CoI- and Co0-bipyridine complexes obtained by reduction of CoBr2bpy: electrochemical behaviour and investigation of their reactions with aromatic halides and vinylic acetates

The electrochemical behaviour of CoBr(2)bpy (bpy=2,2'-bipyridine) catalyst precursor in acetonitrile has been studied, revealing its possible reduction into the corresponding Co(I) and Co(0) complexes. These low-valent cobalt species appear to be stable on the time scale of cyclic voltammetry. In the presence of aromatic halides, both complexes undergo oxidative addition, the latter Co(0) species allowing the activation of poorly reactive aromatic chlorides. The arylcobalt(III) and arylcobalt(II) obtained are reduced at the same potential as the original Co(II) and Co(I) complexes, respectively, resulting in the observation of overall ECE mechanisms in both cases. The electrochemical study shows that vinylic acetates competitively react with electrogenerated Co(0) species, leading to a labile complex. Preparative scale electrolyses carried out from solutions containing aromatic halides (ArX), vinyl acetate (vinylOAc) and a catalytic amount of CoBr(2)bpy lead to a mixture of biaryl (Ar-Ar) and arene (ArH) as long as the potential is set on the plateau of the Co(II) right arrow over left arrow Co(I) reduction wave. The coupling product (Ar-vinyl) is formed only if the electrolysis is performed on the plateau of the Co(I)/Co(0) reduction wave. A mechanism is proposed for the overall cobalt-catalyzed coupling reaction between aromatic halides and allylic acetates.     

Spectroscopic characterization and preparation of low molecular,water‐soluble chitosan with free‐amine group by novel method

Low molecular, water‐soluble chitosan (LMWSC) with a free amine group was prepared by the novel salts‐removal method described in this study. A weight‐average molecular weight and degree of deacetylation (DDA) of LMWSC were determined by viscometry and Kina titration, resulting in 18,579 Da and 93% DDA, respectively. In the Fourier transform infrared spectroscopic, ¹H NMR, and ¹³C NMR spectra the absorption band by the carboxyl group derived from lactic acid and the impurities formed in the enzymatic process disappeared or were significantly lower than that of the control chitosan. Also, from the ¹H NMR and ¹³C NMR spectra the empirical value for the area ratio of the proton and carbon corresponds nearly to its theoretical values. The matrix‐assisted laser desorption/ionization time‐of‐flight mass spectrum identified the difference in the two adjacent peaks as 161. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 3796–3803, 2002     

Lewis-Base Adducts of Group 11 Metal(I) Compounds. LXXVI Structural Studies in the Copper(I) Halide : Norbornadiene System

The structural characterizations of some copper(I) halide (CuX) adducts with norbornadiene (nbd) are recorded. CuCl : nbd (1:1)₄ (a redetermination), (2:1)_2(|), are systems both based around Cu₄Cl₄ cubane-type cluster arrays. CuBr : nbd (7:3)_(|)( 0.5 MeOH), a complex polymer with 3-symmetry, is believed to be the complex previously described as an adduct of 2:1 stoichiometry. Attempts to obtain an iodide counterpart have resulted in the definition of an ephemeral adduct CuI : MeCN (3:2)_(|). 0.5 C₇H₈ in which, remarkably, the nbd is uncoordinated; the complex is a polymer, related to the [AgX(quinoline)]_(|) (X = Cl, Br) saddle polymer.     

β-Cyclodextrin-polyurethane polymer as solid phase extraction material for the analysis of carcinogenic aromatic amines

β-Cyclodextrin-polyurethane (β-CDPU) polymer was synthesized by the reaction of β-cyclodextrin with hexamethylene diisocyanate in dry dimethylformamide and used as a sorbent for the solid phase extraction (SPE) of carcinogenic aromatic amines from water. The polymers were characterized by Fourier transform infrared spectroscopy, thermogravimetric analysis, differential scanning calorimetry and particle size analysis. The separation and quantification was performed by Liquid chromatography with RP-C₁₈ column and diode array detection using standard arylamines for quantification. When compared with commercially available sorbents, β-CDPU gave better recovery for the aromatic amines. From the variation of pH of the extractant from 4.0 to 8.5 recovery was highest at pH 8.5. The breakthrough volume has been ascertained to be 100 ml for 200 mg of the resin. The new SPE material offers better recovery and estimation of banned arylamines.     

Solvent-free microwave extraction of essential oil from aromatic herbs: comparison with conventional hydro-distillation

Solvent-free microwave extraction (SFME) is a combination of microwave heating and dry distillation, performed at atmospheric pressure without added any solvent or water. Isolation and concentration of volatile compounds are performed by a single stage. SFME has been compared with a conventional technique, hydro-distillation (HD), for the extraction of essential oil from three aromatic herbs: basil (Ocimum basilicum L.), garden mint (Mentha crispa L.), and thyme (Thymus vulgaris L.). The essential oils extracted by SFME for 30min were quantitatively (yield) and qualitatively (aromatic profile) similar to those obtained by conventional hydro-distillation for 4.5 h. The SFME method yields an essential oil with higher amounts of more valuable oxygenated compounds, and allows substantial savings of costs, in terms of time, energy and plant material. SFME is a green technology and appears as a good alternative for the extraction of essential oils from aromatic plants.     

