Scavenging of Intermediates Formed in Photolysis of α-Diazocarbonyl Compounds and Hydroxycyclopropenones. Implication on the Mechanism of the Photo-Wolff Reaction

Scavenging of Intermediates Formed in Photolysis of α-Diazocarbonyl Compounds and Hydroxycyclopropenones. Implication on the Mechanism of the Photo-Wolff Reaction

The question of whether α-carbonylcarbene intermediates are formed as ketene precursors in the photo-Wolff reaction of α-diazocarbonyl compounds was addressed by comparing pyridine scavenging of transients generated by laser flash photolysis of benzoyldiazomethane and 1-naphthoyldiazomethane with py...

Ausführliche Beschreibung

Gespeichert in:
Bibliographische Detailangaben
Veröffentlicht in:Journal of the American Chemical Society 1999-06, Vol.121 (25), p.5930-5932
Hauptverfasser: Chiang, Y, Kresge, A. J, Popik, V. V
Format: Artikel
Sprache:eng
Online-Zugang:Volltext
Tags: Tag hinzufügen
Keine Tags, Fügen Sie den ersten Tag hinzu!
container_end_page 5932
container_issue 25
container_start_page 5930
container_title Journal of the American Chemical Society
container_volume 121
creator Chiang, Y
Kresge, A. J
Popik, V. V
description The question of whether α-carbonylcarbene intermediates are formed as ketene precursors in the photo-Wolff reaction of α-diazocarbonyl compounds was addressed by comparing pyridine scavenging of transients generated by laser flash photolysis of benzoyldiazomethane and 1-naphthoyldiazomethane with pyridine scavenging of transients formed by flash photolysis of the corresponding arylhydroxycyclopropenones. The rate laws for the scavenging process in the two different photoreactions in aqueous solution were found to be exactly the same, and since ketene intermediates are common to both reactions but α-carbonylcarbenes are not, the transients were thus identified as ketenes. Formation of these ketene intermediates in the photo-Wolff reaction took place within the duration of the laser pulse (ca. 20 ns), and α-carbonylcarbene intermediates, if formed at all, must have lifetimes shorter than this.
doi_str_mv 10.1021/ja9906406
format Article
fullrecord <record><control><sourceid>acs_cross</sourceid><recordid>TN_cdi_crossref_primary_10_1021_ja9906406</recordid><sourceformat>XML</sourceformat><sourcesystem>PC</sourcesystem><sourcerecordid>b868420508</sourcerecordid><originalsourceid>FETCH-LOGICAL-a295t-246781a1a40c0ae1b4dc8f2ca6e49e796ce7457a87e8f330a354fda095f8ec0d3</originalsourceid><addsrcrecordid>eNptkM1O3DAUhS0EEgN00TfwhgWLTG3H-VvCAGUqEAiourQuzjXjIbEjO1Skr9Mn6IvwTE0YxArpSvdHn87RPYR85WzOmeDf1lBVLJcs3yIzngmWZFzk22TGGBNJUebpLtmLcT2uUpR8Rv7eafiN7tG6R-oNXboeQ4u1hR4jPffTTK2jNyvf-2aINk7U67_k1MIfryE8eDc0dOHbzj-7OlJwNb0Y6uBfBj3oxnfBd-i8wziny7ZrrIbeekfH6ldIr1CvwNnYTrLT4c0o-eUbY-gtgp7gA7JjoIn45b3vk5_nZ_eLi-Ty-vtycXyZgKiyPhEyL0oOHCTTDJA_yFqXRmjIUVZYVLnGQmYFlAWWJk0ZpJk0NbAqMyVqVqf75Gijq4OPMaBRXbAthEFxpqZ01Ue6I5tsWBt7fPkAITypvEiLTN3f3Cnx40SWLJPqZOQPNzzoqNb-Objxk090_wOZOow4</addsrcrecordid><sourcetype>Aggregation Database</sourcetype><iscdi>true</iscdi><recordtype>article</recordtype></control><display><type>article</type><title>Scavenging of Intermediates Formed in Photolysis of α-Diazocarbonyl Compounds and Hydroxycyclopropenones. Implication on the Mechanism of the Photo-Wolff Reaction</title><source>ACS Publications</source><creator>Chiang, Y ; Kresge, A. J ; Popik, V. V</creator><creatorcontrib>Chiang, Y ; Kresge, A. J ; Popik, V. V</creatorcontrib><description>The question of whether α-carbonylcarbene intermediates are formed as ketene precursors in the photo-Wolff reaction of α-diazocarbonyl compounds was addressed by comparing pyridine scavenging of transients generated by laser flash photolysis of