Mechanism of hydroxylation of alkanes by dimethyldioxirane. A radical-clock study
Identifieur interne : 000862 ( Istex/Corpus ); précédent : 000861; suivant : 000863Mechanism of hydroxylation of alkanes by dimethyldioxirane. A radical-clock study
Auteurs : Raffaella Vanni ; Simon J. Garden ; Jeffrey T. Banks ; Keith U. IngoldSource :
- Tetrahedron Letters [ 0040-4039 ] ; 1995.
Abstract
The oxidation of 2-cyclopropylpropane by dimethyldioxirane (DMD) to 2-cyclopropyl-propan-2-ol is not a free-radical chain reaction. It is suggested the free-radical chain observed by Minisci et al.8 when alkane / DMD reactions were carried out in the presence of CCl3Br involves H-atom abstraction from the alkane by Cl3,COO· (in air) and by Me2C(O·)OCCl3, as well as by the Cl3C· radical.
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DOI: 10.1016/0040-4039(95)01666-6
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<record><TEI wicri:istexFullTextTei="biblStruct"><teiHeader><fileDesc><titleStmt><title xml:lang="en">Mechanism of hydroxylation of alkanes by dimethyldioxirane. A radical-clock study</title><author><name sortKey="Vanni, Raffaella" sort="Vanni, Raffaella" uniqKey="Vanni R" first="Raffaella" last="Vanni">Raffaella Vanni</name><affiliation><mods:affiliation>Steacie Institute for Molecular Sciences, National Research Council of Canada, Ottawa, Ontario, Canada K1A OR6</mods:affiliation></affiliation></author><author><name sortKey="Garden, Simon J" sort="Garden, Simon J" uniqKey="Garden S" first="Simon J." last="Garden">Simon J. Garden</name><affiliation><mods:affiliation>Steacie Institute for Molecular Sciences, National Research Council of Canada, Ottawa, Ontario, Canada K1A OR6</mods:affiliation></affiliation></author><author><name sortKey="Banks, Jeffrey T" sort="Banks, Jeffrey T" uniqKey="Banks J" first="Jeffrey T." last="Banks">Jeffrey T. 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A radical-clock study</title><author><name sortKey="Vanni, Raffaella" sort="Vanni, Raffaella" uniqKey="Vanni R" first="Raffaella" last="Vanni">Raffaella Vanni</name><affiliation><mods:affiliation>Steacie Institute for Molecular Sciences, National Research Council of Canada, Ottawa, Ontario, Canada K1A OR6</mods:affiliation></affiliation></author><author><name sortKey="Garden, Simon J" sort="Garden, Simon J" uniqKey="Garden S" first="Simon J." last="Garden">Simon J. Garden</name><affiliation><mods:affiliation>Steacie Institute for Molecular Sciences, National Research Council of Canada, Ottawa, Ontario, Canada K1A OR6</mods:affiliation></affiliation></author><author><name sortKey="Banks, Jeffrey T" sort="Banks, Jeffrey T" uniqKey="Banks J" first="Jeffrey T." last="Banks">Jeffrey T. Banks</name><affiliation><mods:affiliation>Steacie Institute for Molecular Sciences, National Research Council of Canada, Ottawa, Ontario, Canada K1A OR6</mods:affiliation></affiliation></author><author><name sortKey="Ingold, Keith U" sort="Ingold, Keith U" uniqKey="Ingold K" first="Keith U." last="Ingold">Keith U. Ingold</name><affiliation><mods:affiliation>Steacie Institute for Molecular Sciences, National Research Council of Canada, Ottawa, Ontario, Canada K1A OR6</mods:affiliation></affiliation></author></analytic><monogr></monogr><series><title level="j">Tetrahedron Letters</title><title level="j" type="abbrev">TETL</title><idno type="ISSN">0040-4039</idno><imprint><publisher>ELSEVIER</publisher><date type="published" when="1995">1995</date><biblScope unit="volume">36</biblScope><biblScope unit="issue">44</biblScope><biblScope unit="page" from="7999">7999</biblScope><biblScope