Versatile reactions of a para-bromophenylacetylide iron(II) derivative and X-ray structure of the fluoro analogue. Synthesis of new redox-active organoiron(II) synthons

The synthesis of the new (η²-dppe)(η⁵-C₅Me₅)Fe---CC---1,3-(C₆H₄X) (m-2a/2b; X=F/Br) and (η²-dppe)(η⁵-C₅Me₅)Fe---CC---1,4-(C₆H₄I) (2c) complexes, as well as the solid-state structure of the known (η²-dppe)(η⁵-C₅Me₅)Fe---CC---1,4-(C₆H₄F) (2a) complex are described. The catalytic coupling reactions of the bromo complexes with various alkynes were next investigated. Starting from the known (η²-dppe)(η⁵-C₅Me₅)Fe---CC---1,4-(C₆H₄Br) complex (2b), the synthesis of the (η²-dppe)(η⁵-C₅Me₅)Fe---CC---1,4-(C₆H₄)---CC---H complex (6d) and of the corresponding silyl-protected precursors (η²-dppe)(η⁵-C₅Me₅)Fe---CC---1,4-(C₆H₄)CC---SiR₃ (6b/6c; R=ⁱPr/Me) are reported. By use of lithium---bromine exchange reactions on 2b, the silyl- (7a; E=Si; R=Me) and tin- (7b–7d; E=Sn; R=Me, Bu, Ph) substituted analogues (η²-dppe)(η⁵-C₅Me₅)Fe---CC---1,4-(C₆H₄)ER₃ are also isolated. The spectroscopic and electrochemical characterisations of all these new Fe(II)/Fe(III) redox-active building blocks are presented and the electronic substituent parameters for the “(η²-dppe)(η⁵-C₅Me₅)Fe---CC” group are determined by means of ¹⁹F-NMR.     

Alkyl radical adducts of aromatic N-oxides as hydrogen-abstracting agents: The reactivity of phenazine-N,N′-dioxide-methyl radical adduct

An O-methylated analog of protonated phenazine-di-N-oxide radical anion abstracts hydrogen from primary and secondary alcohols in a slow (k ₁ < 500 M⁻¹ s⁻¹) bimolecular reaction. No kinetic evidence has been found for the unimolecular release of free methoxyl radicals through the homolytic N-OMe bond cleavage in these species. DFT calculations at the UB3LYP 6-31G(d) level indicate that protonated and O-alkylated radical anions of pyrazine, quinoxaline and phenazine di-N-oxides are close analogues of aromatic nitroxyl radicals with the highest spin density localized on the oxygen and nitrogen of the nitrone moiety.     

Palladium-catalyzed cascade reactions of benzyl halides with N-allyl-N-(2-butenyl)-p-toluenesulfonamide

Reaction of benzyl halides with N-allyl-N-(2-butenyl)-p-toluenesulfonamide 1 in the presence of a palladium catalyst afforded dihydropyrroles 3 in moderate to excellent yields. It is proposed that the cyclic products were formed via a palladium-catalyzed cascade cyclization-coupling process.     

A novel effective electrophile: β-trifluoroacetylketene diphenyldithioacetal S,S-tetroxide

A synthesis of a novel electrophilic reagent--β-trifluoroacetylketene diphenyldithioacetal S,S-tetroxide 3 is described. The reaction of 3 with various electron-rich aromatics such as 1,3-dimethoxybenzene, 2-methylthiophene, N-methylpyrrole, and 2-methylindole was investigated. In the course of these reactions an unusual migration of a phenylsulfonyl group takes place. An easy and ready for scale-up procedure for the synthesis of previously unknown β-aryl, α-phenylsulphonyl substituted α,β-unsaturated trifluoromethyl ketones is reported.     

Surface properties of the binary mixed systems of alkylpyridinium halides and sodium alkylsulfonates

Surface properties of the binary mixed systems of decyl- and dodecylpyridinium chloride or bromide and sodium pentyl- and heptylsulfonate have been investigated. The surface tension of solutions of equimolar mixtures of surfactants and individual surfactants was measured, and the composition of mixed monolayers and surface interaction parameter β were calculated with the regular solution theory. Our results indicate that the properties of mixed films depend on both ionic strength and the kind of added inorganic electrolyte. With the increase of inorganic electrolyte concentration, the content of more surface active ions in the adsorption films enhances and is the highest in the presence of NaI and the smallest when solutions contain NaCl. Mutual interactions in mixed adsorbed films were found to be attractive. However, the strength of interaction weakens with the increase of ionic strength and depends on the kind of inorganic ions in the order: Cl⁻>Br⁻>I⁻.