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<h1 id="firstHeading" class="firstHeading mw-first-heading"><span class="mw-page-title-main">Bispidin</span></h1>
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<div id="mw-content-text" class="mw-body-content mw-content-ltr" lang="de" dir="ltr"><div class="mw-content-ltr mw-parser-output" lang="de" dir="ltr"><table class="wikitable infobox float-right" id="Vorlage_Infobox_Chemikalie" style="font-size:90%; margin-top:0; width:350px;" summary="Infobox Chemikalie">
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<th colspan="2" style="background:#FFDEAD; color:#202122;">Strukturformel
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<td colspan="2" class="hintergrundfarbe-basis skin-invert-image" style="text-align:center;"><span typeof="mw:File"></span>
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<th colspan="2" style="background:#FFDEAD; color:#202122;">Allgemeines
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<td style="width:33%;">Name
</td>
<td>Bispidin
</td></tr>
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<td>Andere Namen
</td>
<td>
<p>3,7-Diazabicyclo[3.3.1]nonan
</p>
</td></tr>
<tr>
<td><a href="Summenformel" title="Summenformel">Summenformel</a>
</td>
<td>C<sub>7</sub>H<sub>14</sub>N<sub>2</sub>
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<th colspan="2" style="background:#FFDEAD; color:#202122;">Externe Identifikatoren/Datenbanken
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<td colspan="2" style="padding:0;">
<table class="mw-collapsible mw-collapsed wikitable" data-expandtext="+" data-collapsetext="−" style="border-top:none; margin:-1px; width:calc(100% + 2px);">
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<td style="width:33%;"><a href="CAS-Nummer" title="CAS-Nummer">CAS-Nummer</a>
</td>
<td><span title="Untervorlage eingebunden: CASRN"></span><a rel="nofollow" class="external text" href="https://commonchemistry.cas.org/detail?cas_rn=280-74-0">280-74-0</a><span class="editoronly" style="display:none;"></span>
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<td style="background:#FFDEAD; color:#202122; border-top:1px solid #FFDEAD; padding:0.2em 0; vertical-align:bottom; width:5%;">
</td></tr>
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<td><a href="PubChem" title="PubChem">PubChem</a>
</td>
<td colspan="2"><a rel="nofollow" class="external text" href="https://pubchem.ncbi.nlm.nih.gov/compound/192720">192720</a>
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<td style="border-right:1px solid #a2a9b1;"><a href="Wikidata" title="Wikidata">Wikidata</a>
</td>
<td colspan="2"><a href="https://www.wikidata.org/wiki/Q866620" class="extiw external" title="d:Q866620">Q866620</a>
</td></tr></tbody></table>
</td></tr>
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<th colspan="2" style="background:#FFDEAD; color:#202122;">Eigenschaften
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<td><a href="Molare_Masse" title="Molare Masse">Molare Masse</a>
</td>
<td>126,20 g·<a href="Mol" title="Mol">mol</a><sup>−1</sup>
</td></tr>
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<td><a href="Aggregatzustand" title="Aggregatzustand">Aggregatzustand</a>
</td>
<td>
<p>fest
</p>
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<td><a href="Schmelzpunkt" title="Schmelzpunkt">Schmelzpunkt</a>
</td>
<td>
<p>158–161 °C<sup id="cite_ref-Miyahara_1-0" class="reference"><a href="#cite_note-Miyahara-1"><span class="cite-bracket">[</span>1<span class="cite-bracket">]</span></a></sup>
</p>
</td></tr>
<tr>
<td><a href="Siedepunkt" title="Siedepunkt">Siedepunkt</a>
</td>
<td>
<p>190–195 °C (9 Torr)<sup id="cite_ref-2" class="reference"><a href="#cite_note-2"><span class="cite-bracket">[</span>2<span class="cite-bracket">]</span></a></sup>
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<th colspan="2" style="background:#FFDEAD; color:#202122;">Sicherheitshinweise
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<td colspan="2" style="text-align:center"><b><a href="Global_harmonisiertes_System_zur_Einstufung_und_Kennzeichnung_von_Chemikalien" title="Global harmonisiertes System zur Einstufung und Kennzeichnung von Chemikalien">GHS-Gefahrstoffkennzeichnung</a></b><br><i>keine Einstufung verfügbar</i><sup id="cite_ref-NV_3-0" class="reference"><a href="#cite_note-NV-3"><span class="cite-bracket">[</span>3<span class="cite-bracket">]</span></a></sup>
</td></tr></tbody></table>
</td></tr>
<tr>
<td colspan="2" style="background:#FFDEAD; color:#202122; font-size:80%; text-align:center; line-height:150%; padding:.25em;">Wenn nicht anders vermerkt, gelten die angegebenen Daten bei <a href="Standardbedingungen" title="Standardbedingungen">Standardbedingungen</a> (0 °C, 1000 hPa).
