Chiral NMR Discrimination of Piperidines and Piperazines Using (18-Crown-6)-2,3,11,12-tetracarboxylic Acid
Enantiomeric discrimination is observed in the 1H and 13C NMR spectra of piperidines and piperazines in the presence of (−)-(18-crown-6)-2,3,11,12-tetracarboxylic acid. The amines are protonated by the carboxylic acid groups of the crown ether to produce the corresponding ammonium and carboxylate io...
Gespeichert in:
| Veröffentlicht in: | Journal of organic chemistry 2006-11, Vol.71 (24), p.9178-9182 |
|---|---|
| Hauptverfasser: | , |
| Format: | Artikel |
| Sprache: | eng |
| Schlagworte: | |
| Online-Zugang: | Volltext |
| Tags: |
Tag hinzufügen
Keine Tags, Fügen Sie den ersten Tag hinzu!
|
| container_end_page | 9182 |
|---|---|
| container_issue | 24 |
| container_start_page | 9178 |
| container_title | Journal of organic chemistry |
| container_volume | 71 |
| creator | Lovely, Ann E Wenzel, Thomas J |
| description | Enantiomeric discrimination is observed in the 1H and 13C NMR spectra of piperidines and piperazines in the presence of (−)-(18-crown-6)-2,3,11,12-tetracarboxylic acid. The amines are protonated by the carboxylic acid groups of the crown ether to produce the corresponding ammonium and carboxylate ions. Association of the ammonium ion with the crown ether likely involves two hydrogen bonds with the crown ether oxygen atoms and an ion pair with the carboxylate anion. Methyl, hydroxymethyl, phenyl, carboxyl, pyridyl, and cyclohexyl substituent groups α to the nitrogen atom do not inhibit binding of the ammonium ion to the crown ether. The NMR spectra of piperidines with the stereogenic center α or β to the nitrogen atom exhibit substantial enantiomeric discrimination. Dibasic substrates such as the piperizines are likely converted to their diprotonated form in the presence of the crown ether, and both nitrogen atoms appear to associate with the crown ether moiety. |
| doi_str_mv | 10.1021/jo061586w |
| format | Article |
| fullrecord | <record><control><sourceid>proquest_cross</sourceid><recordid>TN_cdi_proquest_miscellaneous_68154932</recordid><sourceformat>XML</sourceformat><sourcesystem>PC</sourcesystem><sourcerecordid>68154932</sourcerecordid><originalsourceid>FETCH-LOGICAL-a447t-e87d1fe8beabdf67f3bcd9b2c729727caf88caf946e6bd786aba5f9fb024a8363</originalsourceid><addsrcrecordid>eNptkFtvEzEQhS0EomnhgT-A9gXUSjH4sr7sYxtuFaVUbSrxZs16bXDYeFN7o7b8ekwTNS_Mw4xG8-nozEHoFSXvKGH0_WIgkgotb5-gCRWMYNmQ-imaEMIY5kzyPbSf84KUEkI8R3tUUdKIup6gxexXSNBX598uqw8h2xSWIcIYhlgNvroIK5dCF6LLFcRus8Ofh_06h_izOqQaz9JwG7E8wmzKp5ROKcOjGxNYSO1wd98HWx3b0L1Azzz02b3czgN0_enjfPYFn33_fDo7PsNQ12rETquOeqdbB23npfK8tV3TMqtYo5iy4LUuramlk22ntIQWhG98S1gNmkt-gN5udFdpuFm7PJplecz1PUQ3rLORmoq64ayARxvQpiHn5LxZlfch3RtKzL9gzWOwhX29FV23S9ftyG2SBXizBSBb6H2CaEPecZpTIqUuHN5wIY_u7vEO6beRiith5hdX5uuPk6vLc9KY-U4XbC5-1imW7P5j8C_rXZq9</addsrcrecordid><sourcetype>Aggregation Database</sourcetype><iscdi>true</iscdi><recordtype>article</recordtype><pqid>68154932</pqid></control><display><type>article</type><title>Chiral NMR Discrimination of Piperidines and Piperazines Using (18-Crown-6)-2,3,11,12-tetracarboxylic Acid</title><source>MEDLINE</source><source>American Chemical Society Journals</source><creator>Lovely, Ann E ; Wenzel, Thomas J</creator><creatorcontrib>Lovely, Ann E ; Wenzel, Thomas J</creatorcontrib><description>Enantiomeric discrimination is observed in the 1H and 13C NMR spectra of piperidines and piperazines in the presence of (−)-(18-crown-6)-2,3,11,12-tetracarboxylic acid. The amines are protonated by the carboxylic acid groups of the crown ether to produce the