unit="page" to="8002">8002</biblScope></imprint><idno type="ISSN">0040-4039</idno></series><idno type="istex">3CA19B4ECA6ACDD9A03341C62BFAC00EC7ADE92D</idno><idno type="DOI">10.1016/0040-4039(95)01666-6</idno><idno type="PII">0040-4039(95)01666-6</idno><idno type="ArticleID">95016666</idno></biblStruct></sourceDesc><seriesStmt><idno type="ISSN">0040-4039</idno></seriesStmt></fileDesc><profileDesc><textClass></textClass><langUsage><language ident="en">en</language></langUsage></profileDesc></teiHeader><front><div type="abstract" xml:lang="en">The oxidation of 2-cyclopropylpropane by dimethyldioxirane (DMD) to 2-cyclopropyl-propan-2-ol is not a free-radical chain reaction. It is suggested the free-radical chain observed by Minisci et al.8 when alkane / DMD reactions were carried out in the presence of CCl3Br involves H-atom abstraction from the alkane by Cl3,COO· (in air) and by Me2C(O·)OCCl3, as well as by the Cl3C· radical.</div></front></TEI><istex><corpusName>elsevier</corpusName><author><json:item><name>Raffaella Vanni</name><affiliations><json:string>Steacie Institute for Molecular Sciences, National Research Council of Canada, Ottawa, Ontario, Canada K1A OR6</json:string></affiliations></json:item><json:item><name>Simon J. Garden</name><affiliations><json:string>Steacie Institute for Molecular Sciences, National Research Council of Canada, Ottawa, Ontario, Canada K1A OR6</json:string></affiliations></json:item><json:item><name>Jeffrey T. Banks</name><affiliations><json:string>Steacie Institute for Molecular Sciences, National Research Council of Canada, Ottawa, Ontario, Canada K1A OR6</json:string></affiliations></json:item><json:item><name>Keith U. Ingold</name><affiliations><json:string>Steacie Institute for Molecular Sciences, National Research Council of Canada, Ottawa, Ontario, Canada K1A OR6</json:string></affiliations></json:item></author><language><json:string>eng</json:string></language><abstract>The oxidation of 2-cyclopropylpropane by dimethyldioxirane (DMD) to 2-cyclopropyl-propan-2-ol is not a free-radical chain reaction. It is suggested the free-radical chain observed by Minisci et al.8 when alkane / DMD reactions were carried out in the presence of CCl3Br involves H-atom abstraction from the alkane by Cl3,COO· (in air) and by Me2C(O·)OCCl3, as well as by the Cl3C· radical.</abstract><qualityIndicators><score>2.373</score><pdfVersion>1.3</pdfVersion><pdfPageSize>612 x 792 pts (letter)</pdfPageSize><refBibsNative>true</refBibsNative><keywordCount>0</keywordCount><abstractCharCount>389</abstractCharCount><pdfWordCount>1665</pdfWordCount><pdfCharCount>9732</pdfCharCount><pdfPageCount>4</pdfPageCount><abstractWordCount>59</abstractWordCount></qualityIndicators><title>Mechanism of hydroxylation of alkanes by dimethyldioxirane. A radical-clock study</title><pii><json:string>0040-4039(95)01666-6</json:string></pii><genre><json:string>research-article</json:string></genre><host><volume>36</volume><pii><json:string>S0040-4039(00)X2309-X</json:string></pii><pages><last>8002</last><first>7999</first></pages><issn><json:string>0040-4039</json:string></issn><issue>44</issue><genre></genre><language><json:string>unknown</json:string></language><title>Tetrahedron