</td></tr></tbody></table><p><span class="editoronly" style="display:none;"></span>
</p><p><b>Bispidin</b> ist eine bicyclische, <a href="Heterocyclen" title="Heterocyclen">heterocyclische Verbindung</a>, deren systematischer Name 3,7-Diazabicyclo[3.3.1]nonan lautet.
</p>
<div class="mw-heading mw-heading2"><h2 id="Vorkommen">Vorkommen</h2></div>
<p>Bispidin bildet den Grundkörper einiger <a href="Alkaloid" class="mw-redirect" title="Alkaloid">Alkaloide</a> wie z. B. <a href="Spartein" title="Spartein">Spartein</a><sup id="cite_ref-4" class="reference"><a href="#cite_note-4"><span class="cite-bracket">[</span>4<span class="cite-bracket">]</span></a></sup> und <a href="Cytisin" title="Cytisin">Cytisin</a>.<sup id="cite_ref-5" class="reference"><a href="#cite_note-5"><span class="cite-bracket">[</span>5<span class="cite-bracket">]</span></a></sup>
</p>
<div class="mw-heading mw-heading2"><h2 id="Darstellung">Darstellung</h2></div>
<p>Die Synthese von Bispidin kann über eine durch <a href="Raney-Nickel" title="Raney-Nickel">Raney-Nickel</a> katalysierte <a href="Hydrierung" title="Hydrierung">Hydrierung</a> von Pyridin-3,5-carbonitril erfolgen.<sup id="cite_ref-6" class="reference"><a href="#cite_note-6"><span class="cite-bracket">[</span>6<span class="cite-bracket">]</span></a></sup> Eine mehrstufige Synthese geht vom Pyridin-3,5-dicarboxyethylester aus, der zunächst über Platinoxid zum Piperidin-3,5-dicarboxyethylester hydriert wird. Eine <a href="Reduktion_(Chemie)" title="Reduktion (Chemie)">Reduktion</a> mittels <a href="Lithiumaluminiumhydrid" title="Lithiumaluminiumhydrid">Lithiumaluminiumhydrid</a> ergibt dann 3,5-Bis(hydroxymethyl)-piperidin. Durch nucleophile Substitution wird der Dialkohol zunächst in das Dibromid und dann in das Diamid überführt, welches zur Zielverbindung zyklisiert.<sup id="cite_ref-Galinovsky_7-0" class="reference"><a href="#cite_note-Galinovsky-7"><span class="cite-bracket">[</span>7<span class="cite-bracket">]</span></a></sup>
<span typeof="mw:File"></span>
</p><p>Eine neuere Synthese geht von <a href="Allylamin" title="Allylamin">Allylamin</a> und <a href="Ethylacrylat" class="mw-redirect" title="Ethylacrylat">Ethylacrylat</a> aus, wo zunächst in einer doppelten <a href="Mannich-Reaktion" title="Mannich-Reaktion">Mannich-Reaktion</a> über 1-Allylpiperidin-4-on das N,N'-Diallylbispidinon gebildet wird. Eine anschließende <a href="Wolff-Kishner-Reduktion" class="mw-redirect" title="Wolff-Kishner-Reduktion">Wolff-Kishner-Reduktion</a> und Deallylierung mit <a href="Chlorameisens%C3%A4ureethylester" title="Chlorameisensäureethylester">Chlorameisensäureethylester</a> ergibt das Bispidin.<sup id="cite_ref-Miyahara_1-1" class="reference"><a href="#cite_note-Miyahara-1"><span class="cite-bracket">[</span>1<span class="cite-bracket">]</span></a></sup>
