Synthesis and Reactivity of New Functionalized Perfluoroalkylfluorophosphates
A new efficient synthesis of functionalized perfluoroalkyl fluorophosphates by oxidative addition of Me2NCH2F to the electron‐deficient phosphanes (C2F5)nPF3−n (n=0–3) is reported. The initially formed zwitterionic, hexacoordinated phosphates [(C2F5)nF5−nP(CH2NMe2−CH2NMe2)] are converted into the co...
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| Veröffentlicht in: | Chemistry : a European journal 2014-06, Vol.20 (25), p.7736-7745 |
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| creator | Allefeld, Nadine Neumann, Beate Stammler, Hans-Georg Röschenthaler, Gerd-Volker Ignat'ev, Nikolai Hoge, Berthold |
| description | A new efficient synthesis of functionalized perfluoroalkyl fluorophosphates by oxidative addition of Me2NCH2F to the electron‐deficient phosphanes (C2F5)nPF3−n (n=0–3) is reported. The initially formed zwitterionic, hexacoordinated phosphates [(C2F5)nF5−nP(CH2NMe2−CH2NMe2)] are converted into the corresponding phosphonium salts [(Me3PCH2NMe2]+[(C2F5)nF5−nP(CH2NMe2)]− by treatment with PMe3. In addition [(C2F5)3F2P(CH2NMe2CH2NMe2)] can undergo a 1,3‐methyl shift from the internal to the terminal nitrogen—a structural characterization was achieved from the CF3 analogue. Reaction of [(C2F5)3F2P(CH2NMeCH2NMe3)] and PMe3 gave rise to the formation of the zwitterionic phosphonium phosphate [(C2F5)3F2P(CH2NMeCH2PMe3)], which was fully characterized by X‐ray diffraction analysis. Moreover, an efficient one‐pot synthesis of Cs+[(C2F5)3F2P(CH2NMe2)]− was pursued. This salt turned out to be a useful nucleophile in several alkylation reactions.
It′s down to the fluorine: Several novel functionalized perfluoroalkylfluorophosphates were synthesized via an efficient one‐pot synthesis, employing Me2NCH2F as an oxidizer. Subsequent treatment with electrophiles (RX), such as HCl or allyl bromides, leads to the formation of zwitterionic ammonium phosphates (see scheme). |
| doi_str_mv | 10.1002/chem.201402421 |
| format | Article |
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It′s down to the fluorine: Several novel functionalized perfluoroalkylfluorophosphates were synthesized via an efficient one‐pot synthesis, employing Me2NCH2F as an oxidizer. Subsequent treatment with electrophiles (RX), such as HCl or allyl bromides, leads to the formation of zwitterionic ammonium phosphates (see scheme).</description><identifier>ISSN: 0947-6539</identifier><identifier>EISSN: 1521-3765</identifier><identifier>DOI: 10.1002/chem.201402421</identifier><identifier>PMID: 24827420</identifier><identifier>CODEN: CEUJED</identifier><language>eng</language><publisher>Weinheim: WILEY-VCH Verlag</publisher><subject>Alkylation ; Chemistry ; Diffraction ; Fluorides - analysis ; Fluorides - chemical synthesis ; fluorine ; Formations ; iminium ; Models, Molecular ; Nucleophiles ; oxidative addition ; Perfluoroalkyl & polyfluoroalkyl substances ; phosphate ; Phosphates ; Phosphates - analysis ; Phosphates - chemical synthesis ; phosphorus ; Salts ; Structural analysis ; Synthesis ; Terminals ; X-rays ; Zwitterions</subject><ispartof>Chemistry : a European journal, 2014-06, Vol.20 (25), p.7736-7745</ispartof><rights>2014 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim</rights><rights>2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.</rights><rights>2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim</rights><rights>Copyright Wiley Subscription Services, Inc. Jun 2014</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c5791-5b10d39cc18fb8ab05ce1a697a2e9f40b70d7b92a4179e118f0c785624d638843</citedby><cites>FETCH-LOGICAL-c5791-5b10d39cc18fb8ab05ce1a697a2e9f40b70d7b92a4179e118f0c785624d638843</cites></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><linktopdf>$$Uhttps://onlinelibrary.wiley.com/doi/pdf/10.1002%2Fchem.201402421$$EPDF$$P50$$Gwiley$$H</linktopdf><linktohtml>$$Uhttps://onlinelibrary.wiley.com/doi/full/10.1002%2Fchem.201402421$$EHTML$$P50$$Gwiley$$H</linktohtml><link.rule.ids>314,776,780,1411,27903,27904,45553,45554</link.rule.ids><backlink>$$Uhttps://www.ncbi.nlm.nih.gov/pubmed/24827420$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink></links><search><creatorcontrib>Allefeld, Nadine</creatorcontrib><creatorcontrib>Neumann, Beate</creatorcontrib><creatorcontrib>Stammler, Hans-Georg</creatorcontrib><creatorcontrib>Röschenthaler, Gerd-Volker</creatorcontrib><creatorcontrib>Ignat'ev, Nikolai</creatorcontrib><creatorcontrib>Hoge, Berthold</creatorcontrib><title>Synthesis and Reactivity of New Functionalized Perfluoroalkylfluorophosphates</title><title>Chemistry : a European journal</title><addtitle>Chem. Eur. J</addtitle><description>A new efficient synthesis of functionalized perfluoroalkyl fluorophosphates by oxidative addition of Me2NCH2F to the electron‐deficient phosphanes (C2F5)nPF3−n (n=0–3) is reported. The initially formed zwitterionic, hexacoordinated phosphates [(C2F5)nF5−nP(CH2NMe2−CH2NMe2)] are converted into the corresponding phosphonium salts [(Me3PCH2NMe2]+[(C2F5)nF5−nP(CH2NMe2)]− by treatment with PMe3. In addition [(C2F5)3F2P(CH2NMe2CH2NMe2)] can undergo a 1,3‐methyl shift from the internal to the terminal nitrogen—a structural characterization was achieved from the CF3 analogue. Reaction of [(C2F5)3F2P(CH2NMeCH2NMe3)] and PMe3 gave rise to the formation of the zwitterionic phosphonium phosphate [(C2F5)3F2P(CH2NMeCH2PMe3)], which was fully characterized by X‐ray diffraction analysis. Moreover, an efficient one‐pot synthesis of Cs+[(C2F5)3F2P(CH2NMe2)]− was pursued. This salt turned out to be a useful nucleophile in several alkylation reactions.