Letters</title><publicationDate>1995</publicationDate></host><categories><wos><json:string>CHEMISTRY, ORGANIC</json:string></wos></categories><publicationDate>1995</publicationDate><copyrightDate>1995</copyrightDate><doi><json:string>10.1016/0040-4039(95)01666-6</json:string></doi><id>3CA19B4ECA6ACDD9A03341C62BFAC00EC7ADE92D</id><fulltext><json:item><original>true</original><mimetype>application/pdf</mimetype><extension>pdf</extension><uri>https://api.istex.fr/document/3CA19B4ECA6ACDD9A03341C62BFAC00EC7ADE92D/fulltext/pdf</uri></json:item><json:item><original>false</original><mimetype>application/zip</mimetype><extension>zip</extension><uri>https://api.istex.fr/document/3CA19B4ECA6ACDD9A03341C62BFAC00EC7ADE92D/fulltext/zip</uri></json:item><istex:fulltextTEI uri="https://api.istex.fr/document/3CA19B4ECA6ACDD9A03341C62BFAC00EC7ADE92D/fulltext/tei"><teiHeader><fileDesc><titleStmt><title level="a" type="main" xml:lang="en">Mechanism of hydroxylation of alkanes by dimethyldioxirane. A radical-clock study</title></titleStmt><publicationStmt><authority>ISTEX</authority><publisher>ELSEVIER</publisher><availability><p>ELSEVIER</p></availability><date>1995</date></publicationStmt><sourceDesc><biblStruct type="inbook"><analytic><title level="a" type="main" xml:lang="en">Mechanism of hydroxylation of alkanes by dimethyldioxirane. A radical-clock study</title><author><persName><forename type="first">Raffaella</forename><surname>Vanni</surname></persName><affiliation>Steacie Institute for Molecular Sciences, National Research Council of Canada, Ottawa, Ontario, Canada K1A OR6</affiliation></author><author><persName><forename type="first">Simon J.</forename><surname>Garden</surname></persName><affiliation>Steacie Institute for Molecular Sciences, National Research Council of Canada, Ottawa, Ontario, Canada K1A OR6</affiliation></author><author><persName><forename type="first">Jeffrey T.</forename><surname>Banks</surname></persName><affiliation>Steacie Institute for Molecular Sciences, National Research Council of Canada, Ottawa, Ontario, Canada K1A OR6</affiliation></author><author><persName><forename type="first">Keith U.</forename><surname>Ingold</surname></persName><affiliation>Steacie Institute for Molecular Sciences, National Research Council of Canada, Ottawa, Ontario, Canada K1A OR6</affiliation></author></analytic><monogr><title level="j">Tetrahedron Letters</title><title level="j" type="abbrev">TETL</title><idno type="pISSN">0040-4039</idno><idno type="PII">S0040-4039(00)X2309-X</idno><imprint><publisher>ELSEVIER</publisher><date type="published" when="1995"></date><biblScope unit="volume">36</biblScope><biblScope unit="issue">44</biblScope><biblScope unit="page" from="7999">7999</biblScope><biblScope unit="page" to="8002">8002</biblScope></imprint></monogr><idno type="istex">3CA19B4ECA6ACDD9A03341C62BFAC00EC7ADE92D</idno><idno type="DOI">10.1016/0040-4039(95)01666-6</idno><idno type="PII">0040-4039(95)01666-6</idno><idno type="ArticleID">95016666</idno></biblStruct></sourceDesc></fileDesc><profileDesc><creation><date>1995</date></creation><langUsage><language ident="en">en</language></langUsage><abstract xml:lang="en"><p>The oxidation of 2-cyclopropylpropane by dimethyldioxirane (DMD) to 2-cyclopropyl-propan-2-ol is not a free-radical chain reaction. It is suggested the free-radical chain observed by Minisci et al.8 when alkane / DMD reactions were carried out in the presence of CCl3Br involves H-atom abstraction from the alkane by Cl3,COO· (in air) and by Me2C(O·)OCCl3, as well as by the Cl3C· radical.