[PdCl2{8-(di-tert-butylphosphinooxy)quinoline)}]: a highly efficient catalyst for Suzuki-Miyaura reaction

The complex [PdCl2(P-N)] containing the basic and sterically demanding 8-(di-tert-butylphosphinooxy)quinoline ligand (P-N) is a highly efficient catalyst for the coupling of phenylboronic acid with aryl bromides or aryl chlorides. The influence of solvent and base has been investigated, the highest rates being observed at 110 C in toluene with K2CO3 as the base. With aryl bromides the reaction rates are almost independent on the electronic properties of the para aryl substituents, on the contrary, reduced reaction rates are observed when bulky substituents are present on the substrate. Nevertheless the coupling of 2-bromo-1,3,5-trimethylbenzene with phenylboronic acid can be carried out to completion in 2 h using a catalyst loading of 0.02 mol %. Under optimized reaction conditions, turnover frequencies as high as 1900 h(-1) can be obtained in the coupling of 4-chloroacetophenone with phenylboronic acid: lower reaction rates are obtained with Substrates bearing EDG substituents on the aryl group. (C) 2009 Elsevier Ltd. All rights reserved

Synthesis of 4-Isobutylbenzaldehyde an Important Intermediate for the Fragrance (+)- and (-)-Silvial®

The synthesis of 4-isobutylbenzaldehyde, a valuable precursor for the fragrance Silvial® (3-(4-isobutylphenyl)-2-methylpropanal), is reported. Three different synthetic approaches are reported starting either from 4-isobutylbenzoic acid (via benzyl alcohol, or via acyl chloride), or by Suzuki-Miyaura cross-coupling reaction between 4-bromobenzaldehyde and 2-methylpropylboronic acid

Biopolymers for a more sustainable leather

Content: A novel class of bio-based polymers have been developed within the LIFE BIOPOL European project aiming to replace traditional re-tanning and fat-liquoring products reducing environmental impacts and increasing the safety of leather. The purpose of the project is to enhance the recovery and reuse of different bio-derived by-products from leather and agro-industrial sector to produce eco-friendly and renewable bio-polymers with high re-tanning and fat-liquoring characteristics. The LIFE BIOPOL project aims to make bio-based polymers in order to reduce the following parameters in re-tanning phase: - 20-30% COD, - 50-60% of inorganic salts (Sulphates and Chlorides), - 90% of Cr (III) salts, - 20% of water used in the leather process. Other important goals of the project are: - reduction 70-90% of hazardous and environmental polluting substances normally found in conventional chemicals, - reactivity enhancement of 30-40% of the new biopolymers compared to the current leather - application technology, - reduction of 70-80% of the Product Environmental Footprint of the new biopolymers related to the state of the art. The vegetal biomasses and the tanned hides by-products were pretreated in order to obtain suitable building blocks for the production of bio-based polymers. Several protocols involving polymerization were used in order to achieve the synthesis of the biopolymers, which have been carried out at lab scale. Macromolecular characterization of the biopolymers was performed in order to rationalize the synthetic strategy and practical application of the products giving important parameters such as molecular weight and chemical composition of the new biopolymers. Performances of new bio-based polymers have been inspected and compared with traditional chemicals through application on different types of leather. The benefits of the new products within leather making process were evaluated through chemical analyses of re-tanning and fat-liquoring effluents. The upgrade of the developed chemistry will be performed within a new devised prototype plant specifically designed and built-up for producing the bio-based polymers at industrial scale Take-Away: Production of leather making biopolymers from biomasses and industrial by-products through Life Cycle Designed Processe

Mechanistic understanding of chromium-based oligomerisation catalysts : an EPR and ENDOR investigation

Electron Paramagnetic Resonance (EPR) and Electron Nuclear Double Resonance (ENDOR) spectroscopies have been used to study the fundamental nature of chromium-based selective oligomerisation catalysts. A series of 'pre-catalyst' complexes were fully characterised CW-EPR revealed each complex to possess an axial g matrix (g > ge > g ) and superhyperfine coupling to two equivalent 31P nuclei, consistent with a low-spin cf species of approximate Cjv symmetry, where the metal contribution to the SOMO is primarily dxy. The isotropic component to the 31P coupling was of a larger magnitude in those Cr(I) complexes bearing PNP ligands than those bearing PCP, indicating that the phosphorus 3s character in the SOMO was higher for the former. CW-ENDOR demonstrated that subtle structural differences in the complexes, namely in the phenyl ring conformations, occurred as a function of ligand type. Pulsed experiments proved that the technique is valid and viable for further work on the activated system. Upon activation of the pre-catalyst with an alkylaluminium, four distinct paramagnetic centres were identified. A Cr(I) bis-arene complex was firstly detected it was found to form either via intramolecular co-ordination of the ligand phenyl groups, or preferentially via solvent-based arene co-ordination, if such groups were available. Two further species (I and III) were subsequently observed at low temperatures the spin Hamiltonian parameters extracted for both showed that a significant modification to the structure of the pre-catalyst had occurred. Half-field transitions indicated the possibility of a dimeric nature to Species III. ENDOR measurements detected an exceptionally large proton coupling in the activated system, possibly due to the co ordination of alkyl fragments to the metal centre. A final, fourth paramagnetic centre (Species IV), was detected and classed as an intermediate species, due to the greater similarity between its g and A matrices with those of the parent complex, than the other activated species. Finally, a preliminary investigation into analogous pre-catalyst complexes bearing N-heterocyclic carbene ligands was performed, due to their similar employment in oligomerisation catalysis CW-EPR spectra revealed information on both their electronic and structural natures.EThOS - Electronic Theses Online ServiceGBUnited Kingdo

Cultura tecnologica e ambiente

Di fronte all’esigenza pressante di adeguare le conoscenze progettuali alle istanze della situazione ambientale fortemente degradata, e allo stesso tempo di fronte alla consapevolezza che il progetto di architettura può contribuire con efficacia ai nuovi equilibri desiderati, questo testo propone una serie di riferimenti fondativi della questione ambientale, insieme a una considerazione complessiva del nuovo ruolo che l’architettura è chiamata ad assumere. La «ragione ecologica» infatti si è ormai affermata come impostazione culturale propria della nostra epoca da quando, a partire dagli anni Sessanta, gli sforzi di portare l’attenzione e la consapevolezza collettiva sui temi dell’ambiente e della sua gestione hanno fatto maturare ricerche, studi, iniziative nei diversi ambiti disciplinari e ai diversi livelli. È dunque necessario un aggiornamento culturale e tecnologico sui diversi fronti, ma c’è ancora un lungo percorso da fare perché i tempi urgenti delle azioni di salvaguardia ambientale possano essere conciliati con le pressioni condizionanti della produzione e del mercato, o delle abitudini del consumo. Questi nodi costituiscono il centro dell’analisi condotta dal testo, la cui finalità è quella di proporre una interpretazione culturale e tecnica del progetto di architettura rinnovata rispetto alle sue manifestazioni storiche, che sappia portare il sistema ambiente e il sistema progetto a una sorta di «felice collisione», per produrre quella qualità complessiva che la collettività si aspetta da universi disciplinari tanto ricchi e maturi