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10-Dimethylamino Derivatives of Benzo[h]quinoline and Benzo[h]quinazolines: Fluorescent Proton Sponge Analogues with Opposed peri-NMe2/–N Groups. How to Distinguish between Proton Sponges and Pseudo-Proton Sponges
For the first time, 10-dimethylamino derivatives of benzo[h]quinoline 6 and benzo[h]quinazoline 7a–e as mixed analogues of archetypal 1,8-bis(dimethylamino)naphthalene (“proton sponge”) 1 and quino[7,8-h]quinoline 2a have been examined. Similar to 1 and 2, compounds 6 and 7 display rather hi...
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| Published in: | Journal of organic chemistry 2016-07, Vol.81 (13), p.5574-5587 |
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| container_end_page | 5587 |
| container_issue | 13 |
| container_start_page | 5574 |
| container_title | Journal of organic chemistry |
| container_volume | 81 |
| creator | Pozharskii, Alexander F Ozeryanskii, Valery A Mikshiev, Vladimir Y Antonov, Alexander S Chernyshev, Anatoly V Metelitsa, Anatoly V Borodkin, Gennady S Fedik, Nikita S Dyablo, Olga V |
| description | For the first time, 10-dimethylamino derivatives of benzo[h]quinoline 6 and benzo[h]quinazoline 7a–e as mixed analogues of archetypal 1,8-bis(dimethylamino)naphthalene (“proton sponge”) 1 and quino[7,8-h]quinoline 2a have been examined. Similar to 1 and 2, compounds 6 and 7 display rather high basicity, forming chelated monocations. At the same time, unexpected specifics of the protonated NMe2/N systems consist of a strong shift of the NH proton to the 10-NMe2 group, contrary to the “aniline–pyridine” basicity rule. In case of 4H + , a rapid migration (in the NMR time scale) of the NH proton between two nitrogen atoms along the N–H···N hydrogen bond was registered at room temperature and frozen below −30 °C with the proton fixed on the NMe2 group. Two different approaches for classification of strong neutral nitrogen organic bases as proton sponges (kinetically inert compounds) or pseudo-proton sponges (kinetically active) are discussed. On this basis, benzoquinoline 6 was identified as staying closer to pseudo-proton sponges while 7a–e to proton sponges due to the presence in their molecules of bulky substituents in the pyrimidine ring. Other remarkable peculiarities of 6 and 7 are their yellow color and luminescence in the visible region distinguishing them from colorless 1 and 2a. |
| doi_str_mv | 10.1021/acs.joc.6b00917 |
| format | article |
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How to Distinguish between Proton Sponges and Pseudo-Proton Sponges</title><source>American Chemical Society:Jisc Collections:American Chemical Society Read & Publish Agreement 2022-2024 (Reading list)</source><creator>Pozharskii, Alexander F ; Ozeryanskii, Valery A ; Mikshiev, Vladimir Y ; Antonov, Alexander S ; Chernyshev, Anatoly V ; Metelitsa, Anatoly V ; Borodkin, Gennady S ; Fedik, Nikita S ; Dyablo, Olga V</creator><creatorcontrib>Pozharskii, Alexander F ; Ozeryanskii, Valery A ; Mikshiev, Vladimir Y ; Antonov, Alexander S ; Chernyshev, Anatoly V ; Metelitsa, Anatoly V ; Borodkin, Gennady S ; Fedik, Nikita S ; Dyablo, Olga V</creatorcontrib><description>For the first time, 10-dimethylamino derivatives of benzo[h]quinoline 6 and benzo[h]quinazoline 7a–e as mixed analogues of archetypal 1,8-bis(dimethylamino)naphthalene (“proton sponge”) 1 and quino[7,8-h]quinoline 2a have been examined. Similar to 1 and 2, compounds 6 and 7 display rather high basicity, forming chelated monocations. At the same time, unexpected specifics of the protonated NMe2/N systems consist of a strong shift of the NH proton to