</p></abstract></profileDesc><revisionDesc><change when="1995-09-09">Registration</change><change when="1995-09-01">Modified</change><change when="1995">Published</change></revisionDesc></teiHeader></istex:fulltextTEI><json:item><original>false</original><mimetype>text/plain</mimetype><extension>txt</extension><uri>https://api.istex.fr/document/3CA19B4ECA6ACDD9A03341C62BFAC00EC7ADE92D/fulltext/txt</uri></json:item></fulltext><metadata><istex:metadataXml wicri:clean="Elsevier doc found" wicri:toSee="Elsevier, no converted or simple article"><istex:xmlDeclaration>version="1.0" encoding="utf-8"</istex:xmlDeclaration><istex:docType PUBLIC="-//ES//DTD journal article DTD version 5.0.1//EN//XML" URI="art501.dtd" name="istex:docType"></istex:docType><istex:document><article version="5.0" xml:lang="en" docsubtype="fla"><item-info><jid>TETL</jid><aid>95016666</aid><ce:pii>0040-4039(95)01666-6</ce:pii><ce:doi>10.1016/0040-4039(95)01666-6</ce:doi><ce:copyright type="unknown" year="1995"></ce:copyright></item-info><head><ce:title>Mechanism of hydroxylation of alkanes by dimethyldioxirane. A radical-clock study</ce:title><ce:author-group><ce:author><ce:given-name>Raffaella</ce:given-name><ce:surname>Vanni</ce:surname><ce:ranking>*</ce:ranking></ce:author><ce:author><ce:given-name>Simon J.</ce:given-name><ce:surname>Garden</ce:surname></ce:author><ce:author><ce:given-name>Jeffrey T.</ce:given-name><ce:surname>Banks</ce:surname></ce:author><ce:author><ce:given-name>Keith U.</ce:given-name><ce:surname>Ingold</ce:surname><ce:ranking>*</ce:ranking></ce:author><ce:affiliation id="aff1"><ce:textfn>Steacie Institute for Molecular Sciences, National Research Council of Canada, Ottawa, Ontario, Canada K1A OR6</ce:textfn></ce:affiliation></ce:author-group><ce:date-received day="24" month="7" year="1995"></ce:date-received><ce:date-revised day="1" month="9" year="1995"></ce:date-revised><ce:date-accepted day="9" month="9" year="1995"></ce:date-accepted><ce:abstract id="ab1" class="author" xml:lang="en"><ce:section-title>Abstract</ce:section-title><ce:abstract-sec><ce:simple-para>The oxidation of 2-cyclopropylpropane by dimethyldioxirane (DMD) to 2-cyclopropyl-propan-2-ol is not a <ce:italic>free</ce:italic>-radical chain reaction. It is suggested the <ce:italic>free</ce:italic>-radical chain observed by Minisci et al.<ce:sup loc="post">8</ce:sup> when alkane / DMD reactions were carried out in the presence of CCl<ce:inf loc="post">3</ce:inf>Br involves H-atom abstraction from the alkane by Cl<ce:inf loc="post">3</ce:inf>,COO· (in air) and by Me<ce:inf loc="post">2</ce:inf>C(O·)OCCl<ce:inf loc="post">3</ce:inf>, as well as by the Cl<ce:inf loc="post">3</ce:inf>C· radical.</ce:simple-para></ce:abstract-sec></ce:abstract></head><tail><ce:bibliography><ce:section-title>References and notes</ce:section-title><ce:bibliography-sec><ce:bib-reference id="bib1"><ce:label>1</ce:label><ce:note><ce:simple-para>Issued as NRCC N∘.39062</ce:simple-para></ce:note></ce:bib-reference><ce:bib-reference id="bib2"><ce:label>2.</ce:label><ce:other-ref><ce:textref>Visiting Scientist, permanent address: BeC, s.r.l., Via C. 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Chem.</sb:maintitle></sb:title><sb:volume-nr>164</sb:volume-nr></sb:series><sb:date>1993</sb:date></sb:issue><sb:pages><sb:first-page>45</sb:first-page><sb:last-page>62</sb:last-page></sb:pages></sb:host></sb:reference></ce:bib-reference><ce:bib-reference id="bib5"><ce:label>5</ce:label><ce:note><ce:simple-para>For example, <ce:italic>cis</ce:italic>- and <ce:italic>trans</ce:italic>-decalins yield the respective 9-decalols, and <ce:italic>cis</ce:italic>- and <ce:italic>trans</ce:italic>-1,2-dimethylcyclohexanes yield the respective 1,2-dimethylcyclohexan-1-ols on oxidation with DMD<ce:sup loc="post">6</ce:sup> and with methyl(trifluoromethyl)dioxirane.<ce:sup loc="post">7</ce:sup></ce:simple-para></ce:note></ce:bib-reference><ce:bib-reference id="bib6"><ce:label>6.</ce:label><sb:reference><sb:contribution langtype="en"><sb:authors><sb:author><ce:surname>Murray</ce:surname><ce:given-name>R.W.