discussed.
doi_str_mv 10.1134/S107042800909005X
format Article
fullrecord <record><control><sourceid>fao_cross</sourceid><recordid>TN_cdi_crossref_primary_10_1134_S107042800909005X</recordid><sourceformat>XML</sourceformat><sourcesystem>PC</sourcesystem><sourcerecordid>US201301692444</sourcerecordid><originalsourceid>FETCH-LOGICAL-c227X-3466e95b61be17ba0562d217b238f0344e5b51709a55fcf71a8639074594620c3</originalsourceid><addsrcrecordid>eNp9kd2KFDEQhRtRcF19AK_MC2Ss_HT3tHey6Lq4IDguzF1Tk6lMZ00nQ5JZmGf0pUwzXilIXdSBU-fjQDXNWwErIZR-vxHQg5ZrgKEOtNtnzZXoYM2VGtTzqqvNF_9l8yrnRwDQQqur5tdXF6g4kxmGPZvJTBhcnlm07BTcHD2Zk8fEJiqUoj9nlxfP4IG4dz-JmTgf4yns8we23d6t2Cb6JwqFkbVkCouBlYlYIvTFPVWBhRbAXzzJZyrT2S8lJD9OFM6eSz6hj7jHGUPBQHnFvtdCyz2aSsPiKv6ICeeFll83Lyz6TG_-7Ovm4fOnHzdf-P2327ubj_fcSNlvudJdR0O768SORL9DaDu5l1VJtbagtKZ214oeBmxba2wvcN2pAXrdDrqTYNR1Iy5ck2LOiex4TG7GdB4FjMs3xn--UTPyksn1NhwojY_xlEKt-d_Qu0vIYhzxkFweHzYShALRDVJrrX4D8DmYjA</addsrcrecordid><sourcetype>Aggregation Database</sourcetype><iscdi>true</iscdi><recordtype>article</recordtype></control><display><type>article</type><title>Kinetics and mechanism of unimolecular heterolysis of cage-like compounds: XXI. Solvent effect on the realtive rate of heterolysis of 2-methyland 2-phenyl-2-haloadamantanes. Role of activation parameters</title><source>SpringerLink Journals - AutoHoldings</source><creator>Dvorko, G. F ; Vasil'kevich, A. I ; Koshchii, I. V ; Mikhal'chuk, K. V</creator><creatorcontrib>Dvorko, G. F ; Vasil'kevich, A. I ; Koshchii, I. V ; Mikhal'chuk, K. V</creatorcontrib><description>The kinetics of heterolysis of 2-chloro-2-methyladamantane, 2-bromo-2-methyladamantane, 2-chloro-2-phenyladamantane, and 2-bromo-2-phenyladamantane in isopropyl alcohol, tert-butyl alcohol, acetonitrile, nitromethane, cyclohexanone, and γ-butyrolactone were studied using the verdazyl technique. The rate constant ratio k Ph/k Me decreases from three orders of magnitude to unity in the solvent series BuOH &gt; i-PrOH &gt; t-BuOH &gt; MeCN &gt; PhNO₂ &gt; cyclohexanone &gt; γ-butyrolactone &gt; sulfolane, which results from weakening of conjugation between the phenyl group and emerging carbocationic center. The effect of solvent on the entropy and enthalpy of heterolysis in going from 2-methyl-substituted 2-haloadamantanes to their 2-phenyl analogs is discussed.</description><identifier>ISSN: 1070-4280</identifier><identifier>EISSN: 1608-3393</identifier><identifier>DOI: 10.1134/S107042800909005X</identifier><language>eng</language><publisher>Dordrecht: Dordrecht : SP MAIK Nauka/Interperiodica</publisher><subject>Chemistry ; Chemistry and Materials Science ; Organic Chemistry</subject><ispartof>Russian journal of organic chemistry, 2009-09, Vol.45 (9), p.1336-1343</ispartof><rights>Pleiades Publishing, Ltd. 2009</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c227X-3466e95b61be17ba0562d217b238f0344e5b51709a55fcf71a8639074594620c3</citedby><cites>FETCH-LOGICAL-c227X-3466e95b61be17ba0562d217b238f0344e5b51709a55fcf71a8639074594620c3</cites></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><linktopdf>$$Uhttps://link.springer.com/content/pdf/10.1134/S107042800909005X$$EPDF$$P50$$Gspringer$$H</linktopdf><linktohtml>$$Uhttps://link.springer.com/10.1134/S107042800909005X$$EHTML$$P50$$Gspringer$$H</linktohtml><link.rule.ids>314,776,780,27901,27902,41464,42533,51294</link.rule.ids></links><search><creatorcontrib>Dvorko, G. F</creatorcontrib><creatorcontrib>Vasil'kevich, A. I</creatorcontrib><creatorcontrib>Koshchii, I. V</creatorcontrib><creatorcontrib>Mikhal'chuk, K. V</creatorcontrib><title>Kinetics