Trimethine pyrylium dyes

The synthesis and electronic absorption spectra of some pyranylidene trimethine pyrylium salts are described.     

Synthesis of 2[(4,6-diphenyl-2H-pyran-2-ylidene)methyl]-4,6-diphenylpyrylium perchlorate

The title compound was prepared by the condensation of 4,6-diphenyl-2H-pyran-2-one and acetophenone in phosphorus oxychloride. The absorption spectrum of this 2,2-methine dye is compared with those of the corresponding 2,4- and 4,4-methine dyes.     

Aquation of (N,Ndimethylformamide) pentaamminecobalt (III) perchlorate in aqueous perchlorate media

The first-order rate constants for aquation of Co(NH₃)₅(DMF)³⁺ were determined in aqueous perchlorate media. The rate constants were independent of hydrogen ion concentration and ionic strength, but decreased with increasing perchlorate ion concentration. Proton magnetic resonance studies showed that dimethylformamide was not hydrolyzed to formic acid and dimethylamine in the aquation step. Mass-spectrometer studies showed that cobalt–oxygen bond breaking occurred in 98 percent, or more, of the aquation acts. Enthalpies and entropies of activation were determined. It was concluded that aquation occurred by an I_d mechanism.     

Demetallation of α,β,γ,δ-tetrakis(p-sulfophenyl) porphiniron(III) in mineral acid–alcohol–water media

Demetallation rates of α,β,γ,δ-tetrakis(p-sulfophenyl)porphiniron(III) in hydrochloric acid–ethanol–water, perchloric acid–ethanol–water, and sulfuric acid–alcohol–water media were determined. For a given acidity value H₀ the order of the rates for the three acids was HCl > H₂SO₄ > HClO₄. This is also the order for complex formation between acid anion and iron(III). Consequently ligands as well as protons are involved in the breaking of bonds between the metal and the porphyrin leading to the formation of the activated complex. The log k values for HCl and HClO₄ media were not linearly related to the Hammett acidity function as they were for sulfuric acid–ethanol–water media. The average ΔH? and ΔS?values for the HCl media were 18.4 ± 1.4 kcal/mol and ? 19 ± 3 cal K mol, respectively, in very close agreement with those for H₂SO₄ media despite the difference in H ₀ dependence. For H₂SO₄–alcohol–water media the order of the rates was butanol > propanol > ethanol with little difference between isomeric alcohols.     

Hydrolysis of acetylcholinesterase inhibitors--organophosphorus acid anhydrolase enzyme immobilization on photoluminescent porous silicon platforms

We report on the immobilization of an OPAA enzyme on luminescent porous silicon devices, and on the utilization of this new platform to hydrolyze p-nitrophenyl-soman.     

The determination of glycerol : General introduction: volumetric determination as the copper complex

A method for the determination of glycerol by means of the copper-glycerol complex is described; the complex is filtered free of excess copper(II) hydroxide and the copper is determined iodimetrically. Earlier difficulties due to adsorption of the complex are overcome by the use of glass-fibre filter discs. The method gives accurate results in the range 40-4% glycerol in the solution (400 to 40 mg glycerol in the aliquot taken).     

The structure of some methyl and benzyl malonate derivatives of pyrimidine

Reaction of 2,4,6-trichloropyrimidine with sodium dibenzylmalonate in p-dioxane gave 4,6-dichloro-2-(dibenzylmalonyl)pyrimidine, while reaction of 2,4,6-trichloropyrimidine with sodium dimethylmalonate yielded both 4,6-dichloro-2-(dimethylmalonyl)pyrimidine and 2,2-bis-(4,6-dichloropyrimidin-2-yl)dimethylmalonate. Structural studies using nmr, ir and uv spectroscopy indicate that for the former two compounds in basic solvent, an equilibrium exists between the keto forms and resonance-stabilized enolate ions.