Elsevier

Tetrahedron

Volume 44, Issue 9, 1988, Pages 2397-2402
Tetrahedron

A novel synthesis of cis-1-[[6-chloro-3-[(2-chloro-3-thienyl)methoxy]-2,3-dihydrobenzo[b]thien-2-yl]methyl]1h-imidazole : A new class of azole antifungal agents

https://doi.org/10.1016/S0040-4020(01)81691-4Get rights and content

Abstract

Ring contraction of cis-3-bromo-7-chloro-3,4-dihydro-2H-1-benzothiopyran-4-ol 4 in the presence of imidazole results in formation of cis-6-chloro-2,3-dihydro-2-(1H-imidazol-1-ylmethyl) benzo[b]thiophene-3-ol 8 as the major product. The structure of 8 was defined unequivocally by X-ray analysis of a solvated (ethyl acetate) and an unsolvated crystal form. Alkylation of 8 with 3-(bromomethyl)-2-chlorothiophene gave cis-1-[[6-chloro-3-[(2-chloro-3-thienyl)methoxy]-2,3-dihydrobenzor[b] thien-2-yl]methyl]lH-imidazole 9, a representative of a new class of azole antifungal agents.

References (11)

  • J.F. Ryley et al.

    Advances in Pharmacology and Chemotherapy

    (1981)
  • H. Hofmann et al.
  • Sae-Lee Chu et al.

    Hua Hsueh Hsueh Pao

    (1956)
  • M.D. Cotterill et al.

    J. Chem. Soc., Perkin Trans. 1

    (1972)
  • A. Chatterjee et al.

    Indian J. Chem.

    (1973)
There are more references available in the full text version of this article.

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