It′s down to the fluorine: Several novel functionalized perfluoroalkylfluorophosphates were synthesized via an efficient one‐pot synthesis, employing Me2NCH2F as an oxidizer. Subsequent treatment with electrophiles (RX), such as HCl or allyl bromides, leads to the formation of zwitterionic ammonium phosphates (see scheme).</description><subject>Alkylation</subject><subject>Chemistry</subject><subject>Diffraction</subject><subject>Fluorides - analysis</subject><subject>Fluorides - chemical synthesis</subject><subject>fluorine</subject><subject>Formations</subject><subject>iminium</subject><subject>Models, Molecular</subject><subject>Nucleophiles</subject><subject>oxidative addition</subject><subject>Perfluoroalkyl & polyfluoroalkyl substances</subject><subject>phosphate</subject><subject>Phosphates</subject><subject>Phosphates - analysis</subject><subject>Phosphates - chemical synthesis</subject><subject>phosphorus</subject><subject>Salts</subject><subject>Structural analysis</subject><subject>Synthesis</subject><subject>Terminals</subject><subject>X-rays</subject><subject>Zwitterions</subject><issn>0947-6539</issn><issn>1521-3765</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2014</creationdate><recordtype>article</recordtype><sourceid>EIF</sourceid><recordid>eNqFkU1r3DAQhkVpaLZJrz0WQy-9eDP6lo7F5AuSbWlSAr0IWZZZJ157I9lNnV9fBadL6aE5zTA87wPDi9B7DEsMQI7c2m-WBDADwgh-hRaYE5xTKfhrtADNZC441fvobYy3AKAFpW_QPmGKSEZggS6vpm5Y-9jEzHZV9s1bNzQ_m2HK-jpb-YfsZOzSpe9s2zz6KvvqQ92Ofehteze187pd93G7toOPh2ivtm30757nAfp-cnxdnOUXX07Pi88XueNS45yXGCqqncOqLpUtgTuPrdDSEq9rBqWESpaaWIal9jhR4KTigrBKUKUYPUCfZu829Pejj4PZNNH5trWd78dosJQKgHIlXkY5TWIlFEnox3_Q234M6fNoCBdYaQqS_Y9KLsY5kRwnajlTLvQxBl-bbWg2NkwGg3lqzjw1Z3bNpcCHZ-1Ybny1w_9UlQA9Aw9N66cXdKY4O778W57P2SYO_tcua8OdEZJKbm5Wp4atfhTFzZUyhP4GMbSyeA</recordid><startdate>20140616</startdate><enddate>20140616</enddate><creator>Allefeld, Nadine</creator><creator>Neumann, Beate</creator><creator>Stammler, Hans-Georg</creator><creator>Röschenthaler, Gerd-Volker</creator><creator>Ignat'ev, Nikolai</creator><creator>Hoge, Berthold</creator><general>WILEY-VCH Verlag</general><general>WILEY‐VCH Verlag</general><general>Wiley Subscription Services, Inc</general><scope>BSCLL</scope><scope>CGR</scope><scope>CUY</scope><scope>CVF</scope><scope>ECM</scope><scope>EIF</scope><scope>NPM</scope><scope>AAYXX</scope><scope>CITATION</scope><scope>7SR</scope><scope>8BQ</scope><scope>8FD</scope><scope>JG9</scope><scope>K9.</scope><scope>7X8</scope></search><sort><creationdate>20140616</creationdate><title>Synthesis and Reactivity of New Functionalized Perfluoroalkylfluorophosphates</title><author>Allefeld, Nadine ; Neumann, Beate ; Stammler, Hans-Georg ; Röschenthaler, Gerd-Volker ; Ignat'ev, Nikolai ; Hoge, Berthold</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c5791-5b10d39cc18fb8ab05ce1a697a2e9f40b70d7b92a4179e118f0c785624d638843</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2014</creationdate><topic>Alkylation</topic><topic>Chemistry</topic><topic>Diffraction</topic><topic>Fluorides - analysis</topic><topic>Fluorides - chemical synthesis</topic><topic>fluorine</topic><topic>Formations</topic><topic>iminium</topic><topic>Models, Molecular</topic><topic>Nucleophiles</topic><topic>oxidative addition</topic><topic>Perfluoroalkyl & polyfluoroalkyl substances</topic><topic>phosphate</topic><topic>Phosphates</topic><topic>Phosphates - analysis</topic><topic>Phosphates - chemical synthesis</topic><topic>phosphorus</topic><topic>Salts</topic><topic>Structural