Selective oxidation of allylic alcohols over highly ordered Pd/meso-Al2 O3 catalysts

Highly ordered mesoporous alumina was prepared via evaporation induced self assembly and was impregnated to afford a family of Pd/meso-Al2O3 catalysts for the aerobic selective oxidation (selox) of allylic alcohols under mild reaction conditions. CO chemisorption and XPS identify the presence of highly dispersed (0.9–2 nm) nanoparticles comprising heavily oxidised PdO surfaces, evidencing a strong palladium-alumina interaction. Surface PdO is confirmed as the catalytically active phase responsible for allylic alcohol selox, with initial rates for Pd/meso-Al2O3 far exceeding those achievable for palladium over either amorphous alumina or mesoporous silica supports. Pd/meso-Al2O3 is exceptionally active for the atom efficient selox of diverse allylic alcohols, with activity inversely proportional to alcohol mass.

Hierarchically ordered nanoporous Pd/SBA-15 catalyst for the aerobic selective oxidation of sterically challenging allylic alcohols

The utility of a hierarchically ordered nanoporous SBA-15 architecture, comprising 270 nm macropores and 5 nm mesopores (MM-SBA-15), for the catalytic aerobic selective oxidation of sterically challenging allylic alcohols is shown. Detailed bulk and surface characterization reveals that incorporation of complementary macropores into mesoporous SBA-15 enhances the dispersion of sub 2 nm Pd nanoparticles and thus their degree of surface oxidation. Kinetic profiling reveals a relationship between nanoparticle dispersion and oxidation rate, identifying surface PdO as the catalytically active phase. Hierarchical nanoporous Pd/MM-SBA-15 outperforms mesoporous analogues in allylic alcohol selective oxidation by (i) stabilizing PdO nanoparticles and (ii) dramatically improving in-pore diffusion and access to active sites by sesquiterpenoid substrates such as farnesol and phytol. © 2013 American Chemical Society.

High-activity, single-site mesoporous Pd/Al2O3 catalysts for selective aerobic oxidation of allylic alcohols

Pd does it alone : Tailored heterogeneous catalysts offer exciting, alternative, clean technologies for regioselective molecular transformations. A mesoporous alumina support stabilizes atomically dispersed PdII surface sites (see picture, C light gray, O red, Pd dark gray, Al purple, H white), thereby dramatically enhancing catalytic performance in the aerobic selective oxidation of alcohols.

Phenols and aromatic amines as thermal stabilizers in polyolefin processing

Scavenging of C- and O-centered free radicals is mandatory in processing stabilization of polypropylene. Phenolic antioxidants act principally as O-radical scavengers only. Aromatic amines, N,N'-disubstituted 1,4-phenylenediamines (PD) and 4,4'disubstituted diphenylamines (DPA), scavenge both C- and O-centered radicals and have consequently a broader activity spectrum. PD cannot be used, however, in polypropylene because of formation of strongly discoloring and staining sacrificial transformation products. Such products formed from DPA have even more discoloring properties. A good processing stability and acceptable extent of discoloration can be achieved by blends of phenols with 4,4'-di-tert.octyl DPA. The effect is considered as a beneficial cooperation between the two chain-breaking antioxidants involving interactions with amine-based transformation products.

Dioxaborine dyes as fluorescent probes for amines and carbon nanotubes

The newly synthesized dioxaborine dyes were studied aiming to probe amines and carbon nanotubes, which are potential toxic industrial polluters. To detect the targeted analytes in efficient way, series of ca. 20 dioxaborine dyes were synthesized and tested for reactivity with amines and carbon nanotubes. The most promising result was showed for styryl dye with the fluorescent sensitivity to amines up to 1 ppm. A fluorescent response of the dioxaborine dyes on presence of carbon nanotubes was revealed.

Reactions of nitrilium salts with indole and pyrrole and their derivatives in the synthesis of imines, ketones and secondary amines

I thank SERC for a CASE studentship (to RG. Giles) with the former Fisons Pharmaceuticals division (with Dr. S. C. Eyley) and Dr. B. R. Buckley, of this department, for provided helpful comments on an earlier version of the manuscript.

Reactions of nitrilium salts with indole and pyrrole and their derivatives in the synthesis of imines, ketones and secondary amines

I thank SERC for a CASE studentship (to RG. Giles) with the former Fisons Pharmaceuticals division (with Dr. S. C. Eyley) and Dr. B. R. Buckley, of this department, for provided helpful comments on an earlier version of the manuscript.

Reactions of nitrilium salts with indole and pyrrole and their derivatives in the synthesis of imines, ketones and secondary amines

I thank SERC for a CASE studentship (to RG. Giles) with the former Fisons Pharmaceuticals division (with Dr. S. C. Eyley) and Dr. B. R. Buckley, of this department, for provided helpful comments on an earlier version of the manuscript.

Recent Advances in the Direct Nucleophilic Substitution of Allylic Alcohols through SN1-Type Reactions

Direct nucleophilic substitution reactions of allylic alcohols are environmentally friendly, since they generate only water as a byproduct, allowing access to new allylic compounds. This reaction has, thus, attracted the interest of the chemical community and several strategies have been developed for its successful accomplishment. This review gathers the latest advances in this methodology involving SN1-type reactions.

