High-pressure access to the Δ9-cis- and Δ9-trans-tetrahydrocannabinols family

Diels-Alder reactions of a range of 1-(alkoxy/alkyl-substituted phenyl)buta-1,3-dienes with methyl vinyl ketone and methyl acrylate carried out in ethanol as the reaction medium under 9 kbar pressure were investigated. The use of high pressure as the activating method of the Diels-Alder reactions allows the efficient and endodiastereoselective generation of a series of cis-cyclohexenyl-benzene cycloadducts, which are selectively converted into their trans-epimers. The cis-cyclohexenyl-benzenes and trans-cyclohexenyl-benzenes produced are useful precursors for accessing substituted privileged cis-6a,7,8,10a-tetrahydro-6H-benzo[c]chromene and trans-6a,7,8,10a-tetrahydro-6H-benzo[c]chromene skeletons. The total syntheses of Δ(9)-cis-tetrahydrocannabinol (THC) and Δ(9)-trans-THC, through the use of selected Diels-Alder adducts, are described. Finally, a route for obtaining Δ(9)-trans-THC in both enantiomeric pure forms based on the (S)-(-)-1-amino-2-(methoxymethyl)pyrrolidine (SAMP)-hydrazone method is also reported.     

Enantioselective Synthesis of Phenylpropanetriols

The four stereomer 1-(4-hydroxy-3-methoxy)-phenyl-1,2,3-propanetriols were obtained in about 30% yields starting from ferulic acid by a synthesis based on osmium catalyzed asymmetric dihydroxylation.     

One-step synthesis of 2,6-lutidine from acetone, ammonia and methanol. Choice of catalyst and reaction conditions

A screening and optimization procedure carried out on more than 40 different oxide mixtures showed that amorphous silica-alumina (7525 by weight), impregnated with Sb and Cu oxides (10 wt.%) is a convenient catalyst for the title reaction at 650–750 K. During reaction, Sb³⁺ and Cu²⁺ ions are slowly reduced to Sb⁰ and Cu⁺ or Cu⁰, respectively. However, a simple treatment in oxygen can easily regenerate the catalyst.     

Gas chromatographic/mass spectrometric determination of vinyl acetate levels in air

The determination of vinyl acetate at parts per 10⁹ by volume (ppbv) levels in air by gas chromatography/mass spectrometry (GC/MS) was achieved by optimizing the GC conditions and choosing specific extraction solvents that are sufficiently pure. The ideal solvent should not give rise to fragment ions at m/z 43, in order to rule out any possible interference during the monitoring of the same vinyl acetate ion. Traces of acetone and butan-2-one in solvents suitable for this GC/MS determination may also mislead the detection of vinyl acetate. A 440 μl volume of a mixture of tetrachloroethylene containing 9% acetonitrile allowed the recovery of more than 90% of the ester with a detection limit of 1.5 ppbv in air together with a good linearity of response.     

Preparation, characterization, activity and selectivity of highly loaded oxide promoted ruthenium catalysts for selective hydrogenation of benzene to cyclohexene

Summary The influence of promoters and precipitants of the catalyst precursor on the activity and selectivity of the hydrogenation of benzene to cyclohexene catalyzed by highly loaded oxide-promoted Ru/ZrO₂catalysts, carried out in a tetraphase reactor (in the presence of an aqueous solution of ZnSO₄), at 423 K and 5 Mpa, was studied. The effect of hydrogen diffusion on the reaction kinetics and on the selectivity has been taken into consideration, the internal pore diffusion being actually the limiting step. Hydrogen chemisorption measurements indicate that the catalyst activity is not influenced by the Ru dispersion, but rather by weakly chemisorbed species.     

Stabilità delle soluzioni di disequazioni variazionali ellittiche e paraboliche quasi lineari

Riassunto In questo lavoro, si studia, per una classe di operatori quasi-lineari, il problema della dipendenza simultanea dai vincoli, dai coefficienti dell'operatore e dai termini noti delle soluzioni di disequazioni variazionali ellittiche e delle soluzioni forti di disequazioni variazionali paraboliche. L'esistenza di queste ultime è consequenza dei risultati precedenti.

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Summary We study the problem of the dependence from the data of the solutions of quasilinear elliptic variational inequalities. We also consider the case of the strong solutions of parabolic variational inequalities, whose existence has been proved as a consequence of the previous results.

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Lavoro eseguito nell'ambito del G.N.A.F.A.—C.N.R.