the 10-NMe2 group, contrary to the “aniline–pyridine” basicity rule. In case of 4H + , a rapid migration (in the NMR time scale) of the NH proton between two nitrogen atoms along the N–H···N hydrogen bond was registered at room temperature and frozen below −30 °C with the proton fixed on the NMe2 group. Two different approaches for classification of strong neutral nitrogen organic bases as proton sponges (kinetically inert compounds) or pseudo-proton sponges (kinetically active) are discussed. On this basis, benzoquinoline 6 was identified as staying closer to pseudo-proton sponges while 7a–e to proton sponges due to the presence in their molecules of bulky substituents in the pyrimidine ring. Other remarkable peculiarities of 6 and 7 are their yellow color and luminescence in the visible region distinguishing them from colorless 1 and 2a.</description><identifier>ISSN: 0022-3263</identifier><identifier>EISSN: 1520-6904</identifier><identifier>DOI: 10.1021/acs.joc.6b00917</identifier><identifier>PMID: 27285083</identifier><language>eng</language><publisher>United States: American Chemical Society</publisher><ispartof>Journal of organic chemistry, 2016-07, Vol.81 (13), p.5574-5587</ispartof><rights>Copyright © 2016 American Chemical Society</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><link.rule.ids>315,786,790,27957,27958</link.rule.ids><backlink>$$Uhttps://www.ncbi.nlm.nih.gov/pubmed/27285083$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink></links><search><creatorcontrib>Pozharskii, Alexander F</creatorcontrib><creatorcontrib>Ozeryanskii, Valery A</creatorcontrib><creatorcontrib>Mikshiev, Vladimir Y</creatorcontrib><creatorcontrib>Antonov, Alexander S</creatorcontrib><creatorcontrib>Chernyshev, Anatoly V</creatorcontrib><creatorcontrib>Metelitsa, Anatoly V</creatorcontrib><creatorcontrib>Borodkin, Gennady S</creatorcontrib><creatorcontrib>Fedik, Nikita S</creatorcontrib><creatorcontrib>Dyablo, Olga V</creatorcontrib><title>10-Dimethylamino Derivatives of Benzo[h]quinoline and Benzo[h]quinazolines: Fluorescent Proton Sponge Analogues with Opposed peri-NMe2/–N Groups. How to Distinguish between Proton Sponges and Pseudo-Proton Sponges</title><title>Journal of organic chemistry</title><addtitle>J. Org. Chem</addtitle><description>For the first time, 10-dimethylamino derivatives of benzo[h]quinoline 6 and benzo[h]quinazoline 7a–e as mixed analogues of archetypal 1,8-bis(dimethylamino)naphthalene (“proton sponge”) 1 and quino[7,8-h]quinoline 2a have been examined. Similar to 1 and 2, compounds 6 and 7 display rather high basicity, forming chelated monocations. At the same time, unexpected specifics of the protonated NMe2/N systems consist of a strong shift of the NH proton to the 10-NMe2 group, contrary to the “aniline–pyridine” basicity rule. In case of 4H + , a rapid migration (in the NMR time scale) of the NH proton between two nitrogen atoms along the N–H···N hydrogen bond was registered at room temperature and frozen below −30 °C with the proton fixed on the NMe2 group. Two different approaches for classification of strong neutral nitrogen organic bases as proton sponges (kinetically inert compounds) or pseudo-proton sponges (kinetically active) are discussed. On this basis, benzoquinoline 6 was identified as staying closer to pseudo-proton sponges while 7a–e to proton sponges due to the presence in their molecules of bulky substituents in the pyrimidine ring. Other remarkable peculiarities of 6 and 7 are their yellow color and luminescence in the visible region distinguishing them from colorless 1 and 2a.