Reaction of Chlorosulfonyl Isocyanate (CSI) with Fluorosubstituted Alkenes: Evidence of a Concerted Pathway for Reaction of CSI with Fluorosubstituted Alkenes (Preprint)
Concerted reactions are indicated for the electrophilic addition of chlorosulfonyl isocyanate with monofluoroalkenes. A vinyl fluorine atom on an alkene raises the energy of a step-wise transition state more than the energy of the competing concerted pathway. This energy shift induces CSI to react w...
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| creator | Shellhamer, Dale Davenport, Kevyn J Hassler, Danielle M Hickle, Kelli R Thorpe, Jacob J Vandenbroek, David J Heasley, Victor L Boatz, Jerry A Reingold, Arnold L Moore, Chris E |
| description | Concerted reactions are indicated for the electrophilic addition of chlorosulfonyl isocyanate with monofluoroalkenes. A vinyl fluorine atom on an alkene raises the energy of a step-wise transition state more than the energy of the competing concerted pathway. This energy shift induces CSI to react with monofluoroalkenes by a one-step process. The low reactivity of CSI with monofluoroalkenes, stereospecific reactions, the absence of 2:1 uracil products with neat fluoroalkenes and quantum chemical calculations support a concerted pathway.
Performed in collaboration with Point Loma Nazarene University, San Diego, CA; and the University of California, La Jolla, CA. Submitted for publication in the Journal of Organic Chemistry. |
| format | Report |
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Performed in collaboration with Point Loma Nazarene University, San Diego, CA; and the University of California, La Jolla, CA. Submitted for publication in the Journal of Organic Chemistry.</description><language>eng</language><subject>ADDITION REACTIONS ; ALKENES ; ANTIBIOTICS ; BETA-LACTAMS ; Biochemistry ; CSI(CHLOROSULFONYL ISOCYANATES) ; FLUORINE ; FLUOROALKENES ; ISOCYANATES ; Medicine and Medical Research ; Organic Chemistry ; Physical Chemistry ; REPRINTS ; SUBSTITUTION REACTIONS ; SULFONYL HALIDES ; Test Facilities, Equipment and Methods ; WUAFRL50260541</subject><creationdate>2010</creationdate><rights>Approved for public release; distribution is unlimited.</rights><oa>free_for_read</oa><woscitedreferencessubscribed>false</woscitedreferencessubscribed></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><link.rule.ids>230,781,886,27571,27572</link.rule.ids><linktorsrc>$$Uhttps://apps.dtic.mil/sti/citations/ADA523002$$EView_record_in_DTIC$$FView_record_in_$$GDTIC$$Hfree_for_read</linktorsrc></links><search><creatorcontrib>Shellhamer, Dale</creatorcontrib><creatorcontrib>Davenport, Kevyn J</creatorcontrib><creatorcontrib>Hassler, Danielle M</creatorcontrib><creatorcontrib>Hickle, Kelli R</creatorcontrib><creatorcontrib>Thorpe, Jacob J</creatorcontrib><creatorcontrib>Vandenbroek, David J</creatorcontrib><creatorcontrib>Heasley, Victor L</creatorcontrib><creatorcontrib>Boatz, Jerry A</creatorcontrib><creatorcontrib>Reingold, Arnold L</creatorcontrib><creatorcontrib>Moore, Chris E</creatorcontrib><creatorcontrib>AIR FORCE RESEARCH LAB EDWARDS AFB CA PROPULSION DIRECTORATE</creatorcontrib><title>Reaction of Chlorosulfonyl Isocyanate (CSI) with Fluorosubstituted Alkenes: Evidence of a Concerted Pathway for Reaction of CSI with Fluorosubstituted Alkenes (Preprint)</title><description>Concerted reactions are indicated for the electrophilic addition of chlorosulfonyl isocyanate with monofluoroalkenes. A vinyl fluorine atom on an alkene raises the energy of a step-wise transition state more than the energy of the competing concerted pathway. This energy shift induces CSI to react with monofluoroalkenes by a one-step process. The low reactivity of CSI with monofluoroalkenes, stereospecific reactions, the absence of 2:1 uracil products with neat fluoroalkenes and quantum chemical calculations support a concerted pathway.
