Chen, Shu-Ling ; Klein, Roland ; Hafner, Klaus (2022)
Synthesis and Properties of syn-[2.2](1,6)- and (4,6)Azulenophanes and Macrocyclic Azulenophanes.
In: European Journal of Organic Chemistry, 1998, 1998 (3)
doi: 10.26083/tuprints-00022401
Artikel, Zweitveröffentlichung, Verlagsversion
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Kurzbeschreibung (Abstract)
A regioselective synthesis of syn-[2.2](1,6)azulenophane (9) and syn-[2.2](4,6)azulenophane (12) is described. Azulenophane 9 is prepared by deprotonation of 1,2-bis(6-methylazulen-1-yl)ethane (5), followed by oxidative coupling of the initially formed dilithium salt 8 with iodine under high-dilution conditions in 17% yield, along with the macrocyclic [2.2.2.2](1,6)azulenophane (10) (3%), and [2.2.2.2.2.2](1,6)azulenophane (11) (1.5%). The azulenophane 12 and the macrocyclic [2.2.2.2](4,6)azulenophane (13) are obtained by coupling of the dianion of 1,2-bis(4-methylazulen-6-yl)ethane (14). The structural assignments of the title compounds are based on their spectral data. Protonation of 9 furnishes the mono- and dications 24 and 25, respectively, of which the first exhibits a charge-transfer band in its electronic spectrum, indicating a transannular interaction between the protonated and unprotonated azulene units. Protonation of 12 yields the mono- and dications 26 and 27, respectively. In contrast to 24, no new band due to an intramolecular transannular charge-transfer interaction is observed in the electronic spectrum of 26, and this is due to an insufficient overlap between the protonated and unprotonated azulene decks in 26. Vilsmeier formylation of 9 with 1.5 mol equivalents of phosphoryl chloride in DMF at room temp. yields 3-formyl-syn-[2.2](1,6)azulenophane (28) in 15% yield. Under the same reaction conditions a double formylation of 9 with 3 mol equivalents of phosphoryl chloride leads to 3,3′-diformyl-syn-[2.2](1,6)azulenophane (29) in 42% yield. The aminomethylation of 9 with paraformaldehyde and N, N, N′, N′-tetramethyldiaminomethane in the presence of acetic acid furnishes the Mannich bases 3-N, N-dimethylaminomethyl-syn-[2.2](1,6)azulenophane (30) and 3,3′-bis(N, N-dimethylaminomethyl)-syn-[2.2](1,6)azulenophane (31) in 40% and 46% yields, respectively.
| Typ des Eintrags: | Artikel |
|---|---|
| Erschienen: | 2022 |
| Autor(en): | Chen, Shu-Ling ; Klein, Roland ; Hafner, Klaus |
| Art des Eintrags: | Zweitveröffentlichung |
| Titel: | Synthesis and Properties of syn-[2.2](1,6)- and (4,6)Azulenophanes and Macrocyclic Azulenophanes |
| Sprache: | Englisch |
| Publikationsjahr: | 2022 |
| Ort: | Darmstadt |
| Publikationsdatum der Erstveröffentlichung: | 1998 |
| Verlag: | Wiley-VCH |
| Titel der Zeitschrift, Zeitung oder Schriftenreihe: | European Journal of Organic Chemistry |
| Jahrgang/Volume einer Zeitschrift: | 1998 |
| (Heft-)Nummer: | 3 |
| DOI: | 10.26083/tuprints-00022401 |
| URL / URN: | https://tuprints.ulb.tu-darmstadt.de/22401 |
| Zugehörige Links: | |
| Herkunft: | Zweitveröffentlichungsservice |
| Kurzbeschreibung (Abstract): | A regioselective synthesis of syn-[2.2](1,6)azulenophane (9) and syn-[2.2](4,6)azulenophane (12) is described. Azulenophane 9 is prepared by deprotonation of 1,2-bis(6-methylazulen-1-yl)ethane (5), followed by oxidative coupling of the initially formed dilithium salt 8 with iodine under high-dilution conditions in 17% yield, along with the macrocyclic [2.2.2.2](1,6)azulenophane (10) (3%), and [2.2.2.2.2.2](1,6)azulenophane (11) (1.5%). The azulenophane 12 and the macrocyclic [2.2.2.2](4,6)azulenophane (13) are obtained by coupling of the dianion of 1,2-bis(4-methylazulen-6-yl)ethane (14). The structural assignments of the title compounds are based on their spectral data. Protonation of 9 furnishes the mono- and dications 24 and 25, respectively, of which the first exhibits a charge-transfer band in its electronic spectrum, indicating a transannular interaction between the protonated and unprotonated azulene units. Protonation of 12 yields the mono- and dications 26 and 27, respectively. In contrast to 24, no new band due to an intramolecular transannular charge-transfer interaction is observed in the electronic spectrum of 26, and this is due to an insufficient overlap between the protonated and unprotonated azulene decks in 26. Vilsmeier formylation of 9 with 1.5 mol equivalents of phosphoryl chloride in DMF at room temp. yields 3-formyl-syn-[2.2](1,6)azulenophane (28) in 15% yield. Under the same reaction conditions a double formylation of 9 with 3 mol equivalents of phosphoryl chloride leads to 3,3′-diformyl-syn-[2.2](1,6)azulenophane (29) in 42% yield. The aminomethylation of 9 with paraformaldehyde and N, N, N′, N′-tetramethyldiaminomethane in the presence of acetic acid furnishes the Mannich bases 3-N, N-dimethylaminomethyl-syn-[2.2](1,6)azulenophane (30) and 3,3′-bis(N, N-dimethylaminomethyl)-syn-[2.2](1,6)azulenophane (31) in 40% and 46% yields, respectively. |
| Freie Schlagworte: | syn-[2.2](1,6)Azulenophane / syn-[2.2](4,6)Azulenophane / [2.2.2.2](1,6)-Azulenophane /[2.2.2.2.2.2](1,6)Azulenophane / [2.2.2.2](4,6)Azulenophane / Phanes |
| Status: | Verlagsversion |
| URN: | urn:nbn:de:tuda-tuprints-224013 |
| Sachgruppe der Dewey Dezimalklassifikatin (DDC): | 500 Naturwissenschaften und Mathematik > 540 Chemie |
| Fachbereich(e)/-gebiet(e): | 07 Fachbereich Chemie 07 Fachbereich Chemie > Clemens-Schöpf-Institut 07 Fachbereich Chemie > Clemens-Schöpf-Institut > Fachgebiet Organische Chemie |
| Hinterlegungsdatum: | 22 Nov 2022 10:14 |
| Letzte Änderung: | 02 Aug 2024 12:45 |
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Verfügbare Versionen dieses Eintrags
- Synthesis and Properties of syn-[2.2](1,6)- and (4,6)Azulenophanes and Macrocyclic Azulenophanes. (deposited 22 Nov 2022 10:14) [Gegenwärtig angezeigt]
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