Chen, Shu-Ling ; Klein, Roland ; Hafner, Klaus (1998)
Synthesis and Properties of syn-[2.2](1,6)- and (4,6)Azulenophanes and Macrocyclic Azulenophanes.
In: European Journal of Organic Chemistry, 1998 (3)
doi: 10.1002/(SICI)1099-0690(199803)1998:3%3C423::AID-EJOC423%3E3.0.CO;2-E
Article, Bibliographie
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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.
| Item Type: | Article |
|---|---|
| Erschienen: | 1998 |
| Creators: | Chen, Shu-Ling ; Klein, Roland ; Hafner, Klaus |
| Type of entry: | Bibliographie |
| Title: | Synthesis and Properties of syn-[2.2](1,6)- and (4,6)Azulenophanes and Macrocyclic Azulenophanes |
| Language: | English |
| Date: | 1998 |
| Place of Publication: | Darmstadt |
| Publisher: | Wiley-VCH |
| Journal or Publication Title: | European Journal of Organic Chemistry |
| Volume of the journal: | 1998 |
| Issue Number: | 3 |
| DOI: | 10.1002/(SICI)1099-0690(199803)1998:3%3C423::AID-EJOC423%3E3.0.CO;2-E |
| Corresponding Links: | |
| 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. |
| Uncontrolled Keywords: | 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 |
| Classification DDC: | 500 Science and mathematics > 540 Chemistry |
| Divisions: | 07 Department of Chemistry 07 Department of Chemistry > Clemens-Schöpf-Institut 07 Department of Chemistry > Clemens-Schöpf-Institut > Organ Chemistry |
| Date Deposited: | 02 Aug 2024 12:45 |
| Last Modified: | 02 Aug 2024 12:45 |
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Synthesis and Properties of syn-[2.2](1,6)- and (4,6)Azulenophanes and Macrocyclic Azulenophanes. (deposited 22 Nov 2022 10:14)
- Synthesis and Properties of syn-[2.2](1,6)- and (4,6)Azulenophanes and Macrocyclic Azulenophanes. (deposited 02 Aug 2024 12:45) [Currently Displayed]
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