Facile Entry to 4‐ and 5‐Hydroxybenzofuran and to Their Amino Derivatives

An innovative one‐step procedure for the synthesis of 4‐hydroxybenzofuran and an improved synthesis of 5‐hydroxybenzofuran is reported. Such compounds were also transformed into their amino derivatives via Smiles rearrangement with good to high overall yields.     

Incoherent X-radiation produced by relativistic electrons in crystals

Differential and integral features of incoherent X-radiation, induced by relativistic electrons in crystals, are studied for observation angles θ_γ several times greater than γ^-1, where γ is the projectile Lorentz factor. The existence of sharp maxima and a minimum of the five-folded incoherent differential cross-section as a function of the final electron angles, and a dip minimum when the cross-section is taken as a function of the photon energies, is demonstrated. At near backward observation angles the three-folded cross-section shows a maximum in the region of several keV photon energies. The obtained results allow us to optimize the conditions for coincidence experiments, minimizing the incoherent contribution to the total radiation yield, and helping to analyse results of finite-size detector experiments with crystal targets. Received: 2 July 2001 / Accepted: 26 November 2001     

Extraction and gas chromatographic evaluation of plasticizers content in food packaging films

Cling films are prepared by adding (5-30% w/w) adipates, citrates, and phthalates. The adverse effects on human health of the plasticizers have been demonstrated, and then their content in food contact plastics and possible migration to foodstuffs must be carefully checked. To offer an easier tool to perform these controls, a Soxhlet extraction by ethyl acetate and a multi residue chromatography analysis, with Flame Ionization Detector, have been optimised for the application in evaluating both the real content of plasticizers in films and freezing bags, and their migrated amounts in simulants. The average extraction yield was 95 ± 10%. The chromatographic analysis was able to determine 16 different compounds, clearly separated, taking only 25 min to complete the assay. The detection limits ranged from 0.07 to 0.7% (w/w). The total amount of plasticizers in the packaging products was comprised between 3 and 10% (w/w). Extracted and migrated amounts were compared, and they resulted in good agreement. No migration of Phthalates, whose presence has been demonstrated in some samples, has been observed. It has been also demonstrated that a prolonged contact (till 60 days) did not increase the amount of migrated plasticizers, and then the risks for health.     

Reactions of stilbene episulphoxides and episulphides with organolithium compounds. Evidence for attack at sulphur and at proton.

The reaction of organolithium compounds with stilbene episulphoxides and episulphides leads to stereospecific desulphurization and to ring opening. The stereochemistry of the latter reaction depends on the structural features.     

First practical asymmetric synthesis of R-(−)-and s-(+)-mevalonolactones from a single achiral precursor

A new asymmetric synthesis of R-(?)- and S-(+)- mevalonolactones is described. Starting from a single achiral precursor, the synthesis proceeds by a nine-steps sequence, $\text{via}$ Sharpless epoxidation of an appropriate allylic alcohol.     

Fluoride Ion Promoted Reactivity of Thiocarbonyl Containing Molecules with Silyl Derivatives: A Novel Access to Allyl Sulfides

Abstract

Fluoride ion induced reaction of allyl- and benzyl-silanes with thiocarbonyls leads, contrary to the corresponding lithium or Grignard reagents, to products of S-functionalization.     

A Positive Mass Theorem on Asymptotically Hyperbolic Manifolds with Corners along a Hypersurface

In this paper we take an approach similar to that in [13] to establish a positive mass theorem for spin asymptotically hyperbolic manifolds admitting corners along a hypersurface. The main analysis uses an integral representation of a solution to a perturbed eigenfunction equation to obtain an asymptotic expansion of the solution in the right order. This allows us to understand the change of the mass aspect of a conformal change of asymptotically hyperbolic metrics. Vincent Bonini: The first named author supported by MSRI Postdoctoral Fellowship. Jie Qing: The second named author supported partially by NSF grant DMS 0402294. Submitted: April 6, 2007. Accepted: September 24, 2007.     

Regio- and stereoselective ring opening of 2,3-diaryl oxiranes by LiBr/Amberlyst 15: a new stereocontrolled access to 1,2-diaryl-2-bromo alcohols

Both symmetrical and nonsymmetrical trans-2,3-diaryloxiranes are regio- and stereoselectively opened by the LiBr/Amberlyst 15 system. In the case of symmetrical trans-stilbene oxide, the syn- versus anti-bromohydrins ratio ranged between 88/12 and 30/70, by varying the reaction temperature from 20 to -30 degrees C. In the case of nonsymmetrical para-substituted trans-2,3-diaryloxiranes, the regioselectivity is determined by electronic effects. If one phenyl bears a strong electron-withdrawing group (as NO2 or CF3), the nucleophilic attack is totally on the beta-carbon with respect to the substituted phenyl ring. With one phenyl bearing a strong electron-releasing group (OCH3), the regioselectivity is reversed. Ab initio calculation at the DFT/B3LYP/6-31G level, run on protonated epoxide structures, supports the formation of a cationic acyclic intermediate. Application of the method on ortho-methoxy and ortho-nitro 2,3-diaryloxiranes afforded the syn-bromohydrins in excellent yield, via regio- and stereoselective opening at either alpha- or beta-carbon, respectively.