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

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 ela...

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Main Authors: Al-jumaili, Mustafa A-jabbar, Woodward, Simon
Format: Article
Published: Elsevier 2017
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Online Access:https://eprints.nottingham.ac.uk/45539/
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author Al-jumaili, Mustafa A-jabbar
Woodward, Simon
author_facet Al-jumaili, Mustafa A-jabbar
Woodward, Simon
author_sort Al-jumaili, Mustafa A-jabbar
building Nottingham Research Data Repository
collection Online Access
description 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.
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spelling nottingham-455392020-05-04T19:10:37Z https://eprints.nottingham.ac.uk/45539/ Efficient synthesis of 2,5-dicarbonyl derivatives of 3,4-ethylenedithiothiophene (EDTT) via addition-elimination reaction Al-jumaili, Mustafa A-jabbar Woodward, Simon 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. Elsevier 2017-10-05 Article PeerReviewed Al-jumaili, Mustafa A-jabbar and Woodward, Simon (2017) Efficient synthesis of 2,5-dicarbonyl derivatives of 3,4-ethylenedithiothiophene (EDTT) via addition-elimination reaction. Tetrahedron, 73 (40). pp. 5847-5852. ISSN 0040-4020 Addition-elimination reaction; 3 4-Ethylenedithiothiophene; 1 2-Ethanedithiol; Organic semiconductors; EDTT http://www.sciencedirect.com/science/article/pii/S0040402017308578?via%3Dihub doi:10.1016/j.tet.2017.08.026 doi:10.1016/j.tet.2017.08.026
spellingShingle Addition-elimination reaction; 3
4-Ethylenedithiothiophene; 1
2-Ethanedithiol; Organic semiconductors; EDTT
Al-jumaili, Mustafa A-jabbar
Woodward, Simon
Efficient synthesis of 2,5-dicarbonyl derivatives of 3,4-ethylenedithiothiophene (EDTT) via addition-elimination reaction
title Efficient synthesis of 2,5-dicarbonyl derivatives of 3,4-ethylenedithiothiophene (EDTT) via addition-elimination reaction
title_full Efficient synthesis of 2,5-dicarbonyl derivatives of 3,4-ethylenedithiothiophene (EDTT) via addition-elimination reaction
title_fullStr Efficient synthesis of 2,5-dicarbonyl derivatives of 3,4-ethylenedithiothiophene (EDTT) via addition-elimination reaction
title_full_unstemmed Efficient synthesis of 2,5-dicarbonyl derivatives of 3,4-ethylenedithiothiophene (EDTT) via addition-elimination reaction
title_short Efficient synthesis of 2,5-dicarbonyl derivatives of 3,4-ethylenedithiothiophene (EDTT) via addition-elimination reaction
title_sort efficient synthesis of 2,5-dicarbonyl derivatives of 3,4-ethylenedithiothiophene (edtt) via addition-elimination reaction
topic Addition-elimination reaction; 3
4-Ethylenedithiothiophene; 1
2-Ethanedithiol; Organic semiconductors; EDTT
url https://eprints.nottingham.ac.uk/45539/
https://eprints.nottingham.ac.uk/45539/
https://eprints.nottingham.ac.uk/45539/