benzoyldiazomethane and 1-naphthoyldiazomethane with pyridine scavenging of transients formed by flash photolysis of the corresponding arylhydroxycyclopropenones. The rate laws for the scavenging process in the two different photoreactions in aqueous solution were found to be exactly the same, and since ketene intermediates are common to both reactions but α-carbonylcarbenes are not, the transients were thus identified as ketenes. Formation of these ketene intermediates in the photo-Wolff reaction took place within the duration of the laser pulse (ca. 20 ns), and α-carbonylcarbene intermediates, if formed at all, must have lifetimes shorter than this.</description><identifier>ISSN: 0002-7863</identifier><identifier>EISSN: 1520-5126</identifier><identifier>DOI: 10.1021/ja9906406</identifier><language>eng</language><publisher>American Chemical Society</publisher><ispartof>Journal of the American Chemical Society, 1999-06, Vol.121 (25), p.5930-5932</ispartof><rights>Copyright © 1999 American Chemical Society</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-a295t-246781a1a40c0ae1b4dc8f2ca6e49e796ce7457a87e8f330a354fda095f8ec0d3</citedby><cites>FETCH-LOGICAL-a295t-246781a1a40c0ae1b4dc8f2ca6e49e796ce7457a87e8f330a354fda095f8ec0d3</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/ja9906406$$EPDF$$P50$$Gacs$$H</linktopdf><linktohtml>$$Uhttps://pubs.acs.org/doi/10.1021/ja9906406$$EHTML$$P50$$Gacs$$H</linktohtml><link.rule.ids>314,780,784,2765,27076,27924,27925,56738,56788</link.rule.ids></links><search><creatorcontrib>Chiang, Y</creatorcontrib><creatorcontrib>Kresge, A. J</creatorcontrib><creatorcontrib>Popik, V. V</creatorcontrib><title>Scavenging of Intermediates Formed in Photolysis of α-Diazocarbonyl Compounds and Hydroxycyclopropenones. Implication on the Mechanism of the Photo-Wolff Reaction</title><title>Journal of the American Chemical Society</title><addtitle>J. Am. Chem. Soc</addtitle><description>The question of whether α-carbonylcarbene intermediates are formed as ketene precursors in the photo-Wolff reaction of α-diazocarbonyl compounds was addressed by comparing pyridine scavenging of transients generated by laser flash photolysis of benzoyldiazomethane and 1-naphthoyldiazomethane with pyridine scavenging of transients formed by flash photolysis of the corresponding arylhydroxycyclopropenones. The rate laws for the scavenging process in the two different photoreactions in aqueous solution were found to be exactly the same, and since ketene intermediates are common to both reactions but α-carbonylcarbenes are not, the transients were thus identified as ketenes. Formation of these ketene intermediates in the photo-Wolff reaction took place within the duration of the laser pulse (ca. 20 ns), and α-carbonylcarbene intermediates, if formed at all, must have lifetimes shorter than this.</description><issn>0002-7863</issn><issn>1520-5126</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>1999</creationdate><recordtype>article</recordtype><recordid>eNptkM1O3DAUhS0EEgN00TfwhgWLTG3H-VvCAGUqEAiourQuzjXjIbEjO1Skr9Mn6IvwTE0YxArpSvdHn87RPYR85WzOmeDf1lBVLJcs3yIzngmWZFzk22TGGBNJUebpLtmLcT2uUpR8Rv7eafiN7tG6R-oNXboeQ4u1hR4jPffTTK2jNyvf-2aINk7U67_k1MIfryE8eDc0dOHbzj-7OlJwNb0Y6uBfBj3oxnfBd-i8wziny7ZrrIbeekfH6ldIr1CvwNnYTrLT4c0o-eUbY-gtgp7gA7JjoIn45b3vk5_nZ_eLi-Ty-vtycXyZgKiyPhEyL0oOHCTTDJA_yFqXRmjIUVZYVLnGQmYFlAWWJk0ZpJk0NbAqMyVqVqf75Gijq4OPMaBRXbAthEFxpqZ01Ue6I5tsWBt7fPkAITypvEiLTN3f3Cnx40SWLJPqZOQPNzzoqNb-Objxk090_wOZOow4</recordid><startdate>19990630</startdate><enddate>19990630</enddate><creator>Chiang, Y</creator><creator>Kresge, A. J</creator><creator>Popik, V. V</creator><general>American Chemical