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Synthesis of Thiocyameluric Acid C6N7S3H3, Its Reaction to Alkali Metal Thiocyamelurates and Organic Tris(dithio)cyamelurates
Thiocyameluric acid C6N7S3H3, the tri‐thio analogue of cyameluric acid, is a key compound for the synthesis of new s‐heptazine (tri‐s‐triazine) derivatives. Here, two different routes for the synthesis of thiocyameluric acid and its reaction to tris(aryldithio)‐ and tris(alkyldithio)cyamelurates C6N...
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| Published in: | Chemistry : a European journal 2019-12, Vol.25 (68), p.15555-15564 |
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| container_end_page | 15564 |
| container_issue | 68 |
| container_start_page | 15555 |
| container_title | Chemistry : a European journal |
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| creator | Posern, Christian Höhne, Carl‐Christoph Böhme, Uwe Vogt, Claudia Kroke, Edwin |
| description | Thiocyameluric acid C6N7S3H3, the tri‐thio analogue of cyameluric acid, is a key compound for the synthesis of new s‐heptazine (tri‐s‐triazine) derivatives. Here, two different routes for the synthesis of thiocyameluric acid and its reaction to tris(aryldithio)‐ and tris(alkyldithio)cyamelurates C6N7(SSR)3 are reported as well as transformation to alkali metal thiocyamelurates M3[C6N7S3], M=Na, K. These compounds were characterised by FTIR, Raman, solution 13C and 1H NMR spectroscopies, thermal gravimetric analysis (TGA) and elemental analysis. The three (de)protonation steps of thiocyameluric acid were investigated by acid–base titration followed via UV/Vis absorption spectroscopy. While it was not possible to determine the three pKa values, it could be postulated that the acid strength probably increases in the following order: cyanuric acid (C3N3O3H3) < thiocyanuric acid (C3N3S3H3) < cyameluric acid (C6N7O3H3) < thiocyameluric acid (C6N7S3H3). Single crystals of Na3[C6N7S3]⋅10 H2O and K3[C6N7S3]⋅6 H2O were obtained and the structures analyzed by single crystal X‐ray diffraction. Additionally, quantum chemical calculations were performed to get insights into the electronic structure of thiocyameluric acid and to clarify the thiol–thione tautomerism. Based on a comparison of calculated and measured vibrational spectra it can be concluded that thiocyameluric acid and the di‐ and mono‐protonated anions exist in the thione form.
Not a fidget spinner! Thiocyameluric acid C6N7S3H3, the tri‐thio analogues of cyameluric acid, is a key compound for the synthesis of new s‐heptazine (tri‐s‐triazine) derivatives. Here, two different routes for the synthesis of thiocyameluric acid and its reaction to tris(aryldithio)‐ and tris(alkyldithio)cyamelurates C6N7(SSR)3 are reported as well as transformation to alkali metal thiocyamelurates M3[C6N7S3], M=Na, K. |
| doi_str_mv | 10.1002/chem.201903400 |
| format | article |