corresponding ammonium and carboxylate ions. Association of the ammonium ion with the crown ether likely involves two hydrogen bonds with the crown ether oxygen atoms and an ion pair with the carboxylate anion. Methyl, hydroxymethyl, phenyl, carboxyl, pyridyl, and cyclohexyl substituent groups α to the nitrogen atom do not inhibit binding of the ammonium ion to the crown ether. The NMR spectra of piperidines with the stereogenic center α or β to the nitrogen atom exhibit substantial enantiomeric discrimination. Dibasic substrates such as the piperizines are likely converted to their diprotonated form in the presence of the crown ether, and both nitrogen atoms appear to associate with the crown ether moiety.</description><identifier>ISSN: 0022-3263</identifier><identifier>EISSN: 1520-6904</identifier><identifier>DOI: 10.1021/jo061586w</identifier><identifier>PMID: 17109544</identifier><identifier>CODEN: JOCEAH</identifier><language>eng</language><publisher>Washington, DC: American Chemical Society</publisher><subject>Alicyclic compounds ; Alicyclic compounds, terpenoids, prostaglandins, steroids ; Carboxylic Acids - chemistry ; Chemistry ; Crown Ethers - chemistry ; Exact sciences and technology ; Heterocyclic compounds ; Heterocyclic compounds with only one n hetero atom and condensed derivatives ; Heterocyclic compounds with several n hetero atoms in the same ring, in separated rings or in fused rings ; Magnetic Resonance Spectroscopy - methods ; Organic chemistry ; Piperazines - analysis ; Piperidines - analysis ; Preparations and properties ; Stereoisomerism</subject><ispartof>Journal of organic chemistry, 2006-11, Vol.71 (24), p.9178-9182</ispartof><rights>Copyright © 2006 American Chemical Society</rights><rights>2007 INIST-CNRS</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-a447t-e87d1fe8beabdf67f3bcd9b2c729727caf88caf946e6bd786aba5f9fb024a8363</citedby><cites>FETCH-LOGICAL-a447t-e87d1fe8beabdf67f3bcd9b2c729727caf88caf946e6bd786aba5f9fb024a8363</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/jo061586w$$EPDF$$P50$$Gacs$$H</linktopdf><linktohtml>$$Uhttps://pubs.acs.org/doi/10.1021/jo061586w$$EHTML$$P50$$Gacs$$H</linktohtml><link.rule.ids>314,780,784,2765,27076,27924,27925,56738,56788</link.rule.ids><backlink>$$Uhttp://pascal-francis.inist.fr/vibad/index.php?action=getRecordDetail&idt=18310668$$DView record in Pascal Francis$$Hfree_for_read</backlink><backlink>$$Uhttps://www.ncbi.nlm.nih.gov/pubmed/17109544$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink></links><search><creatorcontrib>Lovely, Ann E</creatorcontrib><creatorcontrib>Wenzel, Thomas J</creatorcontrib><title>Chiral NMR Discrimination of Piperidines and Piperazines Using (18-Crown-6)-2,3,11,12-tetracarboxylic Acid</title><title>Journal of organic chemistry</title><addtitle>J. Org. Chem</addtitle><description>Enantiomeric discrimination is observed in the 1H and 13C NMR spectra of piperidines and piperazines in the presence of (−)-(18-crown-6)-2,3,11,12-tetracarboxylic acid. The amines are protonated by the carboxylic acid groups of the crown ether to produce the corresponding ammonium and carboxylate ions. Association of the ammonium ion with the crown ether likely involves two hydrogen bonds with the crown ether oxygen atoms and an ion pair with the carboxylate anion. Methyl, hydroxymethyl, phenyl, carboxyl, pyridyl, and cyclohexyl substituent groups α to the nitrogen atom do not inhibit binding of the ammonium ion to the crown ether. The NMR spectra of piperidines with the stereogenic center α or β to the nitrogen atom exhibit substantial enantiomeric discrimination. Dibasic substrates such as the piperizines are likely converted to their diprotonated form in the presence of the crown ether, and both nitrogen atoms appear to associate with the crown ether moiety.