Synthesis of coumarins by ring-closing metathesis using Grubbs’ catalyst

A novel generally applicable synthesis of coumarins from phenolic substrates utilizing ring-closing metathesis is described. This sequence involves O-allylation of phenols followed by ortho-Claisen rearrangement, subsequent based-induced isomerization affording 2-(1-propenyl)phenols, acylation with acryloyl chloride, and finally ring-closing metathesis (RCM) with Grubbs’ second generation catalyst.     

Relations entre structure chimique et grandeurs de retention. VII. Composés de structure cyclopropanique

Résumé Les auteurs ont étudié le comportement chromatographique sur plusieurs phases stationnaires polaires et non polaires de composés cyclopropaniques stéréoisomêres: où R=H ou CH₃ et X=CH, COOCH₃ ou CH₂OH. Les résultats sont interprétés en fonction de la configuration de X par rapport à , de la nature électronique de X et de l'orientation du phényle par rapport au plan du cyclopropane.

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Relationship between chemical structure and retention. VII. Cyclopropane compounds

Summary The chromatographic behaviour, on several polar and non polar phases, of stereoisomeric cyclopropanes has been studied R=H or CH₃ and X=CN, COOCH₃, CH₂OH. The results are interpreted in terms of the X versus configuration, the electronic nature of X and the orientation of the phenyl ring in relation to plane of the cyclopropane ring.

     

Synthesis of 6R(β)-tritylaminopenicillanic-3R(β)-alcohol,a versatile stereoisomer of natural β-lactams

In an attempt to rationalize a synthesis of penicillin analogs modified at C(3), we have isolated the 3R(β)-carbinolamide derivative 4a. The trityl substituent on N(6′) seems to be responsible for the inversion of configuration which occurs at C(3) during the acid hydrolysis of the isocyanate intermediate. An hydrogen bond is formed on the β-face of the bell-shaped bicyclic skeleton between the N(6′)-nitrogen lone pair and the C(3) hydroxyl group. On standing, the carbinolamide analog slowly isomerizes to its expanded bicyclic isomer 4b , but the starting material may be easily recovered by treatment with acid. The postulated intermediate during isomerization, i.e., the open aldehyde form, does not accumulate. Substitutions of the hydroxyl group at C(3) lead to a variety of compounds with the biologically active 3S(α) configuration. These may be used to study the importance of the carboxyl group of penicillins in their interaction with β-lactamases at the molecular level.     

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.