</ce:given-name></sb:author><sb:author><ce:surname>Jeyaraman</ce:surname><ce:given-name>R.</ce:given-name></sb:author><sb:author><ce:surname>Mohan</ce:surname><ce:given-name>L.</ce:given-name></sb:author></sb:authors></sb:contribution><sb:host><sb:issue><sb:series><sb:title><sb:maintitle>J. 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Soc.</sb:maintitle></sb:title><sb:volume-nr>111</sb:volume-nr></sb:series><sb:date>1989</sb:date></sb:issue><sb:pages><sb:first-page>6749</sb:first-page><sb:last-page>6757</sb:last-page></sb:pages></sb:host></sb:reference></ce:bib-reference><ce:bib-reference id="bib8"><ce:label>8.</ce:label><sb:reference><sb:contribution langtype="en"><sb:authors><sb:author><ce:surname>Minisci</ce:surname><ce:given-name>F.</ce:given-name></sb:author><sb:author><ce:surname>Zhao</ce:surname><ce:given-name>L.</ce:given-name></sb:author><sb:author><ce:surname>Fontana</ce:surname><ce:given-name>F.</ce:given-name></sb:author><sb:author><ce:surname>Bravo</ce:surname><ce:given-name>A.</ce:given-name></sb:author></sb:authors></sb:contribution><sb:host><sb:issue><sb:series><sb:title><sb:maintitle>Tetrahedron Lett.</sb:maintitle></sb:title><sb:volume-nr>36</sb:volume-nr></sb:series><sb:date>1995</sb:date></sb:issue><sb:pages><sb:first-page>1697</sb:first-page><sb:last-page>1700</sb:last-page></sb:pages></sb:host></sb:reference></ce:bib-reference><ce:bib-reference id="bib9"><ce:label>9.</ce:label><sb:reference><sb:contribution langtype="en"><sb:authors><sb:author><ce:surname>Griller</ce:surname><ce:given-name>D.</ce:given-name></sb:author><sb:author><ce:surname>Ingold</ce:surname><ce:given-name>K.U.</ce:given-name></sb:author></sb:authors></sb:contribution><sb:host><sb:issue><sb:series><sb:title><sb:maintitle>Acc. Chem. Res.</sb:maintitle></sb:title><sb:volume-nr>13</sb:volume-nr></sb:series><sb:date>1980</sb:date></sb:issue><sb:pages><sb:first-page>317</sb:first-page><sb:last-page>323</sb:last-page></sb:pages></sb:host></sb:reference></ce:bib-reference><ce:bib-reference id="bib10"><ce:label>10</ce:label><ce:note><ce:simple-para>Cyclopropylcarbinyl radical clocks appear to have been employed in only two earlier studies.<ce:sup loc="post">11,12</ce:sup> Rearrangement products were not observed in either study but neither of the clocks had been calibrated (i.e., the rate constants for rearrangement were unknown) and therefore it is doubtful if mechanistic conclusions were warranted.</ce:simple-para></ce:note></ce:bib-reference><ce:bib-reference id="bib11"><ce:label>11.</ce:label><sb:reference><sb:contribution langtype="en"><sb:authors><sb:author><ce:surname>Teager</ce:surname><ce:given-name>D.S.</ce:given-name></sb:author><sb:author><ce:surname>Murray</ce:surname><ce:given-name>R.K.</ce:given-name><ce:suffix>Jr.</ce:suffix></sb:author></sb:authors></sb:contribution><sb:host><sb:issue><sb:series><sb:title><sb:maintitle>J. 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Chem.</sb:maintitle></sb:title><sb:volume-nr>58</sb:volume-nr></sb:series><sb:date>1993</sb:date></sb:issue><sb:pages><sb:first-page>5548</sb:first-page><sb:last-page>5550</sb:last-page></sb:pages></sb:host></sb:reference></ce:bib-reference><ce:bib-reference id="bib12"><ce:label>12.</ce:label><sb:reference><sb:contribution langtype="en"><sb:authors><sb:author><ce:surname>Adam</ce:surname><ce:given-name>W.</ce:given-name></sb:author><sb:author><ce:surname>Prechtl</ce:surname><ce:given-name>F.</ce:given-name></sb:author><sb:author><ce:surname>Richter</ce:surname><ce:given-name>M.J.