Electrophilic aromatic substitution in substituted anilines; kinetics of the reaction with 4,6-dinitrobenzofuroxan
Kinetic results are reported for reaction of aniline and six of its N- and ring-substituted derivatives with 4,6-dinitrobenzofuroxan (DNBF) in water - dimethyl sulfoxide mixtures. In acidic solution -adducts, the result of electrophilic substitution in the anilines, are formed with bonding between a...
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| Veröffentlicht in: | Canadian journal of chemistry 1999-06, Vol.77 (5-6), p.639-646 |
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| container_title | Canadian journal of chemistry |
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| creator | Crampton, Michael R Rabbitt, Lynsey C Terrier, François |
| description | Kinetic results are reported for reaction of aniline and six of its N- and ring-substituted derivatives with 4,6-dinitrobenzofuroxan (DNBF) in water - dimethyl sulfoxide mixtures. In acidic solution -adducts, the result of electrophilic substitution in the anilines, are formed with bonding between a ring-carbon atom of the anilines and the 7-position of DNBF. Reaction normally occurs at the 4-position of the aniline unless this carries a substituent, when reaction occurs at the 2-position. A value of 2.0 for k
H
/k
D
, the kinetic isotope effect, indicates that in the reaction with aniline bond formation is largely rate determining in the substitution pathway. The results allow estimates to be made for the pK
a
values relating to carbon protonation of the anilines.Key words: electrophilic substitution, -adducts, 4,6-dinitrobenzofuroxan, ambident reactivity of anilines. |
| doi_str_mv | 10.1139/v99-033 |
| format | Article |
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H
/k
D
, the kinetic isotope effect, indicates that in the reaction with aniline bond formation is largely rate determining in the substitution pathway. The results allow estimates to be made for the pK
a
values relating to carbon protonation of the anilines.Key words: electrophilic substitution, -adducts, 4,6-dinitrobenzofuroxan, ambident reactivity of anilines.</description><identifier>ISSN: 0008-4042</identifier><identifier>EISSN: 1480-3291</identifier><identifier>DOI: 10.1139/v99-033</identifier><identifier>CODEN: CJCHAG</identifier><language>eng</language><publisher>Ottawa, Canada: NRC Research Press</publisher><subject>Aniline ; Atoms & subatomic particles ; Carbon ; Chemical bonds ; Chemical structure ; Chemistry ; Substitution (Chemistry)</subject><ispartof>Canadian journal of chemistry, 1999-06, Vol.77 (5-6), p.639-646</ispartof><rights>Copyright National Research Council of Canada May/Jun 1999</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c231t-e4a25c84fbd821dbac64d2d5443bb509233bce7dd115cef13dd6f4f99f90f4a23</citedby><cites>FETCH-LOGICAL-c231t-e4a25c84fbd821dbac64d2d5443bb509233bce7dd115cef13dd6f4f99f90f4a23</cites></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><link.rule.ids>314,780,784,27924,27925</link.rule.ids></links><search><creatorcontrib>Crampton, Michael R</creatorcontrib><creatorcontrib>Rabbitt, Lynsey C</creatorcontrib><creatorcontrib>Terrier, François</creatorcontrib><title>Electrophilic aromatic substitution in substituted anilines; kinetics of the reaction with 4,6-dinitrobenzofuroxan</title><title>Canadian journal of chemistry</title><addtitle>Revue canadienne de chimie</addtitle><description>Kinetic results are reported for reaction of aniline and six of its N- and ring-substituted derivatives with 4,6-dinitrobenzofuroxan (DNBF) in water - dimethyl sulfoxide mixtures. In acidic solution -adducts, the result of electrophilic substitution in the anilines, are formed with bonding between a ring-carbon atom of the anilines and the 7-position of DNBF. Reaction normally occurs at the 4-position of the aniline unless this carries a substituent, when reaction occurs at the 2-position. A value of 2.0 for k
H
/k
D
, the kinetic isotope effect, indicates that in the reaction with aniline bond formation is largely rate determining in the substitution pathway. The results allow estimates to be made for the pK
a