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Not a fidget spinner! Thiocyameluric acid C6N7S3H3, the tri‐thio analogues of cyameluric acid, is a key compound for the synthesis of new s‐heptazine (tri‐s‐triazine) derivatives. Here, two different routes for the synthesis of thiocyameluric acid and its reaction to tris(aryldithio)‐ and tris(alkyldithio)cyamelurates C6N7(SSR)3 are reported as well as transformation to alkali metal thiocyamelurates M3[C6N7S3], M=Na, K.</description><identifier>ISSN: 0947-6539</identifier><identifier>EISSN: 1521-3765</identifier><identifier>DOI: 10.1002/chem.201903400</identifier><identifier>PMID: 31550389</identifier><language>eng</language><publisher>Weinheim: Wiley Subscription Services, Inc</publisher><subject>Absorption spectroscopy ; Acids ; Alkali metal compounds ; Alkali metals ; Anions ; Chemical analysis ; Chemistry ; Crystal structure ; Crystals ; cyameluric acid ; Cyanuric acid ; Electronic structure ; Gravimetric analysis ; heterocycles ; Mathematical analysis ; NMR ; Nuclear magnetic resonance ; Organic chemistry ; Protonation ; Quantum chemistry ; Single crystals ; Spectrum analysis ; sulfur ; Tautomerism ; Thermal analysis ; thermal behavior ; Titration ; Triazine ; triazines ; Vibrational spectra</subject><ispartof>Chemistry : a European journal, 2019-12, Vol.25 (68), p.15555-15564</ispartof><rights>2019 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.</rights><rights>2019 Wiley‐VCH Verlag GmbH & Co. KGaA, Weinheim</rights><lds50>peer_reviewed</lds50><oa>free_for_read</oa><woscitedreferencessubscribed>false</woscitedreferencessubscribed><orcidid>0000-0002-6984-6042 ; 0000-0002-7934-6439 ; 0000-0003-1582-1656 ; 0000-0002-0739-5311</orcidid></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.201903400$$EPDF$$P50$$Gwiley$$Hfree_for_read</linktopdf><linktohtml>$$Uhttps://onlinelibrary.wiley.com/doi/full/10.1002%2Fchem.201903400$$EHTML$$P50$$Gwiley$$Hfree_for_read</linktohtml><link.rule.ids>230,315,786,790,891,27957,27958,50923,51032</link.rule.ids></links><search><creatorcontrib>Posern, Christian</creatorcontrib><creatorcontrib>Höhne, Carl‐Christoph</creatorcontrib><creatorcontrib>Böhme, Uwe</creatorcontrib><creatorcontrib>Vogt, Claudia</creatorcontrib><creatorcontrib>Kroke, Edwin</creatorcontrib><title>Synthesis of Thiocyameluric Acid C6N7S3H3, Its Reaction to Alkali Metal Thiocyamelurates and Organic Tris(dithio)cyamelurates</title><title>Chemistry : a European journal</title><description>Thiocyameluric acid C6N7S3H3, the tri‐thio analogue of cyameluric acid, is a key compound for the synthesis of new s‐heptazine (tri‐s‐triazine) derivatives. Here, two different routes for the synthesis of thiocyameluric acid and its reaction to tris(aryldithio)‐ and tris(alkyldithio)cyamelurates C6N7(SSR)3 are reported as well as transformation to alkali metal thiocyamelurates M3[C6N7S3], M=Na, K. These compounds were characterised by FTIR, Raman, solution 13C and 1H NMR spectroscopies, thermal gravimetric analysis (TGA) and elemental analysis. The three (de)protonation steps of thiocyameluric acid were investigated by acid–base titration followed via UV/Vis absorption spectroscopy. While it was not possible to determine the three pKa values, it could be postulated that the acid strength probably increases in the following order: cyanuric acid (C3N3O3H3) < thiocyanuric acid (C3N3S3H3) < cyameluric acid (C6N7O3H3) < thiocyameluric acid (C6N7S3H3). Single crystals of Na3[C6N7S3]⋅10 H2O and K3[C6N7S3]⋅6 H2O were obtained and the structures analyzed by single crystal X‐ray diffraction. Additionally, quantum chemical calculations were performed to get insights into the electronic structure of thiocyameluric acid and to clarify the thiol–thione tautomerism. Based on a comparison of calculated and measured vibrational spectra it can be concluded that thiocyameluric acid and the di‐ and mono‐protonated anions exist in the thione form.
