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Synthesis and Properties of syn-[2.2](1,6)- and (4,6)Azulenophanes and Macrocyclic Azulenophanes

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
Article, Secondary publication, Publisher's Version

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Eur J Org Chem - March 1998 - Chen - Synthesis and Properties of syn‐ 2 2 1 6 ‐ and 4 6 Azulenophanes and Macrocyclic.pdf
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Item Type: Article
Type of entry: Secondary publication
Title: Synthesis and Properties of syn-[2.2](1,6)- and (4,6)Azulenophanes and Macrocyclic Azulenophanes
Language: English
Date: 2022
Place of Publication: Darmstadt
Year of primary publication: 1998
Publisher: Wiley-VCH
Journal or Publication Title: European Journal of Organic Chemistry
Volume of the journal: 1998
Issue Number: 3
DOI: 10.26083/tuprints-00022401
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Origin: Secondary publication service

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 [](1,6)azulenophane (10) (3%), and [](1,6)azulenophane (11) (1.5%). The azulenophane 12 and the macrocyclic [](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.

Uncontrolled Keywords: syn-[2.2](1,6)Azulenophane / syn-[2.2](4,6)Azulenophane / [](1,6)-Azulenophane /[](1,6)Azulenophane / [](4,6)Azulenophane / Phanes
Status: Publisher's Version
URN: urn:nbn:de:tuda-tuprints-224013
Classification DDC: 500 Science and mathematics > 540 Chemistry
Divisions: 07 Department of Chemistry > Clemens-Schöpf-Institut > Organ Chemistry
Date Deposited: 22 Nov 2022 10:14
Last Modified: 21 Apr 2023 12:48
URI: https://tuprints.ulb.tu-darmstadt.de/id/eprint/22401
PPN: 507159578
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