</description><subject>Alicyclic compounds</subject><subject>Alicyclic compounds, terpenoids, prostaglandins, steroids</subject><subject>Carboxylic Acids - chemistry</subject><subject>Chemistry</subject><subject>Crown Ethers - chemistry</subject><subject>Exact sciences and technology</subject><subject>Heterocyclic compounds</subject><subject>Heterocyclic compounds with only one n hetero atom and condensed derivatives</subject><subject>Heterocyclic compounds with several n hetero atoms in the same ring, in separated rings or in fused rings</subject><subject>Magnetic Resonance Spectroscopy - methods</subject><subject>Organic chemistry</subject><subject>Piperazines - analysis</subject><subject>Piperidines - analysis</subject><subject>Preparations and properties</subject><subject>Stereoisomerism</subject><issn>0022-3263</issn><issn>1520-6904</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2006</creationdate><recordtype>article</recordtype><sourceid>EIF</sourceid><recordid>eNptkFtvEzEQhS0EomnhgT-A9gXUSjH4sr7sYxtuFaVUbSrxZs16bXDYeFN7o7b8ekwTNS_Mw4xG8-nozEHoFSXvKGH0_WIgkgotb5-gCRWMYNmQ-imaEMIY5kzyPbSf84KUEkI8R3tUUdKIup6gxexXSNBX598uqw8h2xSWIcIYhlgNvroIK5dCF6LLFcRus8Ofh_06h_izOqQaz9JwG7E8wmzKp5ROKcOjGxNYSO1wd98HWx3b0L1Azzz02b3czgN0_enjfPYFn33_fDo7PsNQ12rETquOeqdbB23npfK8tV3TMqtYo5iy4LUuramlk22ntIQWhG98S1gNmkt-gN5udFdpuFm7PJplecz1PUQ3rLORmoq64ayARxvQpiHn5LxZlfch3RtKzL9gzWOwhX29FV23S9ftyG2SBXizBSBb6H2CaEPecZpTIqUuHN5wIY_u7vEO6beRiith5hdX5uuPk6vLc9KY-U4XbC5-1imW7P5j8C_rXZq9</recordid><startdate>20061124</startdate><enddate>20061124</enddate><creator>Lovely, Ann E</creator><creator>Wenzel, Thomas J</creator><general>American Chemical Society</general><scope>BSCLL</scope><scope>IQODW</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>7X8</scope></search><sort><creationdate>20061124</creationdate><title>Chiral NMR Discrimination of Piperidines and Piperazines Using (18-Crown-6)-2,3,11,12-tetracarboxylic Acid</title><author>Lovely, Ann E ; Wenzel, Thomas J</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-a447t-e87d1fe8beabdf67f3bcd9b2c729727caf88caf946e6bd786aba5f9fb024a8363</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2006</creationdate><topic>Alicyclic compounds</topic><topic>Alicyclic compounds, terpenoids, prostaglandins, steroids</topic><topic>Carboxylic Acids - chemistry</topic><topic>Chemistry</topic><topic>Crown Ethers - chemistry</topic><topic>Exact sciences and technology</topic><topic>Heterocyclic compounds</topic><topic>Heterocyclic compounds with only one n hetero atom and condensed derivatives</topic><topic>Heterocyclic compounds with several n hetero atoms in the same ring, in separated rings or in fused rings</topic><topic>Magnetic Resonance Spectroscopy - methods</topic><topic>Organic chemistry</topic><topic>Piperazines - analysis</topic><topic>Piperidines - analysis</topic><topic>Preparations and properties</topic><topic>Stereoisomerism</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Lovely, Ann E</creatorcontrib><creatorcontrib>Wenzel, Thomas J</creatorcontrib><collection>Istex</collection><collection>Pascal-Francis</collection><collection>Medline</collection><collection>MEDLINE</collection><collection>MEDLINE (Ovid)</collection><collection>MEDLINE</collection><collection>MEDLINE</collection><collection>PubMed</collection><collection>CrossRef</collection><collection>MEDLINE - Academic</collection><jtitle>Journal of organic chemistry</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Lovely, Ann E</au><au>Wenzel, Thomas J</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Chiral NMR Discrimination of Piperidines and Piperazines Using (18-Crown-6)-2,3,11,12-tetracarboxylic Acid</atitle><jtitle>Journal of organic chemistry</jtitle><addtitle>J. Org. Chem</addtitle><date>2006-11-24</date><risdate>2006</risdate><volume>71</volume><issue>24</issue><spage>9178</spage><epage>9182</epage><pages>9178-9182</pages><issn>0022-3263</issn><eissn>1520-6904</eissn><coden>JOCEAH</coden><abstract>Enantiomeric discrimination is observed in the 1H and 13C NMR spectra of piperidines and piperazines in the presence of (−)-(18-crown-6)-2,3,11,12-tetracarboxylic acid. The amines are protonated by the carboxylic acid groups of the crown ether to produce the corresponding ammonium and carboxylate ions. Association of the ammonium ion with the crown ether likely involves two hydrogen bonds with the crown ether oxygen atoms and an ion pair with the carboxylate anion. Methyl, hydroxymethyl, phenyl, carboxyl, pyridyl, and cyclohexyl substituent groups α to the nitrogen atom do not inhibit binding of the ammonium ion to the crown ether. The NMR spectra of piperidines with the stereogenic center α or β to the nitrogen atom exhibit substantial enantiomeric discrimination. Dibasic substrates such as the piperizines are likely converted to their diprotonated form in the presence of the crown ether, and both nitrogen atoms appear to associate with the crown ether moiety.</abstract><cop>Washington, DC</cop><pub>American Chemical Society</pub><pmid>17109544</pmid><doi>10.1021/jo061586w</doi><tpages>5</tpages></addata></record> |
| fulltext | fulltext |
| identifier | ISSN: 0022-3263 |
| ispartof | Journal of organic chemistry, 2006-11, Vol.71 (24), p.9178-9182 |
| issn | 0022-3263 1520-6904 |
| language | eng |
| recordid | cdi_proquest_miscellaneous_68154932 |
| source | MEDLINE; American Chemical Society Journals |
| subjects | Alicyclic compounds Alicyclic compounds, terpenoids, prostaglandins, steroids Carboxylic Acids - chemistry Chemistry Crown Ethers - chemistry Exact sciences and technology Heterocyclic compounds Heterocyclic compounds with only one n hetero atom and condensed derivatives Heterocyclic compounds with several n hetero atoms in the same ring, in separated rings or in fused rings Magnetic Resonance Spectroscopy - methods Organic chemistry Piperazines - analysis Piperidines - analysis Preparations and properties Stereoisomerism |
| title | Chiral NMR Discrimination of Piperidines and Piperazines Using (18-Crown-6)-2,3,11,12-tetracarboxylic Acid |
| url | https://sfx.bib-bvb.de/sfx_tum?ctx_ver=Z39.88-2004&ctx_enc=info:ofi/enc:UTF-8&ctx_tim=2025-01-01T14%3A23%3A24IST&url_ver=Z39.88-2004&url_ctx_fmt=infofi/fmt:kev:mtx:ctx&rfr_id=info:sid/primo.exlibrisgroup.com:primo3-Article-proquest_cross&rft_val_fmt=info:ofi/fmt:kev:mtx:journal&rft.genre=article&rft.atitle=Chiral%20NMR%20Discrimination%20of%20Piperidines%20and%20Piperazines%20Using%20(18-Crown-6)-2,3,11,12-tetracarboxylic%20Acid&rft.jtitle=Journal%20of%20organic%20chemistry&rft.au=Lovely,%20Ann%20E&rft.date=2006-11-24&rft.volume=71&rft.issue=24&rft.spage=9178&rft.epage=9182&rft.pages=9178-9182&rft.issn=0022-3263&rft.eissn=1520-6904&rft.coden=JOCEAH&rft_id=info:doi/10.1021/jo061586w&rft_dat=%3Cproquest_cross%3E68154932%3C/proquest_cross%3E%3Curl%3E%3C/url%3E&disable_directlink=true&sfx.directlink=off&sfx.report_link=0&rft_id=info:oai/&rft_pqid=68154932&rft_id=info:pmid/17109544&rfr_iscdi=true |