Isolation of pure (2S,1'S,2'S)-2-(2'-carboxycyclopropyl)glycine from Blighia sapida (Akee)

The isolation of (2S,1'S,2'S)-2-(2'-carboxycyclopropyl)glycine (CCG I, 2) from Blighia sapida (Akee) was achieved through column chromatography on deactivated silica gel followed by ion-exchange chromatography. A HPLC method has also been devised in order to assess the purity of the isolated product.     

A new synthesis of hydroxyphthalides

Cyclization of suitable enamino ketones can produce hydroxyphthalides.     

Thermal decomposition of dicyclopentadienylarylvanadium compounds

The thermolysis of compounds of the type Cp₂VR (R = aryl) in the solid state has been studied. A distinct increase in thermal stability is observed upon substitution of the ortho-position of the aryl group. Thermal decomposition occurs with formation of RH, Cp₂ V, a vanadocene homologue with the group R substituted in one of the Cp rings and, probably, a vanadocene homologue with two substituted Cp rings. It is shown that the abstraction of the hydrogen atom from the cyclopentadienyl ring, necessary for the formation of RH, is an intermolecular process, whereas the substitution of the aryl group in the Cp ring is intramolecular. A decomposition mechanism is proposed in which the group R is transferred from the vanadium atom to the C₅H₅ ring of the same molecule by interaction with an aryl group of another molecule. The thermal decomposition of Cp₂VR is compared with that of the analogous titanium compounds.     

lα-hydroxy previtamin D3, and its selective formation from 1-keto previtamin D3

An efficient method for the preparation of crystalline α-hydroxy previtamin D₃ is described. Also the stereoselective reduction of 1-keto previtamin $\text{9}$ is discussed; it was observed that with aluminum hydride $\text{7}$ is the most abundant product. This stands in contrast with previously reported LiAlH₄ and NaBH₄ mediated reductions.     

Differentiation between dexamethasone and betamethasone in a mixture using multiple mass spectrometry

Direct gas chromatographic methods to analyse phenylurea pesticides are discouraged by the thermal instability of these compounds, that in conventional hot splitless inlet systems leads to extensive and irreproducible formation of isocyanates and amines. However a careful control of the operating conditions, like the inlet temperature, the pressure and the presence of suitable chemical additives (as acetic acid, low-molecular-mass amines, organic anhydrides) can either: (i) minimise the thermal decomposition enabling the direct GC-MS analysis of phenylureas, or (ii) lead to reproducible conversion to isocyanates. Experimental design was employed to study the effect of the experimental variables on the thermal transformation of phenylurea pesticides in splitless inlet system. Two strategies were alternatively optimised: (i) the minimisation of degradation reactions to increase the signal of phenylureas; (ii) the maximisation of the degradation to isocyanates that are in turn determined. The maximal yields in isocyanate were obtained with high inlet temperatures, low carrier flows in the injection phase and the presence of acetic anhydride. By contrast, the use of relatively low inlet temperatures, high carrier flows during the injection and the presence of an amine maximise the response of the parent compounds.     

Determination of cisplatin and related platinum complexes in plasma ultrafiltrate and urine by high-performance liquid chromatography with on-line radioactivity detection

A reversed-phase ion-pair chromatographic method with on-line radioactivity detection for the simultaneous determination of 195mPt-labelled cisplatin and related platinum complexes has been developed. With this system a good resolution of various radiolabelled platinum complexes can be achieved. The detection limit of the radioactivity detector is 10 ng of cisplatin (specific activity of 15 MBq/mg cisplatin) per millilitre of urine or plasma ultrafiltrate. The detector response is independent of both the chemical structure of the platinum complexes and the matrix composition of the samples. This method may serve as a reference system for other high-performance liquid chromatographic systems with less specific and sensitive detectors.     

On the synthesis of geometric isomers of 2-methyl (or phenyl)-4-[α-arylethylidene]-5(4H)-oxazolones

Several Z-2-methyl(or phenyl)-4-[α-arylethylidene]-5(4H)-oxazolones 3Z, 4Z were prepared. The results obtained were compared by diazomethane insertion and condensation procedure. In order to synthesize E-2-phenyl-4-[α-arylethylidene]-5(4H)-oxazolones 4E hydrogen bromide isomerization in dry benzene was used.     

High-speed liquid and thin-layer chromatography of polychlorinated biphenyls.

High-speed liquid chromatography in the system silica gel/dry n-hexane and ultraviolet spectrometry have been used to study the composition of various types of commercially available mixtures of chlorinated biphenyls. Special attention has been paid to the analysis of highly chlorinated products. In addition to data previously published, retention times are recorded for 11 individual polychlorinated biphenyls. The results of high-speed liquid chromatography are compared with those obtained in several normal and reversed-phase thin-layer chromatographic systems.     

Conformation and chiroptical properties of mandelic acids

Using CD data (solution, solid state, various temperatures), X-ray data and MO calculations for a number of substituted mandelic acids (phenylglycolic acids) an attempt was made to explain the different results for the relation between sign of the ¹L_b CD band and substitution pattern as described in the literature for various types of aromatic compounds. Moreover the reported sector rule has been reconsidered taking into account the sign and magnitude of the spectroscopic moments. It has been found that in any explanation of the signs of the ¹L_b CD bands of substituted aromatic compounds both the conformational behaviour and the spectroscopic moments should be taken into account.     

Solvent extraction of phosphonium salts and their analytical applications : Separation and spectrophotometric determination of hexacyanoferrate(III)

The potentiometric determination of zinc in chloride solutions with a coated wire electrode is described. The electroactive membrane contains the chlorozincate(II) salt of Aliquat 336S in poly (vinyl chloride). The electrode shows a useful response over the range 10^-5 M–10^-1 M zinc(II) in 3 M total chloride solutions in the pH range 1.5–6. The electrode is more responsive to the divalent tetrachlorozincate(II) than to the monovalent trichlorozincate(II) species. Applications in compleximetric titrations, and to the analysis of zinc oxide and zinc concentrates are reported.