and mechanism of unimolecular heterolysis of cage-like compounds: XXI. Solvent effect on the realtive rate of heterolysis of 2-methyland 2-phenyl-2-haloadamantanes. Role of activation parameters</title><title>Russian journal of organic chemistry</title><addtitle>Russ J Org Chem</addtitle><description>The kinetics of heterolysis of 2-chloro-2-methyladamantane, 2-bromo-2-methyladamantane, 2-chloro-2-phenyladamantane, and 2-bromo-2-phenyladamantane in isopropyl alcohol, tert-butyl alcohol, acetonitrile, nitromethane, cyclohexanone, and γ-butyrolactone were studied using the verdazyl technique. The rate constant ratio k Ph/k Me decreases from three orders of magnitude to unity in the solvent series BuOH &gt; i-PrOH &gt; t-BuOH &gt; MeCN &gt; PhNO₂ &gt; cyclohexanone &gt; γ-butyrolactone &gt; sulfolane, which results from weakening of conjugation between the phenyl group and emerging carbocationic center. The effect of solvent on the entropy and enthalpy of heterolysis in going from 2-methyl-substituted 2-haloadamantanes to their 2-phenyl analogs is discussed.</description><subject>Chemistry</subject><subject>Chemistry and Materials Science</subject><subject>Organic Chemistry</subject><issn>1070-4280</issn><issn>1608-3393</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2009</creationdate><recordtype>article</recordtype><recordid>eNp9kd2KFDEQhRtRcF19AK_MC2Ss_HT3tHey6Lq4IDguzF1Tk6lMZ00nQ5JZmGf0pUwzXilIXdSBU-fjQDXNWwErIZR-vxHQg5ZrgKEOtNtnzZXoYM2VGtTzqqvNF_9l8yrnRwDQQqur5tdXF6g4kxmGPZvJTBhcnlm07BTcHD2Zk8fEJiqUoj9nlxfP4IG4dz-JmTgf4yns8we23d6t2Cb6JwqFkbVkCouBlYlYIvTFPVWBhRbAXzzJZyrT2S8lJD9OFM6eSz6hj7jHGUPBQHnFvtdCyz2aSsPiKv6ICeeFll83Lyz6TG_-7Ovm4fOnHzdf-P2327ubj_fcSNlvudJdR0O768SORL9DaDu5l1VJtbagtKZ214oeBmxba2wvcN2pAXrdDrqTYNR1Iy5ck2LOiex4TG7GdB4FjMs3xn--UTPyksn1NhwojY_xlEKt-d_Qu0vIYhzxkFweHzYShALRDVJrrX4D8DmYjA</recordid><startdate>200909</startdate><enddate>200909</enddate><creator>Dvorko, G. F</creator><creator>Vasil'kevich, A. I</creator><creator>Koshchii, I. V</creator><creator>Mikhal'chuk, K. V</creator><general>Dordrecht : SP MAIK Nauka/Interperiodica</general><general>SP MAIK Nauka/Interperiodica</general><scope>FBQ</scope><scope>AAYXX</scope><scope>CITATION</scope></search><sort><creationdate>200909</creationdate><title>Kinetics and mechanism of unimolecular heterolysis of cage-like compounds: XXI. Solvent effect on the realtive rate of heterolysis of 2-methyland 2-phenyl-2-haloadamantanes. Role of activation parameters</title><author>Dvorko, G. F ; Vasil'kevich, A. I ; Koshchii, I. V ; Mikhal'chuk, K. V</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c227X-3466e95b61be17ba0562d217b238f0344e5b51709a55fcf71a8639074594620c3</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2009</creationdate><topic>Chemistry</topic><topic>Chemistry and Materials Science</topic><topic>Organic Chemistry</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Dvorko, G. F</creatorcontrib><creatorcontrib>Vasil'kevich, A. I</creatorcontrib><creatorcontrib>Koshchii, I. V</creatorcontrib><creatorcontrib>Mikhal'chuk, K. V</creatorcontrib><collection>AGRIS</collection><collection>CrossRef</collection><jtitle>Russian