</ce:given-name></sb:author><sb:author><ce:surname>Smerz</ce:surname><ce:given-name>A.K.</ce:given-name></sb:author></sb:authors></sb:contribution><sb:host><sb:issue><sb:series><sb:title><sb:maintitle>Tetrahedron Lett.</sb:maintitle></sb:title><sb:volume-nr>34</sb:volume-nr></sb:series><sb:date>1993</sb:date></sb:issue><sb:pages><sb:first-page>8427</sb:first-page><sb:last-page>8430</sb:last-page></sb:pages></sb:host></sb:reference></ce:bib-reference><ce:bib-reference id="bib13"><ce:label>13</ce:label><ce:note><ce:simple-para>We also attempted to probe for the presence of caged radicals using substrates which (by analogy with those developed by Professor Newcomb)<ce:sup loc="post">14</ce:sup> would yield ultrafast radical clocks (<ce:italic>κ</ce:italic> > 10<ce:sup loc="post">12</ce:sup> s<ce:sup loc="post">−1</ce:sup>), viz., two 9-fluorenylcyclopropanes substituted in the cyclopropane ring either with four methyl groups or with one isopropyl group. Unfortunately, neither of these hydrocarbons reacted with DMD.</ce:simple-para></ce:note></ce:bib-reference><ce:bib-reference id="bib14"><ce:label>14.</ce:label><sb:reference><sb:contribution langtype="en"><sb:authors><sb:author><ce:surname>Martin-Esker</ce:surname><ce:given-name>A.A.</ce:given-name></sb:author><sb:author><ce:surname>Johnson</ce:surname><ce:given-name>C.C.</ce:given-name></sb:author><sb:author><ce:surname>Horner</ce:surname><ce:given-name>J.H.</ce:given-name></sb:author><sb:author><ce:surname>Newcomb</ce:surname><ce:given-name>M.</ce:given-name></sb:author></sb:authors></sb:contribution><sb:host><sb:issue><sb:series><sb:title><sb:maintitle>J. Am. Chem. Soc.</sb:maintitle></sb:title><sb:volume-nr>116</sb:volume-nr></sb:series><sb:date>1994</sb:date></sb:issue><sb:pages><sb:first-page>9174</sb:first-page><sb:last-page>9181</sb:last-page></sb:pages></sb:host></sb:reference></ce:bib-reference><ce:bib-reference id="bib15"><ce:label>15.</ce:label><sb:reference><sb:contribution langtype="en"><sb:authors><sb:author><ce:surname>Bowry</ce:surname><ce:given-name>V.W.</ce:given-name></sb:author><sb:author><ce:surname>Lusztyk</ce:surname><ce:given-name>J.</ce:given-name></sb:author><sb:author><ce:surname>Ingold</ce:surname><ce:given-name>K.U.</ce:given-name></sb:author></sb:authors></sb:contribution><sb:host><sb:issue><sb:series><sb:title><sb:maintitle>J. Am. Chem. Soc.</sb:maintitle></sb:title><sb:volume-nr>113</sb:volume-nr></sb:series><sb:date>1991</sb:date></sb:issue><sb:pages><sb:first-page>5687</sb:first-page><sb:last-page>5698</sb:last-page></sb:pages></sb:host></sb:reference></ce:bib-reference><ce:bib-reference id="bib16"><ce:label>16</ce:label><ce:note><ce:simple-para>Not only will the new radical center yield CH<ce:inf loc="post">2</ce:inf>OH, then CHO, then CO<ce:inf loc="post">2</ce:inf>H but also the double bond will be subject to facile epoxidation.</ce:simple-para></ce:note></ce:bib-reference><ce:bib-reference id="bib17"><ce:label>17</ce:label><ce:note><ce:simple-para>The fraction, <ce:italic>f</ce:italic>, of cage-escaped 2-cyclopropylprop-2-yl radicals which could yield the tertiary alcohol via reaction 4 (and 7) rather than giving ring-opened products via reaction 5 is given by <ce:italic>f</ce:italic>= <ce:italic>k</ce:italic><ce:inf loc="post">4</ce:inf> [DMD]<ce:inf loc="post">mean</ce:inf>/<ce:italic>k</ce:italic><ce:inf loc="post">5</ce:inf> Even with the unlikely assumption that reaction 4 is diffusion-controlled, i. e., <ce:italic>k</ce:italic><ce:inf loc="post">4<ce:sup loc="post">~</ce:sup></ce:inf> 10<ce:sup loc="post">9</ce:sup> M<ce:sup loc="post">−1</ce:sup> s<ce:sup loc="post">−1</ce:sup>,<ce:italic>f</ce:italic>values are small under our conditions, e. g. ~ 0.24 for Expt. 2 and ~ 0.028 for Expt. 3. If <ce:italic>k</ce:italic><ce:inf loc="post">4</ce:inf>is < 10<ce:sup loc="post">9</ce:sup> M<ce:sup loc="post">−1</ce:sup> s<ce:sup loc="post">−1</ce:sup> virtually no radicals would survive long enough to make any of the tertiary alcohol.