Thermal reactions of tributyltin hydride with alpha-azido esters: unexpected intervention of tin triazene adducts under both nonradical and radical conditions

Thermal reaction of various alpha-azido esters with Bu(3)SnH in refluxing benzene results in smooth production of 3-(tributylstannyl)-1-triazene adducts affording cyclized 1,2,3-triazol-4-ones in preference to reduced amines and thence provides a new useful method for the preparation of these triazole derivatives. In the presence of AIBN the occurrence of triazene products still remains important or even exclusive and, consequently, generation of the expected stannylaminyl radicals is seriously limited. With 2-azidomalonates and alpha-azido-beta-keto esters stannyltriazenes can similarly occur in the absence of the radical initiator, but in the latter cases the ensuing triazenes undergo preferential cyclization onto the ketone moiety to give reactive hydroxytriazolines. Contrary to alpha-azido esters, in the presence of AIBN alpha-azido-beta-keto esters as well as azidomalonates give rise only to the usual stannylaminyl radicals. A possible explanation for the different behavior of the mono- and dicarbonyl azides in the presence of AIBN is put forward.     

Intramolecular cyclization of acyl radicals onto the azido group: a new radical approach to cyclized lactams

[reaction: see text] Aryl- and alkyl-derived azidoacyl radicals, generated from thiolesters by intramolecular homolytic substitution at the sulfur, can undergo five- and six-membered cyclization onto the azido moiety to give cyclized lactams.     

alpha-(Arylthio)imidoyl Radicals: [3 + 2] Radical Annulation of Aryl Isothiocyanates with 2-Cyano-Substituted Aryl Radicals

A novel cascade radical reaction is described involving aryl isothiocyanates and 2-cyanoaryl radicals. The mechanism entails the formation of an alpha-(arylthio)imidoyl radical, a 5-exo-dig cyclization onto a cyano group, and a final 6-membered ring closure of an iminyl radical. The competitive 5-membered spiro-cyclization of the iminyl, leading to an isomeric product, was only observed in the case of a disubstituted aryl isothiocyanate. The whole process involves a rare example of [3 + 2] radical annulation and allows the one-pot synthesis of tetracondensed nitrogen heterocycles in good yields.     

Generation and intramolecular reactivity of acyl radicals from alkynylthiol esters under reducing tin-free conditions

[reaction: see text] The radical chain reaction of benzenethiol with alkynylthiol esters provides a new, valuable protocol for the tin-free generation of acyl radicals that arise from intramolecular substitution at sulfur by the initial sulfanylvinyl radicals.     

Chemical and physical analysis of cotton fabrics plasma-treated with a low pressure DC glow discharge

This paper focuses on the modification of cotton fabrics using a low pressure DC glow discharge obtained in air. The influence of different operating parameters such as treatment time, discharge power and operating pressure on the chemical and physical properties of the cotton fabrics is studied in detail. Surface analysis and characterization of the plasma-treated cotton fabrics is performed using vertical wicking experiments, X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM) and weight loss measurements. The cotton fabrics show a significant increase in wicking behaviour; an effect which increases with increasing treatment time, increasing discharge power and increasing pressure. Results also show that low pressure DC glow treatment leads to surface erosion of the cellulose fibres, accompanied by an incorporation of oxygen-containing groups (C–O, C=O, O–C–O and O–C=O) on the cotton fibres. The DC glow treatment has thus the potential to influence not only the chemical but also the physical properties of cotton fabrics and this without the use of water or chemicals.     

Surface modification of polypropylene with an atmospheric pressure plasma jet sustained in argon and an argon/water vapour mixture

In this paper, an atmospheric pressure plasma jet sustained in pure argon and an argon/water vapour mixture has been used to modify the surface of polypropylene (PP) films. The gas temperature of the plasma jet was found to be 625 K in an active zone between the electrodes and was found to increase in the afterglow. Based on these results, the PP films are placed as close as possible to the edge of the capillary in order to avoid thermal damage to the polymer. XPS results on the untreated and modified PP samples revealed incorporation of a significant amount of oxygen on the polymer surface, however, this oxygen inclusion is more pronounced for the argon/water vapour jet due to the higher radicals density in the jet afterglow. One can therefore conclude that adding water vapour to an argon plasma jet can be a convenient way to increase the efficiency of plasma surface modification.