Society</general><scope>BSCLL</scope><scope>AAYXX</scope><scope>CITATION</scope></search><sort><creationdate>19990630</creationdate><title>Scavenging of Intermediates Formed in Photolysis of α-Diazocarbonyl Compounds and Hydroxycyclopropenones. Implication on the Mechanism of the Photo-Wolff Reaction</title><author>Chiang, Y ; Kresge, A. J ; Popik, V. V</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-a295t-246781a1a40c0ae1b4dc8f2ca6e49e796ce7457a87e8f330a354fda095f8ec0d3</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>1999</creationdate><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Chiang, Y</creatorcontrib><creatorcontrib>Kresge, A. J</creatorcontrib><creatorcontrib>Popik, V. V</creatorcontrib><collection>Istex</collection><collection>CrossRef</collection><jtitle>Journal of the American Chemical Society</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Chiang, Y</au><au>Kresge, A. J</au><au>Popik, V. V</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Scavenging of Intermediates Formed in Photolysis of α-Diazocarbonyl Compounds and Hydroxycyclopropenones. Implication on the Mechanism of the Photo-Wolff Reaction</atitle><jtitle>Journal of the American Chemical Society</jtitle><addtitle>J. Am. Chem. Soc</addtitle><date>1999-06-30</date><risdate>1999</risdate><volume>121</volume><issue>25</issue><spage>5930</spage><epage>5932</epage><pages>5930-5932</pages><issn>0002-7863</issn><eissn>1520-5126</eissn><abstract>The question of whether α-carbonylcarbene intermediates are formed as ketene precursors in the photo-Wolff reaction of α-diazocarbonyl compounds was addressed by comparing pyridine scavenging of transients generated by laser flash photolysis of benzoyldiazomethane and 1-naphthoyldiazomethane with pyridine scavenging of transients formed by flash photolysis of the corresponding arylhydroxycyclopropenones. The rate laws for the scavenging process in the two different photoreactions in aqueous solution were found to be exactly the same, and since ketene intermediates are common to both reactions but α-carbonylcarbenes are not, the transients were thus identified as ketenes. Formation of these ketene intermediates in the photo-Wolff reaction took place within the duration of the laser pulse (ca. 20 ns), and α-carbonylcarbene intermediates, if formed at all, must have lifetimes shorter than this.</abstract><pub>American Chemical Society</pub><doi>10.1021/ja9906406</doi><tpages>3</tpages></addata></record>
fulltext fulltext
identifier ISSN: 0002-7863
ispartof Journal of the American Chemical Society, 1999-06, Vol.121 (25), p.5930-5932
issn 0002-7863
1520-5126
language eng
recordid cdi_crossref_primary_10_1021_ja9906406
source ACS Publications
title Scavenging of Intermediates Formed in Photolysis of α-Diazocarbonyl Compounds and Hydroxycyclopropenones. Implication on the Mechanism of the Photo-Wolff Reaction
url https://sfx.bib-bvb.de/sfx_tum?ctx_ver=Z39.88-2004&ctx_enc=info:ofi/enc:UTF-8&ctx_tim=2025-01-04T20%3A53%3A08IST&url_ver=Z39.88-2004&url_ctx_fmt=infofi/fmt:kev:mtx:ctx&rfr_id=info:sid/primo.exlibrisgroup.com:primo3-Article-acs_cross&rft_val_fmt=info:ofi/fmt:kev:mtx:journal&rft.genre=article&rft.atitle=Scavenging%20of%20Intermediates%20Formed%20in%20Photolysis%20of%20%CE%B1-Diazocarbonyl%20Compounds%20and%20Hydroxycyclopropenones.%20Implication%20on%20the%20Mechanism%20of%20the%20Photo-Wolff%20Reaction&rft.jtitle=Journal%20of%20the%20American%20Chemical%20Society&rft.au=Chiang,%20Y&rft.date=1999-06-30&rft.volume=121&rft.issue=25&rft.spage=5930&rft.epage=5932&rft.pages=5930-5932&rft.issn=0002-7863&rft.eissn=1520-5126&rft_id=info:doi/10.1021/ja9906406&rft_dat=%3Cacs_cross%3Eb868420508%3C/acs_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