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Synthesis, structures and conformational studies of 1,2-dimethyl[2.10]metacyclophane-1-enes

Akther, Thamina; Islam, Md Monarul; Rahman, Shofiur; Georghiou, Paris E.; Matsumoto, Taisuke; Tanaka, Junji; Thuéry, Pierre; Redshaw, Carl; Yamato, Takehiko

Authors

Thamina Akther

Md Monarul Islam

Shofiur Rahman

Paris E. Georghiou

Taisuke Matsumoto

Junji Tanaka

Pierre Thuéry

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Professor Carl Redshaw C.Redshaw@hull.ac.uk
Professor of Inorganic Materials Chemistry and REF Lead for Chemistry

Takehiko Yamato

Abstract

A series of 1,2-dimethyl[2.10]metacyclophan-1-enes (MCP-1-enes) containing different substituent groups has been synthesized to illustrate their conformational behavior. 4,22-dimethoxy-1,2-dimethyl[2.10]MCP-1-ene 3 was synthesized by a Grignard coupling reaction, Friedel-Crafts acylation reactions and McMurry coupling reaction from 1,10-dibromodecane. The formation of 4,22-dihydroxy-1,2-dimethyl[2.10]MCP-1-ene 4 was carried out by demethylation of compound 3 with boron tribromide at room temperature. The syn type conformation of 4 was characterized by X-ray diffraction and was found to form both intramolecular and intermolecular hydrogen bonds between the two hydroxyl groups. From this reaction an interesting compound [10]tetrahydrobenzofuranophane 5 was afforded on prolonging the reaction time. 5,21-diformyl-4,22-dihydroxy-1,2-dimethyl[2.10]MCP-1-ene 6 has been prepared from 4,22-dihydroxy-1,2-dimethyl[2.10]MCP-1-ene 4 by using the Duff method in the presence of hexamethylenetetramine. Structural analysis by 1H NMR spectroscopy and X-ray diffraction confirmed that both the solution and the crystalline state of compound 6 adopts an anti-conformation which forms an intramolecular hydrogen bond between the formyl group and the hydroxyl group, which is an interesting finding for long carbon chain MCP compounds.

Journal Article Type Article
Publication Date Aug 16, 2016
Journal ChemistrySelect
Electronic ISSN 2365-6549
Publisher Wiley
Peer Reviewed Peer Reviewed
Volume 1
Issue 13
Pages 3594-3600
Institution Citation Akther, T., Islam, M. M., Rahman, S., Georghiou, P. E., Matsumoto, T., Tanaka, J., …Yamato, T. (2016). Synthesis, structures and conformational studies of 1,2-dimethyl[2.10]metacyclophane-1-enes. ChemistrySelect, 1(13), 3594-3600. doi:10.1002/slct.201600670
DOI https://doi.org/10.1002/slct.201600670
Keywords Metacyclophane derivatives, Demethylation, McMurry cyclization, Conformational studies, Intramolecular hydrogen bond
Publisher URL http://onlinelibrary.wiley.com/doi/10.1002/slct.201600670/abstract;jsessionid=DFE8A09A12C0B772E2576B3079DF37CA.f04t04
Additional Information This is the peer reviewed version of the following article: T. Akther, M. M. Islam, S. Rahman, P. E. Georghiou, T. Matsumoto, J. Tanaka, P. Thuéry, C. Redshaw, T. Yamato, ChemistrySelect 2016, 1, 3594, which has been published in final form at http://dx.doi.org/ 10.1002/slct.201600670. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Self-Archiving.

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