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International audience; (E)-3-Arylidenechroman-4-ones 1a–e (Ar = Ph, p-MeC6H4, p-MeOC6H4, p-MeSC6H4, p-ClC6H4) react regioselectively (100%) with ethyl diazoacetate 2 in refluxing toluene to afford in good yields spiro-Δ2-pyrazolines ethyl 4’-oxo-4-aryl-spiro[chromanone-3’,5-pyrazole]-3-carboxylate 3a–e. The occurrence of Δ1-pyrazolines as reaction intermediates has been evidenced. The regio- and stereochemistry of spiranic compounds 3a-e has been established on the basis of spectroscopic data and elemental analyses, corroborated by a single crystal X-ray crystallographic analysis of one product 3a. The spiro-adducts 3a–e were brominated by NBS to give spirocyclic-substituted 3-bromo-4,5-dihydro-3H-pyrazoles 4a–e. The latter compounds evolve straightforwardly N2 in refluxing toluene to afford substituted spirocyclic 1-bromocyclopropane-1-carboxylates. The molecular structure of cyclopropane derivative 5e has been determined by means of a single-crystal X-ray diffraction study.

Potentiometric titrations, fluorescence versus pH titrations, dynamic light scattering and fluorescence polarization anisotropy studies demonstrate that inside the nanodimensioned Triton X-100 micelles, 1-pyrenecarboxylic acid, PCOO-, forms an apical complex with the Zn2+ cation encircled by a lipophilic cyclen ligand and hugely increasing its fluorescence. The ability of the Zn2+-cyclen-PCOO- complex plus its micellar container to act as a fluorescent sensor to evaluate the lipophilicity of molecular species is demonstrated on the fatty acid series CH 3(CH2)xCOOH (x=0-16). At pH 7.4 a decrease in fluorescence is observed on the addition of fatty acids that is directly related to their chain length, that is, to their tendency to enter the micellar containers, where they dislocate PCOO- from the Zn2+ centre. The independent determination of fatty acid pKa values in the presence of Triton X-100 micelles confirms that our fluorescent micellar device is capable of sensing their lipophilicity. © 2008 Wiley-VCH Verlag GmbH & Co. KGaA.