</p><p>Bispidinderivate können zum Beispiel durch selektive <a href="Michael-Addition" title="Michael-Addition">Michael-Additionen</a> dargestellt werden.<sup id="cite_ref-8" class="reference"><a href="#cite_note-8"><span class="cite-bracket">[</span>8<span class="cite-bracket">]</span></a></sup><sup id="cite_ref-9" class="reference"><a href="#cite_note-9"><span class="cite-bracket">[</span>9<span class="cite-bracket">]</span></a></sup><sup id="cite_ref-10" class="reference"><a href="#cite_note-10"><span class="cite-bracket">[</span>10<span class="cite-bracket">]</span></a></sup>
</p>
<div class="mw-heading mw-heading2"><h2 id="Eigenschaften">Eigenschaften</h2></div>
<p>Bispidin ist ein weißer kristalliner Feststoff, der schon ab 135 °C zu sublimieren beginnt.<sup id="cite_ref-11" class="reference"><a href="#cite_note-11"><span class="cite-bracket">[</span>11<span class="cite-bracket">]</span></a></sup> Im geschlossenen Röhrchen kann ein Schmelzpunkt bei 158–161 °C beobachtet werden.<sup id="cite_ref-Miyahara_1-2" class="reference"><a href="#cite_note-Miyahara-1"><span class="cite-bracket">[</span>1<span class="cite-bracket">]</span></a></sup>
</p><p>Die Umsetzung mit <a href="Formaldehyd" title="Formaldehyd">Formaldehyd</a> ergibt das Diazaadamantan.<sup id="cite_ref-Galinovsky_7-1" class="reference"><a href="#cite_note-Galinovsky-7"><span class="cite-bracket">[</span>7<span class="cite-bracket">]</span></a></sup>
</p><p><span typeof="mw:File"></span>
</p>
<div class="mw-heading mw-heading2"><h2 id="Verwendung">Verwendung</h2></div>
<p>Bispidinderivate finden Anwendung in der Chemie als <a href="Chelatkomplexe" title="Chelatkomplexe">Chelatliganden</a><sup id="cite_ref-12" class="reference"><a href="#cite_note-12"><span class="cite-bracket">[</span>12<span class="cite-bracket">]</span></a></sup> für <a href="%C3%9Cbergangsmetalle" title="Übergangsmetalle">Übergangsmetalle</a>.
</p>
<div class="mw-heading mw-heading2"><h2 id="Einzelnachweise">Einzelnachweise</h2></div>
<ol class="references">
<li id="cite_note-Miyahara-1"><span class="mw-cite-backlink">↑ <sup><a href="#cite_ref-Miyahara_1-0">a</a></sup> <sup><a href="#cite_ref-Miyahara_1-1">b</a></sup> <sup><a href="#cite_ref-Miyahara_1-2">c</a></sup></span> <span class="reference-text">Y. Miyahara, K. Goto, T. Inazu: <i>Convenient Synthesis of 3,7-Diazabicyclo[3.3.1]nonane (Bispidine)</i> in <a href="Synthesis" title="Synthesis">Synthesis</a> 2001, 364–366, <a href="Digital_Object_Identifier" title="Digital Object Identifier">doi</a>:<span class="uri-handle" style="white-space:nowrap"><a rel="nofollow" class="external text" href="https://doi.org/10.1055/s-2001-11427">10.1055/s-2001-11427</a></span>.</span>
</li>
<li id="cite_note-2"><span class="mw-cite-backlink"><a href="#cite_ref-2">↑</a></span> <span class="reference-text">H. Stetter, R. Merten: <i>Über Verbindungen mit Urotropin-Struktur, IX. Zur Kenntnis des Bispidins</i> in <a href="Chem._Ber." class="mw-redirect" title="Chem. Ber.">Chem. Ber.</a> 90 (1957) 868–875, <a href="Digital_Object_Identifier" title="Digital Object Identifier">doi</a>:<span class="uri-handle" style="white-space:nowrap"><a rel="nofollow" class="external text" href="https://doi.org/10.1002/cber.19570900605">10.1002/cber.19570900605</a></span></span>
</li>
