Reductive lithiation of 1,3-dimethyl-2-arylimidazolidines

Naphthalene catalyzed lithiation of 1,3-dimethyl-2-phenylimidazolidine led to cleavage of the benzylic carbon-nitrogen bond, with formation of an intermediate dianion. Under similar conditions, 1,3-dimethyl-2-(4-chlorophenyl)imidazolidine underwent regioselective cleavage of the aromatic carbon-chlorine bond, leading to a 4-formylphenyllithium equivalent, whilst 1,3-dimethyl-2-(4-methoxymethylphenyl)imidazolidine underwent regioselective cleavage of the benzylic carbon-oxygen bond, leading to a 4-formylbenzyllithium equivalent.     

Electrochemical measurement of mercury concentration profiles in the pore-waters of sediments of the Venice Lagoon by ion-exchange voltammetry at polymer modified electrodes

Glassy carbon electrodes modified with coatings of poly-[1-methyl-3-(pyrrol-1-ylmethyl)pyridinium], poly-MPP, were employed for preconcentrating and detecting the anionic complex HgCl4(2-), which is the prevailing inorganic Hg(II) species in salt waters such as the pore-waters of sediments here examined. The application of ion-exchange voltammetry at poly-MPP coated electrodes in combination with an in situ pore-water sampler allowed the measurement of concentration vs. depth profiles for mercury dissolved in the pore-waters of a salt-marsh and of a mud-flat located in a polluted area of the Venice Lagoon. The trends of the mercury profiles are discussed in comparison with the trends measured from the same location for other trace metals (Zn, Cd, Cu and Pb) and reduced species such as S(-II) and Fe(II).     

On testing quality and traceability of virgin olive oil by calorimetry

Extra Virgin olive oils (7 samples) originating from different areas of Tuscany, defective olive oils (5 samples), commercial edible seed oils (4 samples) and two commercial samples of olive oil (one declared ‘extra virgin olive oil’ and one ‘olive oil’) were studied by different calorimetric techniques: high sensitivity isothermal, differential scanning, and modulated scanning calorimetry. The temperature interval (–60) – (+30)°C was explored for monitoring: i) the main features of the liquid↔solid phase transitions, ii) the nucleation and growth rate of the polymorphous crystalline phases of the triacylglicerols, and iii) the melting process. This investigation was planned for verifying the utility and effectiveness of calorimetry for screening quality and origin of olive oil. To this end, the main calorimetric operation modes have been applied, the experimental results reported and their utility for developing an effective and reliable screening protocol discussed.     

Voltammetric probe of milk samples by using a platinum microelectrode

Milk is a complex heterogeneous fluid containing many components in several states of dispersion. When used as a bulk solvent for studying electrochemical processes of some of the electroactive species present, it displayed mainly aqueous solution properties. With microelectrodes (25 μm in diameter) some typical constituents can be detected and the reproducibility of the processes studied was found to be satisfactory, with relative standard deviations (r.s.d.s.) lower than 2%, whereas measurements with conventional-sized platinum electrode (3 mm in diameter) gave r.s.d.s, of about 10%. Moreover, because of enhanced mass transport associated with the smallest electrodes, it was possible to diagnose the formation of precipitates of calcium phosphates on the electrode surface, as a consequence of a CEC electrode process at ?0.920 V vs. SCE, involving protons released by H₂PO^?₄, HPO^2?₄ formed in the electrode reaction and Ca²⁺. The reduction of acidic groups from casein, the oxidation of ascorbate and oxygen effects were also studied.     

Determination of atropine (hyoscyamine) sulfate in commercial products by liquid chromatography with UV absorbance and fluorescence detection: multilaboratory study

A liquid chromatographic (LC) method with 2 detection systems for determining atropine (hyoscyamine) sulfate in commercial products was tested in a multilaboratory study. Depending on the type of product, sample solutions are prepared in methanol or methanol-water (1 + 1). The standard solution contains about 1.0 mg atropine sulfate/100 mL and is prepared in the same solvent used in sample preparation. LC separations are performed on a 7.5 cm Novapak silica column. The mobile phase is prepared by mixing 970 mL methanol with 30 mL of a 1% aqueous solution of 1-pentanesulfonic acid, sodium salt. Detection is by 2 systems, UV absorbance detection at 220 nm and fluorescence detection with excitation at 255 nm and emission at 285 nm. The injection volume is 100 or 200 microL. The following materials were used for the study: 2 separate samples of tablets labeled to contain 0.4 mg atropine sulfate, 2 separate samples of extended-release tablets labeled to contain 0.375 mg hyoscyamine sulfate, one sample of atropine sulfate injection labeled to contain 2 mg/mL, and one sample of 1% (v/v) atropine sulfate ophthalmic. Eight participants analyzed 2 separate portions of the 6 samples by both detection systems. A ninth participant analyzed the samples in duplicate but only by UV absorbance detection because of the unavailability of a fluorescence detector. The relative standard deviation (RSD) between laboratories ranged from 1.4 to 3.3% for samples of tablets and injections but higher for ophthalmic solutions (5.1-5.2%). A linearity study was conducted in the originating laboratory before the multilaboratory study with 5 solutions ranging in concentration from 0.80 to 1.20 mg atropine sulfate in 100 mL. Average recoveries were 100.0% by UV absorbance detection and 99.9% by fluorescence detection; the RSDs were 1.1 and 1.2%, respectively.     

Rearrangement of N-Allyl-α,α-dichloroamides, β- or γ- Functionalized,to Substituted Analogues of the γ-Aminobutyric Acid (GABA)

The rearrangement of γ-chlm, β-hydroxy or β-vmyl N-allyl-N-benzyl-α,α-dichlorocarboxyamides to γ-aminobutynic acid analogues is efficiently promoted by CuCI\N,N,N′,N′-tetramethylethylendiamine. With the β-vinyl functionalization a tandem radical-radical reaction, yieldmg 3-aza-2-oxo-bicyclo[3,3,0]actatre adducts, is also observed.     

Carbonyl Regeneration from Oximes and Semicarbazones by Trimethylchlorosilane-Dimethylsulphoxide

Treatment of oximes and semicarbazones of saturated and α,β-unsaturated ketones and aldehydes with trimethylchlorosilane-dimethyl sulphoxide in dry acetonitrile affords the corresponding carbonyl compounds in excellent yields under mild conditions.     

The CuBr/Fe0 Promoted Radical Addition of Methyl 2-Br-2-Cl-Carboxylates to OLEFINS

Methyl 2-Br-2-Cl-carboxylates afford 2-alkyl-2-Cl-4-Br-carboxylates in fair yields by reaction with terminal alkenes, under mild conditions, through a radical process promoted by CuBr/Fe⁰ in DMF/CH₂C1₂.