journal of organic chemistry</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Dvorko, G. F</au><au>Vasil'kevich, A. I</au><au>Koshchii, I. V</au><au>Mikhal'chuk, K. V</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Kinetics and mechanism of unimolecular heterolysis of cage-like compounds: XXI. Solvent effect on the realtive rate of heterolysis of 2-methyland 2-phenyl-2-haloadamantanes. Role of activation parameters</atitle><jtitle>Russian journal of organic chemistry</jtitle><stitle>Russ J Org Chem</stitle><date>2009-09</date><risdate>2009</risdate><volume>45</volume><issue>9</issue><spage>1336</spage><epage>1343</epage><pages>1336-1343</pages><issn>1070-4280</issn><eissn>1608-3393</eissn><abstract>The kinetics of heterolysis of 2-chloro-2-methyladamantane, 2-bromo-2-methyladamantane, 2-chloro-2-phenyladamantane, and 2-bromo-2-phenyladamantane in isopropyl alcohol, tert-butyl alcohol, acetonitrile, nitromethane, cyclohexanone, and γ-butyrolactone were studied using the verdazyl technique. The rate constant ratio k Ph/k Me decreases from three orders of magnitude to unity in the solvent series BuOH &gt; i-PrOH &gt; t-BuOH &gt; MeCN &gt; PhNO₂ &gt; cyclohexanone &gt; γ-butyrolactone &gt; sulfolane, which results from weakening of conjugation between the phenyl group and emerging carbocationic center. The effect of solvent on the entropy and enthalpy of heterolysis in going from 2-methyl-substituted 2-haloadamantanes to their 2-phenyl analogs is discussed.</abstract><cop>Dordrecht</cop><pub>Dordrecht : SP MAIK Nauka/Interperiodica</pub><doi>10.1134/S107042800909005X</doi><tpages>8</tpages></addata></record>
fulltext fulltext
identifier ISSN: 1070-4280
ispartof Russian journal of organic chemistry, 2009-09, Vol.45 (9), p.1336-1343
issn 1070-4280
1608-3393
language eng
recordid cdi_crossref_primary_10_1134_S107042800909005X
source SpringerLink Journals - AutoHoldings
subjects Chemistry
Chemistry and Materials Science
Organic Chemistry
title Kinetics and mechanism of unimolecular heterolysis of cage-like compounds: XXI. Solvent effect on the realtive rate of heterolysis of 2-methyland 2-phenyl-2-haloadamantanes. Role of activation parameters
url https://sfx.bib-bvb.de/sfx_tum?ctx_ver=Z39.88-2004&ctx_enc=info:ofi/enc:UTF-8&ctx_tim=2025-01-28T14%3A52%3A00IST&url_ver=Z39.88-2004&url_ctx_fmt=infofi/fmt:kev:mtx:ctx&rfr_id=info:sid/primo.exlibrisgroup.com:primo3-Article-fao_cross&rft_val_fmt=info:ofi/fmt:kev:mtx:journal&rft.genre=article&rft.atitle=Kinetics%20and%20mechanism%20of%20unimolecular%20heterolysis%20of%20cage-like%20compounds:%20XXI.%20Solvent%20effect%20on%20the%20realtive%20rate%20of%20heterolysis%20of%202-methyland%202-phenyl-2-haloadamantanes.%20Role%20of%20activation%20parameters&rft.jtitle=Russian%20journal%20of%20organic%20chemistry&rft.au=Dvorko,%20G.%20F&rft.date=2009-09&rft.volume=45&rft.issue=9&rft.spage=1336&rft.epage=1343&rft.pages=1336-1343&rft.issn=1070-4280&rft.eissn=1608-3393&rft_id=info:doi/10.1134/S107042800909005X&rft_dat=%3Cfao_cross%3EUS201301692444%3C/fao_cross%3E%3Curl%3E%3C/url%3E&disable_directlink=true&sfx.directlink=off&sfx.report_link=0&rft_id=info:oai/&rft_id=info:pmid/&rfr_iscdi=true