<li id="cite_note-NV-3"><span class="mw-cite-backlink"><a href="#cite_ref-NV_3-0">↑</a></span> <span class="reference-text">Dieser Stoff wurde in Bezug auf seine Gefährlichkeit entweder noch nicht eingestuft oder eine verlässliche und zitierfähige Quelle hierzu wurde noch nicht gefunden.</span>
</li>
<li id="cite_note-4"><span class="mw-cite-backlink"><a href="#cite_ref-4">↑</a></span> <span class="reference-text">D. Hoppe, T. Hense: <i>Enantioselektive Synthese mit Lithium/(−)-Spartein-Carbanion-Paaren</i> in <a href="Angew._Chem." class="mw-redirect" title="Angew. Chem.">Angew. Chem.</a> 109 (1997) 2376–2410, <a href="Digital_Object_Identifier" title="Digital Object Identifier">doi</a>:<span class="uri-handle" style="white-space:nowrap"><a rel="nofollow" class="external text" href="https://doi.org/10.1002/ange.19971092105">10.1002/ange.19971092105</a></span>.</span>
</li>
<li id="cite_note-5"><span class="mw-cite-backlink"><a href="#cite_ref-5">↑</a></span> <span class="reference-text">D. Stead, P. O’Brien, A. J. Sanderson: <i>Concise Synthesis of (±)-Cytisine via Lithiation of N-Boc-bispidine</i> in <a href="Org._Lett." class="mw-redirect" title="Org. Lett.">Org. Lett.</a> 7 (2005) 4459–4462, <a href="Digital_Object_Identifier" title="Digital Object Identifier">doi</a>:<span class="uri-handle" style="white-space:nowrap"><a rel="nofollow" class="external text" href="https://doi.org/10.1021/ol0516869">10.1021/ol0516869</a></span>.</span>
</li>
<li id="cite_note-6"><span class="mw-cite-backlink"><a href="#cite_ref-6">↑</a></span> <span class="reference-text">F. Bohlmann, N. Ottawa, R. Keller: <i>Aufbau des Tetrahydro-chinolizons und des „Bispidins“ Beiträge zur Synthese des Cytisins</i> in <a href="Liebigs_Ann._Chem." class="mw-redirect" title="Liebigs Ann. Chem.">Liebigs Ann. Chem.</a> 587 (1954) 162–176, <a href="Digital_Object_Identifier" title="Digital Object Identifier">doi</a>:<span class="uri-handle" style="white-space:nowrap"><a rel="nofollow" class="external text" href="https://doi.org/10.1002/jlac.19545870210">10.1002/jlac.19545870210</a></span>.</span>
</li>
<li id="cite_note-Galinovsky-7"><span class="mw-cite-backlink">↑ <sup><a href="#cite_ref-Galinovsky_7-0">a</a></sup> <sup><a href="#cite_ref-Galinovsky_7-1">b</a></sup></span> <span class="reference-text">F. Galinovsky, H. Langer: <i>Synthese des 1,3-Diaza-adamantans und des Bispidins</i> in <a href="Gesellschaft_%C3%96sterreichischer_Chemiker" class="mw-redirect" title="Gesellschaft Österreichischer Chemiker">Monatshefte für Chemie</a> 86 (1955) 449–453, <a href="Digital_Object_Identifier" title="Digital Object Identifier">doi</a>:<span class="uri-handle" style="white-space:nowrap"><a rel="nofollow" class="external text" href="https://doi.org/10.1007/BF00903631">10.1007/BF00903631</a></span>.</span>
</li>