analysis</topic><topic>Synthesis</topic><topic>Terminals</topic><topic>X-rays</topic><topic>Zwitterions</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Allefeld, Nadine</creatorcontrib><creatorcontrib>Neumann, Beate</creatorcontrib><creatorcontrib>Stammler, Hans-Georg</creatorcontrib><creatorcontrib>Röschenthaler, Gerd-Volker</creatorcontrib><creatorcontrib>Ignat'ev, Nikolai</creatorcontrib><creatorcontrib>Hoge, Berthold</creatorcontrib><collection>Istex</collection><collection>Medline</collection><collection>MEDLINE</collection><collection>MEDLINE (Ovid)</collection><collection>MEDLINE</collection><collection>MEDLINE</collection><collection>PubMed</collection><collection>CrossRef</collection><collection>Engineered Materials Abstracts</collection><collection>METADEX</collection><collection>Technology Research Database</collection><collection>Materials Research Database</collection><collection>ProQuest Health & Medical Complete (Alumni)</collection><collection>MEDLINE - Academic</collection><jtitle>Chemistry : a European journal</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Allefeld, Nadine</au><au>Neumann, Beate</au><au>Stammler, Hans-Georg</au><au>Röschenthaler, Gerd-Volker</au><au>Ignat'ev, Nikolai</au><au>Hoge, Berthold</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Synthesis and Reactivity of New Functionalized Perfluoroalkylfluorophosphates</atitle><jtitle>Chemistry : a European journal</jtitle><addtitle>Chem. Eur. J</addtitle><date>2014-06-16</date><risdate>2014</risdate><volume>20</volume><issue>25</issue><spage>7736</spage><epage>7745</epage><pages>7736-7745</pages><issn>0947-6539</issn><eissn>1521-3765</eissn><coden>CEUJED</coden><abstract>A new efficient synthesis of functionalized perfluoroalkyl fluorophosphates by oxidative addition of Me2NCH2F to the electron‐deficient phosphanes (C2F5)nPF3−n (n=0–3) is reported. The initially formed zwitterionic, hexacoordinated phosphates [(C2F5)nF5−nP(CH2NMe2−CH2NMe2)] are converted into the corresponding phosphonium salts [(Me3PCH2NMe2]+[(C2F5)nF5−nP(CH2NMe2)]− by treatment with PMe3. In addition [(C2F5)3F2P(CH2NMe2CH2NMe2)] can undergo a 1,3‐methyl shift from the internal to the terminal nitrogen—a structural characterization was achieved from the CF3 analogue. Reaction of [(C2F5)3F2P(CH2NMeCH2NMe3)] and PMe3 gave rise to the formation of the zwitterionic phosphonium phosphate [(C2F5)3F2P(CH2NMeCH2PMe3)], which was fully characterized by X‐ray diffraction analysis. Moreover, an efficient one‐pot synthesis of Cs+[(C2F5)3F2P(CH2NMe2)]− was pursued. This salt turned out to be a useful nucleophile in several alkylation reactions.
It′s down to the fluorine: Several novel functionalized perfluoroalkylfluorophosphates were synthesized via an efficient one‐pot synthesis, employing Me2NCH2F as an oxidizer. Subsequent treatment with electrophiles (RX), such as HCl or allyl bromides, leads to the formation of zwitterionic ammonium phosphates (see scheme).</abstract><cop>Weinheim</cop><pub>WILEY-VCH Verlag</pub><pmid>24827420</pmid><doi>10.1002/chem.201402421</doi><tpages>10</tpages></addata></record> |
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| subjects | Alkylation Chemistry Diffraction Fluorides - analysis Fluorides - chemical synthesis fluorine Formations iminium Models, Molecular Nucleophiles oxidative addition Perfluoroalkyl & polyfluoroalkyl substances phosphate Phosphates Phosphates - analysis Phosphates - chemical synthesis phosphorus Salts Structural analysis Synthesis Terminals X-rays Zwitterions |
| title | Synthesis and Reactivity of New Functionalized Perfluoroalkylfluorophosphates |
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