Not a fidget spinner! Thiocyameluric acid C6N7S3H3, the tri‐thio analogues of cyameluric acid, is a key compound for the synthesis of new s‐heptazine (tri‐s‐triazine) derivatives. Here, two different routes for the synthesis of thiocyameluric acid and its reaction to tris(aryldithio)‐ and tris(alkyldithio)cyamelurates C6N7(SSR)3 are reported as well as transformation to alkali metal thiocyamelurates M3[C6N7S3], M=Na, K.</description><subject>Absorption spectroscopy</subject><subject>Acids</subject><subject>Alkali metal compounds</subject><subject>Alkali metals</subject><subject>Anions</subject><subject>Chemical analysis</subject><subject>Chemistry</subject><subject>Crystal structure</subject><subject>Crystals</subject><subject>cyameluric acid</subject><subject>Cyanuric acid</subject><subject>Electronic structure</subject><subject>Gravimetric analysis</subject><subject>heterocycles</subject><subject>Mathematical analysis</subject><subject>NMR</subject><subject>Nuclear magnetic resonance</subject><subject>Organic chemistry</subject><subject>Protonation</subject><subject>Quantum chemistry</subject><subject>Single crystals</subject><subject>Spectrum analysis</subject><subject>sulfur</subject><subject>Tautomerism</subject><subject>Thermal analysis</subject><subject>thermal behavior</subject><subject>Titration</subject><subject>Triazine</subject><subject>triazines</subject><subject>Vibrational spectra</subject><issn>0947-6539</issn><issn>1521-3765</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2019</creationdate><recordtype>article</recordtype><sourceid>24P</sourceid><sourceid>WIN</sourceid><recordid>eNpVkc9LwzAUx4MoOn9cPQe8KNj50temyUUYY7qBOtDeQ9pkW7RrtcmUHfzf7ZgMPT0e7_M-fOFLyDmDPgOIb8qFXfZjYBIwAdgjPZbGLMKMp_ukBzLJIp6iPCLH3r8CgOSIh-QIWZoCCtkj3y_rOiysd542M5ovXFOu9dJWq9aVdFA6Q4f8KXvBMV7TSfD02eoyuKamoaGD6k1Xjj7aoKt_rzpYT3Vt6LSd67oT5a3zl8aFjrn6C52Sg5muvD37nSckvxvlw3H0ML2fDAcP0Rx5ChE3QppYx8BtwgyIgiWQgRQSZpkuUiGF0dKmJUDBMpZhbHkimRYz5NIKgyfkdqt9XxVLa0pbh1ZX6r11S92uVaOd-n-p3ULNm0_FJeOYiE5w8Stom4-V9UG9Nqu27iKrGGOGXZgk6Si5pb5cZdc7PQO1qUptqlK7qtRwPHrcbfgDBoiJWg</recordid><startdate>20191205</startdate><enddate>20191205</enddate><creator>Posern, Christian</creator><creator>Höhne, Carl‐Christoph</creator><creator>Böhme, Uwe</creator><creator>Vogt, Claudia</creator><creator>Kroke, Edwin</creator><general>Wiley Subscription Services, Inc</general><general>John Wiley and Sons Inc</general><scope>24P</scope><scope>WIN</scope><scope>7SR</scope><scope>8BQ</scope><scope>8FD</scope><scope>JG9</scope><scope>K9.</scope><scope>5PM</scope><orcidid>https://orcid.org/0000-0002-6984-6042</orcidid><orcidid>https://orcid.org/0000-0002-7934-6439</orcidid><orcidid>https://orcid.org/0000-0003-1582-1656</orcidid><orcidid>https://orcid.org/0000-0002-0739-5311</orcidid></search><sort><creationdate>20191205</creationdate><title>Synthesis of Thiocyameluric Acid C6N7S3H3, Its Reaction to Alkali Metal Thiocyamelurates and Organic Tris(dithio)cyamelurates</title><author>Posern, Christian ; Höhne, Carl‐Christoph ; Böhme, Uwe ; Vogt, Claudia ; Kroke, Edwin</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-g3650-6d89d2a206e41d08b140709890f7ab5898da9e5c00b171732e6491a8f369e8d3</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2019</creationdate><topic>Absorption spectroscopy</topic><topic>Acids</topic><topic>Alkali metal compounds</topic><topic>Alkali metals</topic><topic>Anions</topic><topic>Chemical analysis</topic><topic>Chemistry</topic><topic>Crystal structure</topic><topic>Crystals</topic><topic>cyameluric acid</topic><topic>Cyanuric acid</topic><topic>Electronic structure</topic><topic>Gravimetric analysis</topic><topic>heterocycles</topic><topic>Mathematical analysis</topic><topic>NMR</topic><topic>Nuclear magnetic resonance</topic><topic>Organic chemistry</topic><topic>Protonation</topic><topic>Quantum chemistry</topic><topic>Single crystals</topic><topic>Spectrum analysis</topic><topic>sulfur</topic><topic>Tautomerism</topic><topic>Thermal analysis</topic><topic>thermal behavior</topic><topic>Titration</topic><topic>Triazine</topic><topic>triazines</topic><topic>Vibrational