<li id="cite_note-8"><span class="mw-cite-backlink"><a href="#cite_ref-8">↑</a></span> <span class="reference-text">M. Breuning, M. Steiner: <i>Convenient Multigram Synthesis of (R)-Homopipecolic Acid Methyl Ester</i> in <a href="Synthesis" title="Synthesis">Synthesis</a> 2006, 1386–1389, <a href="Digital_Object_Identifier" title="Digital Object Identifier">doi</a>:<span class="uri-handle" style="white-space:nowrap"><a rel="nofollow" class="external text" href="https://doi.org/10.1055/s-2006-926419">10.1055/s-2006-926419</a></span>.</span>
</li>
<li id="cite_note-9"><span class="mw-cite-backlink"><a href="#cite_ref-9">↑</a></span> <span class="reference-text">M. Breuning, D. Hein: <i>First asymmetric synthesis of a C2-symmetric 2-endo,6-endo-disubstituted bispidine</i> in <a href="Tetrahedron" title="Tetrahedron">Tetrahedron Asym.</a> 18 (2007) 1410–1418, <a href="Digital_Object_Identifier" title="Digital Object Identifier">doi</a>:<span class="uri-handle" style="white-space:nowrap"><a rel="nofollow" class="external text" href="https://doi.org/10.1016/j.tetasy.2007.06.010">10.1016/j.tetasy.2007.06.010</a></span>.</span>
</li>
<li id="cite_note-10"><span class="mw-cite-backlink"><a href="#cite_ref-10">↑</a></span> <span class="reference-text">Uni-Würzburg: <style data-mw-deduplicate="TemplateStyles:r261891140">
/* start https://de.wikipedia.org/ */
.mw-parser-output .webarchiv-memento a{color:inherit}
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</style><a rel="nofollow" class="external text" href="https://web.archive.org/web/20130624081636/http://www-organik.chemie.uni-wuerzburg.de/lehrstuehlearbeitskreise/ehemalige/breuning/forschungsgebiete/chirale_bispidine_und_9_oxabispidine/">Chirale Bispidine und 9-Oxabispidine</a> (<span class="webarchiv-memento"><a href="Webarchivierung#Begrifflichkeiten" title="Webarchivierung">Memento</a></span> vom 24. Juni 2013 im <i><a href="Internet_Archive" title="Internet Archive">Internet Archive</a></i>)</span>
</li>
<li id="cite_note-11"><span class="mw-cite-backlink"><a href="#cite_ref-11">↑</a></span> <span class="reference-text">F. Galinovsky, F. Sparatore, H. Langer: <i>Eine neue Synthese des Tetrahydro-desoxy-cytisins. Zur Kenntnis des Bispidins</i> in <a href="Gesellschaft_%C3%96sterreichischer_Chemiker" class="mw-redirect" title="Gesellschaft Österreichischer Chemiker">Monatshefte für Chemie</a> 87 (1956) 100–105, <a href="Digital_Object_Identifier" title="Digital Object Identifier">doi</a>:<span class="uri-handle" style="white-space:nowrap"><a rel="nofollow" class="external text" href="https://doi.org/10.1007/BF00903593">10.1007/BF00903593</a></span></span>
</li>
<li id="cite_note-12"><span class="mw-cite-backlink"><a href="#cite_ref-12">↑</a></span> <span class="reference-text">P. Comba, M. Maurer, P. Vadivelu: <i>Oxidation of Cyclohexane by High-Valent Iron Bispidine Complexes: Tetradentate versus Pentadentate Ligands</i> in <a href="Inorg._Chem." class="mw-redirect" title="Inorg. Chem.">Inorg. Chem.</a> 48 (2009) 10389–10396, <a href="Digital_Object_Identifier" title="Digital Object Identifier">doi</a>:<span class="uri-handle" style="white-space:nowrap"><a rel="nofollow" class="external text" href="https://doi.org/10.1021/ic901702s">10.1021/ic901702s</a></span>.</span>
</li>
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