The synthesis and reactions of thienopyridines

  • Kenneth Wilson

    Student thesis: Doctoral Thesis

    Abstract

    The synthesis of ortho-halogenated pyridine derivatives (A-D; R = CN, CO2Et; R1 = CN, CO2Me, CO2Et) containing methylene groups activated by the nitrile or ester functionality is described. Derivatives (A-D) are reacted with carbon disulfide in the presence of base, followed by alkylation with iodomethane, to afford novel thienopyridines (E-H; R = CN, CO2Et; R1 = CN, CO2Me, CO2Et; X = SMe).

    Pyridine derivative (B; R = CN) also reacts with phenyl isothiocyanate to form thienopyridine (F; R = CN; X = NHPh). Reaction of the nitriles (A, C and D; R, R1 = CN) under identical conditions, however, does not give the bicyclic compounds but ketene dithioacetals (I, J and K). Increasing the reaction temperature allows formation of thienopyridines (E, G and H; R, R1 = CN; X = NHPh). Thienopyridines R = CO2Et; R1 = CO2Me, CO2Et; X = NHPh) are also synthesised from the ruction of the derivatives (A-D; R = CO2Et; = CO2Me; CO2Et) with phenyl isothiocyanate.

    Reaction of nitrile (A; R1 = CN) with carbon disulfide in the presence of base, followed by quenching with ethyl chloroacetate affords thienopyridine (E; R1 = CN; X = SCH2CO2Et) which in turn cyclises with base to give tricyclic compound (L).

    Thienopyridines (E; R1 = NH2; X = CN, Ph, CO2Et, COMe, COPh, COCH2CO2Et) are synthesised from reactions of 3-cyanopyridine-2(lH)-thione with compounds containing a halogen atom adjacent to an active methylene group.

    Nucleophilic reactions of thienopyridines (E; R1 = CN; X = SMe, SOMe, SO2Me) are investigated, in an attempt to prepare tricyclic compounds.
    Date of AwardJan 1992
    LanguageEnglish
    SupervisorDavid H. Bremner (Supervisor)

    Cite this

    The synthesis and reactions of thienopyridines
    Wilson, K. (Author). Jan 1992

    Student thesis: Doctoral Thesis