</description><issn>0022-3263</issn><issn>1520-6904</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2016</creationdate><recordtype>article</recordtype><recordid>eNpVUctu1DAUtRAVHQprdpWXSCjTaztxku76oA-ptJWAFUKRk9yZ8Six09juqF3xDyz4GP6EJR_AN2A6w2Lu5krnnnvu4xDyhsGUAWcHqnHTpW2msgYoWf6MTFjGIZElpM_JBIDzRHApdslL55YQI8uyF2SX57zIoBAT8otBcqp79IuHTvXaWHqKo75XXt-jo3ZGj9E82i-Lr3chFjttkCrTbqHq8Ql3h_SsC3ZE16Dx9Ha03hr6cbBmjvTIqM7OQ5Rcab-gN8NgHbZ0iLOS6w_ID35_-37958dPej7aMLgpvbAr6uMy2nlt5kG7Ba3RrxDNtrJ7WufWYWhtsl15RXZmqnP4epP3yOez959OLpKrm_PLk6OrRPE090lW1rNCQqZkDqUAwesGOGJeypgaXpQ8R87yGaS1lIqVos2ZkK2MLU3K0lLskbdr3WG0d_FEX_U6_qDrlEEbXMUKYKkQUEKk7m-ooe6xrYZR92p8qP77EQnv1oRobLW0YYx_iwpQ_XO7WoNNtXFb_AWxG6GO</recordid><startdate>20160701</startdate><enddate>20160701</enddate><creator>Pozharskii, Alexander F</creator><creator>Ozeryanskii, Valery A</creator><creator>Mikshiev, Vladimir Y</creator><creator>Antonov, Alexander S</creator><creator>Chernyshev, Anatoly V</creator><creator>Metelitsa, Anatoly V</creator><creator>Borodkin, Gennady S</creator><creator>Fedik, Nikita S</creator><creator>Dyablo, Olga V</creator><general>American Chemical Society</general><scope>NPM</scope><scope>7X8</scope></search><sort><creationdate>20160701</creationdate><title>10-Dimethylamino Derivatives of Benzo[h]quinoline and Benzo[h]quinazolines: Fluorescent Proton Sponge Analogues with Opposed peri-NMe2/–N Groups. 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How to Distinguish between Proton Sponges and Pseudo-Proton Sponges</atitle><jtitle>Journal of organic chemistry</jtitle><addtitle>J. Org. Chem</addtitle><date>2016-07-01</date><risdate>2016</risdate><volume>81</volume><issue>13</issue><spage>5574</spage><epage>5587</epage><pages>5574-5587</pages><issn>0022-3263</issn><eissn>1520-6904</eissn><notes>ObjectType-Article-1</notes><notes>SourceType-Scholarly Journals-1</notes><notes>ObjectType-Feature-2</notes><notes>content type line 23</notes><abstract>For the first time, 10-dimethylamino derivatives of benzo[h]quinoline 6 and benzo[h]quinazoline 7a–e as mixed analogues of archetypal 1,8-bis(dimethylamino)naphthalene (“proton sponge”) 1 and quino[7,8-h]quinoline 2a have been examined. Similar to 1 and 2, compounds 6 and 7 display rather high basicity, forming chelated monocations. At the same time, unexpected specifics of the protonated NMe2/N systems consist of a strong shift of the NH proton to the 10-NMe2 group, contrary to the “aniline–pyridine” basicity rule. In case of 4H + , a rapid migration (in the NMR time scale) of the NH proton between two nitrogen atoms along the N–H···N hydrogen bond was registered at room temperature and frozen below −30 °C with the proton fixed on the NMe2 group. Two different approaches for classification of strong neutral nitrogen organic bases as proton sponges (kinetically inert compounds) or pseudo-proton sponges (kinetically active) are discussed. On this basis, benzoquinoline 6 was identified as staying closer to pseudo-proton sponges while 7a–e to proton sponges due to the presence in their molecules of bulky substituents in the pyrimidine ring. Other remarkable peculiarities of 6 and 7 are their yellow color and luminescence in the visible region distinguishing them from colorless 1 and 2a.</abstract><cop>United States</cop><pub>American Chemical Society</pub><pmid>27285083</pmid><doi>10.1021/acs.joc.6b00917</doi><tpages>14</tpages></addata></record> |
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| title | 10-Dimethylamino Derivatives of Benzo[h]quinoline and Benzo[h]quinazolines: Fluorescent Proton Sponge Analogues with Opposed peri-NMe2/–N Groups. How to Distinguish between Proton Sponges and Pseudo-Proton Sponges |
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