values relating to carbon protonation of the anilines.Key words: electrophilic substitution, -adducts, 4,6-dinitrobenzofuroxan, ambident reactivity of anilines.</description><subject>Aniline</subject><subject>Atoms & subatomic particles</subject><subject>Carbon</subject><subject>Chemical bonds</subject><subject>Chemical structure</subject><subject>Chemistry</subject><subject>Substitution (Chemistry)</subject><issn>0008-4042</issn><issn>1480-3291</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>1999</creationdate><recordtype>article</recordtype><sourceid>8G5</sourceid><sourceid>ABUWG</sourceid><sourceid>AFKRA</sourceid><sourceid>AZQEC</sourceid><sourceid>BENPR</sourceid><sourceid>CCPQU</sourceid><sourceid>DWQXO</sourceid><sourceid>GNUQQ</sourceid><sourceid>GUQSH</sourceid><sourceid>M2O</sourceid><recordid>eNp90EtLAzEQB_AgCtYqfoXgQUFczWvXDZ6k1AcUvOg5ZPNgU9ukJllfn95oC570NDPwmxn4A3CI0TnGlF-8cl4hSrfACLMWVZRwvA1GCKG2YoiRXbCX0ryMl4jUIxCnC6NyDKveLZyCMoalzKVJQ5eyy0N2wUPnf2ejofTFepOu4HMpRScYLMy9gdFI9bPx5nIP2VlTaeddOd8Z_xnsEMO79Ptgx8pFMgebOgZPN9PHyV01e7i9n1zPKkUozpVhktSqZbbTLcG6k6phmuiaMdp1NeKE0k6ZS60xrpWxmGrdWGY5txzZskvH4Gh9dxXDy2BSFvMwRF9eCoLbpsGsQQWdrJGKIaVorFhFt5TxQ2AkvvMUJU9R8izydC19VNEkI6Pq_8HHf-MNEitt6RfbA4aw</recordid><startdate>19990601</startdate><enddate>19990601</enddate><creator>Crampton, Michael R</creator><creator>Rabbitt, Lynsey C</creator><creator>Terrier, François</creator><general>NRC Research Press</general><general>Canadian Science Publishing NRC Research Press</general><scope>AAYXX</scope><scope>CITATION</scope><scope>3V.</scope><scope>7XB</scope><scope>88I</scope><scope>8AF</scope><scope>8AO</scope><scope>8FE</scope><scope>8FG</scope><scope>8FK</scope><scope>8FQ</scope><scope>8FV</scope><scope>8G5</scope><scope>ABJCF</scope><scope>ABUWG</scope><scope>AEUYN</scope><scope>AFKRA</scope><scope>AZQEC</scope><scope>BENPR</scope><scope>BGLVJ</scope><scope>BHPHI</scope><scope>BKSAR</scope><scope>CCPQU</scope><scope>D1I</scope><scope>DWQXO</scope><scope>GNUQQ</scope><scope>GUQSH</scope><scope>HCIFZ</scope><scope>KB.</scope><scope>M2O</scope><scope>M2P</scope><scope>M3G</scope><scope>MBDVC</scope><scope>PADUT</scope><scope>PCBAR</scope><scope>PDBOC</scope><scope>PQEST</scope><scope>PQQKQ</scope><scope>PQUKI</scope><scope>Q9U</scope></search><sort><creationdate>19990601</creationdate><title>Electrophilic aromatic substitution in substituted anilines; 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kinetics of the reaction with 4,6-dinitrobenzofuroxan</atitle><jtitle>Canadian journal of chemistry</jtitle><addtitle>Revue canadienne de chimie</addtitle><date>1999-06-01</date><risdate>1999</risdate><volume>77</volume><issue>5-6</issue><spage>639</spage><epage>646</epage><pages>639-646</pages><issn>0008-4042</issn><eissn>1480-3291</eissn><coden>CJCHAG</coden><abstract>Kinetic results are reported for reaction of aniline and six of its N- and ring-substituted derivatives with 4,6-dinitrobenzofuroxan (DNBF) in water - dimethyl sulfoxide mixtures. In acidic solution -adducts, the result of electrophilic substitution in the anilines, are formed with bonding between a ring-carbon atom of the anilines and the 7-position of DNBF. Reaction normally occurs at the 4-position of the aniline unless this carries a substituent, when reaction occurs at the 2-position. A value of 2.0 for k
H
/k
D
, the kinetic isotope effect, indicates that in the reaction with aniline bond formation is largely rate determining in the substitution pathway. The results allow estimates to be made for the pK
a
values relating to carbon protonation of the anilines.Key words: electrophilic substitution, -adducts, 4,6-dinitrobenzofuroxan, ambident reactivity of anilines.</abstract><cop>Ottawa, Canada</cop><pub>NRC Research Press</pub><doi>10.1139/v99-033</doi><tpages>8</tpages></addata></record> |
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| source | Free Full-Text Journals in Chemistry |
| subjects | Aniline Atoms & subatomic particles Carbon Chemical bonds Chemical structure Chemistry Substitution (Chemistry) |
| title | Electrophilic aromatic substitution in substituted anilines; kinetics of the reaction with 4,6-dinitrobenzofuroxan |
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