Efficient synthesis of 2,5-dicarbonyl derivatives of 3,4-ethylenedithiothiophene (EDTT) via addition-elimination reaction

Al-jumaili, Mustafa A-jabbar; Woodward, Simon

Abstract

Derivatives of 3,4-ethylenedithiothiophene (EDTT) are reported starting from tetrabromothiophene. Selective 2,5-dilithiation followed by reaction with a range of aldehydes gives diols as mixtures of diastereomers. Only the 2 and 5 positions in thiophene react leaving the 3,4-bromides for further elaboration. The diols are oxidised to their corresponding diketones using activated MnO2. Reaction with 1,2-ethanedithiol, by addition-elimination, provides access to novel monomers for the preparation of conjugated copolymers of 3,4-ethylenedithiothiophene (EDTT). A range of these monomers can be attained by applying the synthesis of a series of ketones applicable to further synthesis of π-extended thiophene-based organic semiconductors. Finally, this new route was compared to 3,4-ethylenedioxythiophene (EDOT) dialdehyde derivatives synthesised by an alternative to literature chemistry.

Citation

Al-jumaili, M. A.-J., & Woodward, S. (2017). Efficient synthesis of 2,5-dicarbonyl derivatives of 3,4-ethylenedithiothiophene (EDTT) via addition-elimination reaction. Tetrahedron, 73(40), https://doi.org/10.1016/j.tet.2017.08.026

• Journal Article Type: Article
• Acceptance Date: Aug 14, 2017
• Online Publication Date: Aug 18, 2017
• Publication Date: Oct 5, 2017
• Deposit Date: Sep 8, 2017
• Publicly Available Date: Aug 19, 2018
• Journal: Tetrahedron
• Print ISSN: 0040-4020
• Electronic ISSN: 0040-4020
• Publisher: Elsevier
• Peer Reviewed: Peer Reviewed
• Volume: 73
• Issue: 40
• DOI: https://doi.org/10.1016/j.tet.2017.08.026
• Keywords: Addition-elimination reaction; 3,4-Ethylenedithiothiophene; 1,2-Ethanedithiol; Organic semiconductors; EDTT
• Public URL: https://nottingham-repository.worktribe.com/output/886239
• Publisher URL: http://www.sciencedirect.com/science/article/pii/S0040402017308578?via%3Dihub
• Contract Date: Sep 8, 2017