Pyrolysis of aminonitriles,cyanohydrazones, and cyanoacetamides. Part I. Elimination reaction of 1-arylmethyleneamino-1,2-dihydro-4,6-dimethyl-2-oxopyridine-3-carbonitriles and substituted benzaldehyde cyanoacetylhydrazones

Pyrolysis of the Schiff bases of 1-arylmethyleneamino-1,2-dihydro-4,6-dimethyl-2-oxopyridine-3-carbonitriles (1–5) has been studied. These compounds eliminate via a six-membered transition state to produce substituted benzonitriles and 2-hydroxy-4,6-dimethylpyridine-3-carbonitrile. These eliminations are unimolecular first-order reactions. The kinetic data gave a good correlation with σ⁰ values of the substituents on the aryl group with ρ = 0.83 at 520 K. Utilization of the pyrolytic reaction in synthesis of various benzonitriles is considered, and mechanistic information has been obtained by comparing the kinetic data and product analysis of the Schiff bases with their open-chain substituted benzaldehyde cyanoacetylhydrazones (6–9) analogues. © 1996 John Wiley & Sons, Inc.     

Carbon–chalcogen bond formation initiated by [Al(NONDipp)(E)]− anions containing Al–E{16} (E{16} = S,Se) multiple bonds

Multiply-bonded main group metal compounds are of interest as a new class of reactive species able to activate and functionalize a wide range of substrates. The aluminium sulfido compound K[Al(NON^Dipp)(S)] (NON^Dipp = [O(SiMe₂NDipp)₂]²⁻, Dipp = 2,6-ⁱPr₂C₆H₃), completing the series of [Al(NON^Dipp)(E)]⁻ anions containing Al–E{16} multiple bonds (E{16} = O, S, Se, Te), was accessed via desulfurisation of K[Al(NON^Dipp)(S₄)] using triphenylphosphane. The crystal structure showed a tetrameric aggregate joined by multiple K⋯S and K⋯π(arene) interactions that were disrupted by the addition of 2.2.2-cryptand to form the separated ion pair, [K(2.2.2-crypt)][Al(NON^Dipp)(S)]. Analysis of the anion using density functional theory (DFT) confirmed multiple-bond character in the Al–S group. The reaction of the sulfido and selenido anions K[Al(NON^Dipp)(E)] (E = S, Se) with CO₂ afforded K[Al(NON^Dipp)(κ²E,O-EC{O}O)] containing the thio- and seleno-carbonate groups respectively, consistent with a [2 + 2]-cycloaddition reaction and C–E bond formation. An analogous cycloaddition reaction took place with benzophenone affording compounds containing the diphenylsulfido- and diphenylselenido-methanolate ligands, [κ²E,O-EC{O}Ph₂]²⁻. In contrast, when K[Al(NON^Dipp)(E)] (E = S, Se) was reacted with benzaldehyde, two equivalents of substrate were incorporated into the product accompanied by formation of a second C–E bond and complete cleavage of the Al–E{16} bonds. The products contained the hitherto unknown κ²O,O-thio- and κ²O,O-seleno-bis(phenylmethanolate) ligands, which were exclusively isolated as the cis-stereoisomers. The mechanisms of these cycloaddition reactions were investigated using DFT methods.

Reaction of Al–E (E = S, Se) multiple bonds with C O functionalities generates new C–E bonds.     

Copper(II) tetrafluroborate-promoted Meinwald rearrangement reactions of epoxides

Epoxides undergo a highly efficient Meinwald rearrangement in the presence of catalytic quantities of copper(II) tetrafluoroborate to give carbonyl compounds in high yields and with excellent selectivity. The low toxicity and ease of handling of this reagent make it an attractive alternative to the more corrosive or costly Lewis acids frequently employed.     

Synthesis of alkylpyrroles by use of a vinamidinium salt

The synthesis of alkyl-substituted 2-pyrrolecarboxylate esters has been accomplished by the condensation reaction of a symmetrical vinamidinium salt and glycine ester derivatives.     