</ce:simple-para></ce:note></ce:bib-reference><ce:bib-reference id="bib18"><ce:label>18</ce:label><ce:note><ce:simple-para>In this connection we note that Curci et al.<ce:sup loc="post">7</ce:sup> found no chlorinated products when methyl(trifluoromethyl)dioxirane reacted with a variety of hydrocarbons in CH<ce:inf loc="post">2</ce:inf>Cl<ce:inf loc="post">2</ce:inf> / CF<ce:inf loc="post">3</ce:inf>COCH<ce:inf loc="post">3</ce:inf> (ca. 9:1 v/v) at −21 to 5°C but, of course, CH<ce:inf loc="post">2</ce:inf>Cl<ce:inf loc="post">2</ce:inf> is a much poorer halogen atom donor than CCl<ce:inf loc="post">3</ce:inf>Br. However, it should also be noted that Minisci et al.<ce:sup loc="post">19</ce:sup> have demonstrated that at least some R·<ce:italic>free</ce:italic>-radicals are formed in the DMD oxidation of RH = cyclohexane and adamantane by trapping the R· with protonated heteroaromatic bases.</ce:simple-para></ce:note></ce:bib-reference><ce:bib-reference id="bib19"><ce:label>19.</ce:label><sb:reference><sb:contribution langtype="en"><sb:authors><sb:author><ce:surname>Minisci</ce:surname><ce:given-name>F.</ce:given-name></sb:author><sb:author><ce:surname>Zhao</ce:surname><ce:given-name>L.</ce:given-name></sb:author><sb:author><ce:surname>Fontana</ce:surname><ce:given-name>F.</ce:given-name></sb:author><sb:author><ce:surname>Bravo</ce:surname><ce:given-name>A.</ce:given-name></sb:author></sb:authors></sb:contribution><sb:host><sb:issue><sb:series><sb:title><sb:maintitle>Tetrahedron Lett.</sb:maintitle></sb:title><sb:volume-nr>36</sb:volume-nr></sb:series><sb:date>1995</sb:date></sb:issue><sb:pages><sb:first-page>1895</sb:first-page><sb:last-page>1898</sb:last-page></sb:pages></sb:host></sb:reference></ce:bib-reference><ce:bib-reference id="bib20"><ce:label>20.</ce:label><ce:other-ref><ce:textref>Bravo A., Fontana F., Fronza G., Mele A., Minisci F. <ce:italic>J. Chem. Soc, Chem. Comm.</ce:italic> in press.</ce:textref></ce:other-ref></ce:bib-reference><ce:bib-reference id="bib21"><ce:label>21.</ce:label><sb:reference><sb:contribution langtype="en"><sb:authors><sb:author><ce:surname>Minisci</ce:surname><ce:given-name>F.</ce:given-name></sb:author><sb:author><ce:surname>Fontana</ce:surname><ce:given-name>F.</ce:given-name></sb:author><sb:author><ce:surname>Pianese</ce:surname><ce:given-name>G.</ce:given-name></sb:author><sb:author><ce:surname>Yan</ce:surname><ce:given-name>Y.M.</ce:given-name></sb:author></sb:authors></sb:contribution><sb:host><sb:issue><sb:series><sb:title><sb:maintitle>J. Org. Chem.</sb:maintitle></sb:title><sb:volume-nr>58</sb:volume-nr></sb:series><sb:date>1993</sb:date></sb:issue><sb:pages><sb:first-page>4207</sb:first-page><sb:last-page>4211</sb:last-page></sb:pages></sb:host></sb:reference></ce:bib-reference></ce:bibliography-sec></ce:bibliography></tail></article></istex:document></istex:metadataXml><mods version="3.6"><titleInfo lang="en"><title>Mechanism of hydroxylation of alkanes by dimethyldioxirane. A radical-clock study</title></titleInfo><titleInfo type="alternative" lang="en" contentType="CDATA"><title>Mechanism of hydroxylation of alkanes by dimethyldioxirane. A radical-clock study</title></titleInfo><name type="personal"><namePart type="given">Raffaella</namePart><namePart type="family">Vanni</namePart><affiliation>Steacie Institute for Molecular Sciences, National Research Council of Canada, Ottawa, Ontario, Canada K1A OR6</affiliation><role><roleTerm type="text">author</roleTerm></role></name><name type="personal"><namePart type="given">Simon J.