Performed in collaboration with Point Loma Nazarene University, San Diego, CA; and the University of California, La Jolla, CA. Submitted for publication in the Journal of Organic Chemistry.</description><subject>ADDITION REACTIONS</subject><subject>ALKENES</subject><subject>ANTIBIOTICS</subject><subject>BETA-LACTAMS</subject><subject>Biochemistry</subject><subject>CSI(CHLOROSULFONYL ISOCYANATES)</subject><subject>FLUORINE</subject><subject>FLUOROALKENES</subject><subject>ISOCYANATES</subject><subject>Medicine and Medical Research</subject><subject>Organic Chemistry</subject><subject>Physical Chemistry</subject><subject>REPRINTS</subject><subject>SUBSTITUTION REACTIONS</subject><subject>SULFONYL HALIDES</subject><subject>Test Facilities, Equipment and Methods</subject><subject>WUAFRL50260541</subject><fulltext>true</fulltext><rsrctype>report</rsrctype><creationdate>2010</creationdate><recordtype>report</recordtype><sourceid>1RU</sourceid><recordid>eNqFjbEOgjAYhFkcjPoGDv8IgwmBuLiRCpGNiDup5W9obFrT_kh4JN9SMC5OTHfJfXe3Dt5X5IKUNWAlsE5bZ32vpTWjhtJbMXLDCSFkdRnBoKiDQvdf6O5JUU_YQqYfaNCfIH-pFo3AeYsDs5N1M1Bx6gY-grQO_v7qcmETwsrh0ylD0TZYSa497n66CfZFfmOXQ0tKNFPRIDXZOTsmaRwn6UL8AX2XVJo</recordid><startdate>201006</startdate><enddate>201006</enddate><creator>Shellhamer, Dale</creator><creator>Davenport, Kevyn J</creator><creator>Hassler, Danielle M</creator><creator>Hickle, Kelli R</creator><creator>Thorpe, Jacob J</creator><creator>Vandenbroek, David J</creator><creator>Heasley, Victor L</creator><creator>Boatz, Jerry A</creator><creator>Reingold, Arnold L</creator><creator>Moore, Chris E</creator><scope>1RU</scope><scope>BHM</scope></search><sort><creationdate>201006</creationdate><title>Reaction of Chlorosulfonyl Isocyanate (CSI) with Fluorosubstituted Alkenes: Evidence of a Concerted Pathway for Reaction of CSI with Fluorosubstituted Alkenes (Preprint)</title><author>Shellhamer, Dale ; Davenport, Kevyn J ; Hassler, Danielle M ; Hickle, Kelli R ; Thorpe, Jacob J ; Vandenbroek, David J ; Heasley, Victor L ; Boatz, Jerry A ; Reingold, Arnold L ; Moore, Chris E</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-dtic_stinet_ADA5230023</frbrgroupid><rsrctype>reports</rsrctype><prefilter>reports</prefilter><language>eng</language><creationdate>2010</creationdate><topic>ADDITION REACTIONS</topic><topic>ALKENES</topic><topic>ANTIBIOTICS</topic><topic>BETA-LACTAMS</topic><topic>Biochemistry</topic><topic>CSI(CHLOROSULFONYL ISOCYANATES)</topic><topic>FLUORINE</topic><topic>FLUOROALKENES</topic><topic>ISOCYANATES</topic><topic>Medicine and Medical Research</topic><topic>Organic Chemistry</topic><topic>Physical Chemistry</topic><topic>REPRINTS</topic><topic>SUBSTITUTION REACTIONS</topic><topic>SULFONYL HALIDES</topic><topic>Test Facilities, Equipment and Methods</topic><topic>WUAFRL50260541</topic><toplevel>online_resources</toplevel><creatorcontrib>Shellhamer, Dale</creatorcontrib><creatorcontrib>Davenport, Kevyn J</creatorcontrib><creatorcontrib>Hassler, Danielle M</creatorcontrib><creatorcontrib>Hickle, Kelli R</creatorcontrib><creatorcontrib>Thorpe, Jacob J</creatorcontrib><creatorcontrib>Vandenbroek, David J</creatorcontrib><creatorcontrib>Heasley, Victor L</creatorcontrib><creatorcontrib>Boatz, Jerry A</creatorcontrib><creatorcontrib>Reingold, Arnold L</creatorcontrib><creatorcontrib>Moore, Chris E</creatorcontrib><creatorcontrib>AIR FORCE RESEARCH LAB EDWARDS AFB CA PROPULSION DIRECTORATE</creatorcontrib><collection>DTIC Technical Reports</collection><collection>DTIC STINET</collection></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext_linktorsrc</fulltext></delivery><addata><au>Shellhamer, Dale</au><au>Davenport, Kevyn J</au><au>Hassler, Danielle M</au><au>Hickle, Kelli R</au><au>Thorpe, Jacob J</au><au>Vandenbroek, David J</au><au>Heasley, Victor L</au><au>Boatz, Jerry A</au><au>Reingold, Arnold L</au><au>Moore, Chris E</au><aucorp>AIR FORCE RESEARCH LAB EDWARDS AFB CA PROPULSION DIRECTORATE</aucorp><format>book</format><genre>unknown</genre><ristype>RPRT</ristype><btitle>Reaction of Chlorosulfonyl Isocyanate (CSI) with Fluorosubstituted Alkenes: Evidence of a Concerted Pathway for Reaction of CSI with Fluorosubstituted Alkenes (Preprint)</btitle><date>2010-06</date><risdate>2010</risdate><abstract>Concerted reactions are indicated for the electrophilic addition of chlorosulfonyl isocyanate with monofluoroalkenes. A vinyl fluorine atom on an alkene raises the energy of a step-wise transition state more than the energy of the competing concerted pathway. This energy shift induces CSI to react with monofluoroalkenes by a one-step process. The low reactivity of CSI with monofluoroalkenes, stereospecific reactions, the absence of 2:1 uracil products with neat fluoroalkenes and quantum chemical calculations support a concerted pathway.
Performed in collaboration with Point Loma Nazarene University, San Diego, CA; and the University of California, La Jolla, CA. Submitted for publication in the Journal of Organic Chemistry.</abstract><oa>free_for_read</oa></addata></record> |
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| source | DTIC Technical Reports |
| subjects | ADDITION REACTIONS ALKENES ANTIBIOTICS BETA-LACTAMS Biochemistry CSI(CHLOROSULFONYL ISOCYANATES) FLUORINE FLUOROALKENES ISOCYANATES Medicine and Medical Research Organic Chemistry Physical Chemistry REPRINTS SUBSTITUTION REACTIONS SULFONYL HALIDES Test Facilities, Equipment and Methods WUAFRL50260541 |
| title | Reaction of Chlorosulfonyl Isocyanate (CSI) with Fluorosubstituted Alkenes: Evidence of a Concerted Pathway for Reaction of CSI with Fluorosubstituted Alkenes (Preprint) |
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