Synthesis of Benzothiadiazole Derivatives by Applying C–C Cross-Couplings

Juha P. Heiskanen, Paola Vivo, Niko M. Saari, Terttu I. Hukka, Tuuva Kastinen, Kimmo Kaunisto, Helge J. Lemmetyinen, Osmo E.O. Hormi

    Research output: Contribution to journalArticleScientificpeer-review

    23 Citations (Scopus)

    Abstract

    The benzothiadiazole moiety has been extensively exploited as a building block in the syntheses of efficient organic semiconducting materials during the past decade. In this paper, parallel synthetic routes to benzothiadiazole derivatives, inspired by previous computational findings, are reported. The results presented here show that various C–C cross-couplings of benzothiadiazole, thiophene, and thiazole derivatives can be efficiently performed by applying Xantphos as a ligand of the catalyst system. Moreover, improved and convenient methods to synthesize important chemical building blocks, e.g., 4,7-dibromo-2,1,3-benzothiadiazole, in good to quantitative yields are presented. Additionally, the feasibility of Suzuki–Miyaura and direct coupling methods are compared in the synthesis of target benzothiadiazole derivatives. The computational characterization of the prepared benzothiadiazole derivatives shows that these compounds have planar molecular backbones and the possibility of intramolecular charge transfer upon excitation. The experimental electrochemical and spectroscopic studies reveal that although the compounds have similar electronic and optical properties in solution, they behave differently in solid state due to the different alkyl side-group substitutions in the molecular backbone. These benzothiadiazole derivatives can be potentially used as building blocks in the construction of more advanced small molecule organic semiconductors with acceptor–donor–acceptor motifs.
    Original languageEnglish
    Pages (from-to)1535–1546
    Number of pages12
    JournalJournal of Organic Chemistry
    Volume81
    Issue number4
    DOIs
    Publication statusPublished - 15 Jan 2016
    Publication typeA1 Journal article-refereed

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    • Publication forum level 2

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