Flotation-spectrophotometric method for the determination of mercury using iodide and brilliant green

This paper describes a sensitive spectrophotometric method for the determination of mercury, based on the flotation of a mercury iodide-brilliant green complex with cyclohexane at pH 5 and dissolution of the complex in acetone. The absorbance of the complex is measured at 625 nm. Beer's law is obeyed from 4–500 g/l of mercury. The method is highly sensitive ( = 5.96 × 10⁵ 1 mol^–1 cm^–1) and selective, as it is free from interferences by almost all cations and anions in the presence of EDTA. Furthermore, a two-level orthogonal array design as a chemometric method has been used for optimization of the various parameters involved. The method has been successfully applied to paper industry effluents.     

Redox-Mediated Alcohol Oxidation Coupled to Hydrogen Gas Formation in a Dye-Sensitized Photosynthesis Cell

This work reports a dye-sensitized photoelectrochemical cell (DSPEC) that couples redox-mediated light-driven oxidative organic transformations to reductive hydrogen (H₂) formation. The DSPEC photoanode consists of a mesoporous anatase TiO₂ film on FTO (fluorine-doped tin oxide), sensitized with the thienopyrroledione-based dye AP11 , while H₂ was formed at a FTO-Pt cathode. Irradiation of the dye-sensitized photoanode transforms 2,2,6,6-tetramethylpiperidine 1-oxyl (TEMPO) to the oxidized TEMPO (TEMPO⁺), which acts as a chemical oxidant for the conversion of benzyl alcohol. The TEMPO^0/+ couple, previously used as redox mediator in DSSC, mediates efficient electron transfer from the organic substrate to the photo-oxidized dye. A DSPEC photoreactor was designed that allows in situ monitoring the reaction progress by infrared spectroscopy and gas chromatography. Sustained light-driven oxidation of benzyl alcohol to benzaldehyde within the DSPEC photoreactor, using of TEMPO as mediator, demonstrated the efficiency of the device, with a photocurrent of 0.4 mA cm⁻², approaching quantitative Faradaic efficiency and exhibiting excellent device stability.     

Disposition Kinetics of Amitraz in Lactating Does

Amitraz, a member of the formamidine pesticide family, commonly used for ectoparasite control, is applied as a dip or low-pressure hand spray to cattle and swine, and the neck collar on dogs. Data on amitraz were generated mainly on laboratory animals, hens, dogs, and baboons. The data on the toxicity and disposition of amitraz in animals and its residues in the milk are inadequate. Therefore, the present study was intended to analyze the disposition kinetics of amitraz and its pattern of elimination in the milk of lactating does after a single dermal application at a concentration of 0.25%. Blood at predetermined time intervals and milk twice daily were collected for eight days post application. The drug concentration was assayed by high-performance liquid chromatography (HPLC). Amitraz was detected in whole blood as early as 0.5 h, which attained a peak concentration at 12 ± 5 h, followed by a steady decline; however, detection persisted until 168 h. Amitraz was present in the blood at its 50% C_max even after 48 h, and was still detectable after 7 days. The disposition after a single dermal application was best described non-compartmentally. The mean terminal half-life (t_1/2), mean residence time (MRT), and area under the curve (AUC_0–t) were 111 ± 31 h, 168 ± 39 h, and 539 ± 211 µg/mL/h, respectively. The apparent volume of distribution (Vd_area) was 92 ± 36 mL/g with an observed clearance (Cl) of 0.57 ± 0.33 mL/kg/h. Thus, the drug was well absorbed, widely distributed and slowly eliminated from the animal body. Amitraz achieved milk concentration approximating 0.2 per cent of the total dose after a single exposure and the steady-state elimination of amitraz in milk above the recommended maximum residue limit (MRL) of 0.01 mg/kg can act as a source of public health concern when applied on lactating animals.