spectra</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Posern, Christian</creatorcontrib><creatorcontrib>Höhne, Carl‐Christoph</creatorcontrib><creatorcontrib>Böhme, Uwe</creatorcontrib><creatorcontrib>Vogt, Claudia</creatorcontrib><creatorcontrib>Kroke, Edwin</creatorcontrib><collection>Wiley Online Library</collection><collection>Wiley Free Archive</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>PubMed Central (Full Participant titles)</collection><jtitle>Chemistry : a European journal</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Posern, Christian</au><au>Höhne, Carl‐Christoph</au><au>Böhme, Uwe</au><au>Vogt, Claudia</au><au>Kroke, Edwin</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Synthesis of Thiocyameluric Acid C6N7S3H3, Its Reaction to Alkali Metal Thiocyamelurates and Organic Tris(dithio)cyamelurates</atitle><jtitle>Chemistry : a European journal</jtitle><date>2019-12-05</date><risdate>2019</risdate><volume>25</volume><issue>68</issue><spage>15555</spage><epage>15564</epage><pages>15555-15564</pages><issn>0947-6539</issn><eissn>1521-3765</eissn><abstract>Thiocyameluric acid C6N7S3H3, the tri‐thio analogue of cyameluric acid, is a key compound for the synthesis of new s‐heptazine (tri‐s‐triazine) derivatives. Here, two different routes for the synthesis of thiocyameluric acid and its reaction to tris(aryldithio)‐ and tris(alkyldithio)cyamelurates C6N7(SSR)3 are reported as well as transformation to alkali metal thiocyamelurates M3[C6N7S3], M=Na, K. These compounds were characterised by FTIR, Raman, solution 13C and 1H NMR spectroscopies, thermal gravimetric analysis (TGA) and elemental analysis. The three (de)protonation steps of thiocyameluric acid were investigated by acid–base titration followed via UV/Vis absorption spectroscopy. While it was not possible to determine the three pKa values, it could be postulated that the acid strength probably increases in the following order: cyanuric acid (C3N3O3H3) < thiocyanuric acid (C3N3S3H3) < cyameluric acid (C6N7O3H3) < thiocyameluric acid (C6N7S3H3). Single crystals of Na3[C6N7S3]⋅10 H2O and K3[C6N7S3]⋅6 H2O were obtained and the structures analyzed by single crystal X‐ray diffraction. Additionally, quantum chemical calculations were performed to get insights into the electronic structure of thiocyameluric acid and to clarify the thiol–thione tautomerism. Based on a comparison of calculated and measured vibrational spectra it can be concluded that thiocyameluric acid and the di‐ and mono‐protonated anions exist in the thione form.
Not a fidget spinner! Thiocyameluric acid C6N7S3H3, the tri‐thio analogues of cyameluric acid, is a key compound for the synthesis of new s‐heptazine (tri‐s‐triazine) derivatives. Here, two different routes for the synthesis of thiocyameluric acid and its reaction to tris(aryldithio)‐ and tris(alkyldithio)cyamelurates C6N7(SSR)3 are reported as well as transformation to alkali metal thiocyamelurates M3[C6N7S3], M=Na, K.</abstract><cop>Weinheim</cop><pub>Wiley Subscription Services, Inc</pub><pmid>31550389</pmid><doi>10.1002/chem.201903400</doi><tpages>10</tpages><orcidid>https://orcid.org/0000-0002-6984-6042</orcidid><orcidid>https://orcid.org/0000-0002-7934-6439</orcidid><orcidid>https://orcid.org/0000-0003-1582-1656</orcidid><orcidid>https://orcid.org/0000-0002-0739-5311</orcidid><oa>free_for_read</oa></addata></record> |
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| subjects | Absorption spectroscopy Acids Alkali metal compounds Alkali metals Anions Chemical analysis Chemistry Crystal structure Crystals cyameluric acid Cyanuric acid Electronic structure Gravimetric analysis heterocycles Mathematical analysis NMR Nuclear magnetic resonance Organic chemistry Protonation Quantum chemistry Single crystals Spectrum analysis sulfur Tautomerism Thermal analysis thermal behavior Titration Triazine triazines Vibrational spectra |
| title | Synthesis of Thiocyameluric Acid C6N7S3H3, Its Reaction to Alkali Metal Thiocyamelurates and Organic Tris(dithio)cyamelurates |
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