GABA receptor antagonists and insecticides: common structural features of 4-alkyl-1-phenylpyrazoles and 4-alkyl-1-phenyltrioxabicyclooctanes

Bioorg Med Chem. 2004 Jun 15;12(12):3345-55. doi: 10.1016/j.bmc.2004.03.069.

Abstract

Fipronil [5-amino-3-cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)-4-trifluoromethylsulfinylpyrazole] is one of the most important insecticides. Structure-activity studies described here reveal that fipronil retains its very high binding potency at the human beta3 and house fly gamma-aminobutyric acid (GABA) receptors and toxicity to house flies on replacing the pyrazole trifluoromethylsulfinyl moiety with tert-butyl or isopropyl and the phenyl trifluoromethyl substituent with ethynyl, trifluoromethoxy, bromo or chloro. Among the compounds studied, those with other alkyl groups at the 4-position of the pyrazole, as well as phenyl substitution without one or both of the 2,6-dichloro groups, are less effective. 5-Amino-4-tert-butyl-3-cyano-1-(2,6-dichloro-4-ethynylphenyl)pyrazole is highly effective and almost isosteric with 4-tert-butyl-3-cyano-1-(4-ethynylphenyl)-2,6,7-trioxabicyclo[2.2.2]octane (the most potent 4-alkyl-1-phenyltrioxabicyclooctane) as a noncompetitive GABA antagonist and insecticide. These findings are interpreted as three binding subsites in the GABA receptor: a hydrophobic site undergoing steric interaction with the tert-butyl or equivalent group; a hydrogen bonding site to pyrazole N-2; a pi bonding site to the face of the phenyl moiety; with supplemental enhancement by the 3-cyano and 4-ethynyl substituents.

Publication types

  • Research Support, U.S. Gov't, P.H.S.

MeSH terms

  • Alkylation
  • Animals
  • Cyclooctanes / chemical synthesis
  • Cyclooctanes / chemistry*
  • Cyclooctanes / pharmacology*
  • Cyclooctanes / toxicity
  • Diptera / drug effects
  • Diptera / physiology
  • GABA Antagonists / chemistry*
  • GABA Antagonists / pharmacology
  • Humans
  • Inhibitory Concentration 50
  • Insecticides / chemistry*
  • Insecticides / pharmacology
  • Insecticides / toxicity
  • Molecular Conformation
  • Molecular Structure
  • Pyrazoles / chemical synthesis
  • Pyrazoles / chemistry*
  • Pyrazoles / pharmacology*
  • Pyrazoles / toxicity
  • Receptors, GABA / metabolism*
  • Structure-Activity Relationship

Substances

  • Cyclooctanes
  • GABA Antagonists
  • Insecticides
  • Pyrazoles
  • Receptors, GABA
  • fipronil