</namePart><namePart type="family">Garden</namePart><affiliation>Steacie Institute for Molecular Sciences, National Research Council of Canada, Ottawa, Ontario, Canada K1A OR6</affiliation><role><roleTerm type="text">author</roleTerm></role></name><name type="personal"><namePart type="given">Jeffrey T.</namePart><namePart type="family">Banks</namePart><affiliation>Steacie Institute for Molecular Sciences, National Research Council of Canada, Ottawa, Ontario, Canada K1A OR6</affiliation><role><roleTerm type="text">author</roleTerm></role></name><name type="personal"><namePart type="given">Keith U.</namePart><namePart type="family">Ingold</namePart><affiliation>Steacie Institute for Molecular Sciences, National Research Council of Canada, Ottawa, Ontario, Canada K1A OR6</affiliation><role><roleTerm type="text">author</roleTerm></role></name><typeOfResource>text</typeOfResource><genre type="research-article" displayLabel="Full-length article"></genre><originInfo><publisher>ELSEVIER</publisher><dateIssued encoding="w3cdtf">1995</dateIssued><dateValid encoding="w3cdtf">1995-09-09</dateValid><dateModified encoding="w3cdtf">1995-09-01</dateModified><copyrightDate encoding="w3cdtf">1995</copyrightDate></originInfo><language><languageTerm type="code" authority="iso639-2b">eng</languageTerm><languageTerm type="code" authority="rfc3066">en</languageTerm></language><physicalDescription><internetMediaType>text/html</internetMediaType></physicalDescription><abstract lang="en">The oxidation of 2-cyclopropylpropane by dimethyldioxirane (DMD) to 2-cyclopropyl-propan-2-ol is not a free-radical chain reaction. It is suggested the free-radical chain observed by Minisci et al.8 when alkane / DMD reactions were carried out in the presence of CCl3Br involves H-atom abstraction from the alkane by Cl3,COO· (in air) and by Me2C(O·)OCCl3, as well as by the Cl3C· radical.</abstract><relatedItem type="host"><titleInfo><title>Tetrahedron Letters</title></titleInfo><titleInfo type="abbreviated"><title>TETL</title></titleInfo><genre type="Journal">journal</genre><originInfo><dateIssued encoding="w3cdtf">19951030</dateIssued></originInfo><identifier type="ISSN">0040-4039</identifier><identifier type="PII">S0040-4039(00)X2309-X</identifier><part><date>19951030</date><detail type="volume"><number>36</number><caption>vol.</caption></detail><detail type="issue"><number>44</number><caption>no.</caption></detail><extent unit="issue pages"><start>7945</start><end>8144</end></extent><extent unit="pages"><start>7999</start><end>8002</end></extent></part></relatedItem><identifier type="istex">3CA19B4ECA6ACDD9A03341C62BFAC00EC7ADE92D</identifier><identifier type="DOI">10.1016/0040-4039(95)01666-6</identifier><identifier type="PII">0040-4039(95)01666-6</identifier><identifier type="ArticleID">95016666</identifier><recordInfo><recordContentSource>ELSEVIER</recordContentSource></recordInfo></mods></metadata><enrichments><istex:catWosTEI uri="https://api.istex.fr/document/3CA19B4ECA6ACDD9A03341C62BFAC00EC7ADE92D/enrichments/catWos"><teiHeader><profileDesc><textClass><classCode scheme="WOS">CHEMISTRY, ORGANIC</classCode></textClass></profileDesc></teiHeader></istex:catWosTEI></enrichments><serie></serie></istex></record>Pour manipuler ce document sous Unix (Dilib)
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