The dehydrogenation reactions between LiH and organic amines for solid state hydrogen storage systems

Hydrogen is considered as an appealing alternative to fossil fuels in the pursuit of sustainable, secure and prosperous growth in the UK and abroad. However there exists a persisting bottleneck in the effective storage of hydrogen for mobile applications in order to facilitate a wide implementation of hydrogen fuel cells in the fossil fuel dependent transportation industry. To address this issue, new means of solid state chemical hydrogen storage are proposed in this thesis. This involves the coupling of LiH with three different organic amines: melamine, urea and dicyandiamide. In principle, thermodynamically favourable hydrogen release from these systems proceeds via the deprotonation of the protic N-H moieties by the hydridic metal hydride. Simultaneously hydrogen kinetics is expected to be enhanced over heavier hydrides by incorporating lithium ions in the proposed binary hydrogen storage systems. Whilst the concept has been successfully demonstrated by the results obtained in this work, it was observed that optimising the ball milling conditions is central in promoting hydrogen desorption in the proposed systems. The theoretical amount of 6.97 wt% by dry mass of hydrogen was released when heating a ball milled mixture of LiH and melamine (6:1 stoichiometry) to 320 °C. It was observed that ball milling introduces a disruption in the intermolecular hydrogen bonding network that exists in pristine melamine. This effect extends to a molecular level electron redistribution observed as a function of shifting IR bands. It was postulated that stable phases form during the first stages of dehydrogenation which contain the triazine skeleton. Dehydrogenation of this system yields a solid product Li2NCN, which has been rehydrogenated back to melamine via hydrolysis under weak acidic conditions. On the other hand, the LiH and urea system (4:1 stoichiometry) desorbed approximately 5.8 wt% of hydrogen, from the theoretical capacity of 8.78 wt% (dry mass), by 270 °C accompanied by undesirable ammonia and trace amount of water release. The thermal dehydrogenation proceeds via the formation of Li(HN(CO)NH2) at 104.5 °C; which then decomposes to LiOCN and unidentified phases containing C-N moieties by 230 °C. The final products are Li2NCN and Li2O (270 °C) with LiCN and Li2CO3 also detected under certain conditions. It was observed that ball milling can effectively supress ammonia formation. Furthermore results obtained from energetic ball milling experiments have indicated that the barrier to full dehydrogenation between LiH and urea is principally kinetic. Finally the dehydrogenation reaction between LiH and dicyandiamide system (4:1 stoichiometry) occurs through two distinct pathways dependent on the ball milling conditions. When ball milled at 450 RPM for 1 h, dehydrogenation proceeds alongside dicyandiamide condensation by 400 °C whilst at a slower milling speed of 400 RPM for 6h, decomposition occurs via a rapid gas desorption (H2 and NH3) at 85 °C accompanied by sample foaming. The reactant dicyandiamide can be generated by hydrolysis using the product Li2NCN.

Impact of salt reduction on biogenic amines, fatty acids, microbiota, texture and sensory profile in traditional blood dry-cured sausages

Meat industry needs to reduce salt in their products due to health issues. The present study evaluated the effect of salt reduction from 6% to 3% in two Portuguese traditional blood dry-cured sausages. Physicochemical and microbiological parameters, biogenic amines, fatty acids and texture profiles and sensory panel evaluations were considered. Differences due to salt reduction were perceptible in a faint decline of water activity, which slightly favoured microbial growth. Total biogenic amines content ranged from 88.86 to 796.68 mg kg 1 fresh matter, with higher amounts, particularly of cadaverine, histamine and tyramine, in low-salt products. Still, histamine and other vasoactive amines remained at low levels, thus not affecting consumers’ health. Regarding fatty acids, no significant differences were observed due to salt. However, texture profile analysis revealed lower resilience and cohesiveness in low-salt products, although no textural changes were observed by the sensory panel. Nevertheless, low-salt sausages were clearly preferred by panellists.

Determination of bioactive amines in tropical wines produced at Brazilian's Northeast.

The wine production in the region of the Sub-middle São Francisco river Valley has started there are few years ago.The region has a climate variability that allows to obtain two or three harvests per year, which influences significantly the composition of the grapes. This work aimed to evaluate the amount of amines present in white and red tropical wines produced in the Northeast of Brazil. The winemaking was done by the traditional method. After stabilizing the wines were bottled and then analyzed for the determination of the amines putrescine, spermidine and spermine, by thin layer chromatography (TLC). The harvests were in June (harvest I) and November (harvest II) 2009. The results showed that the edaphoclimatic conditions of the two harvests had significant influence (p> 0.05) on bioactive amines concentration, with high values for red wines. In addition, tropical wines from Sub-middle São Francisco river Valley showed adequate correlation between bioactive amines as compared to other wines in the world.

Synthesis of profluorescent isoindoline nitroxides via palladium-catalysed Heck alkenylation

The synthesis of a new structural class of isoindoline nitroxides (aminoxyls), accessible via the palladium-catalysed Heck reaction, is presented. Reaction of the aryl bromoamine, 5-bromo-1,1,3,3-tetramethylisoindoline (4) or dibromoamine, 5,6-dibromo-1,1,3,3-tetramethylisoindoline (5) or the analogous bromonitroxides 6 and 7 with methyl acrylate gives the acrylate substituted tetramethylisoindoline amines 8 and 10 and nitroxides 12 and 14. Similarly, the reaction of the aryl bromides and dibromides 4–7 with methyl 4-vinylbenzoate gives the carboxystyryl substituted tetramethylisoindoline amines 9 and 11 and the analogous nitroxides 13 and 15. The carboxystyryl tetramethylisoindoline nitroxides demonstrate strongly suppressed fluorescence, which is revealed upon removal of the free radical by reduction or radical coupling.

The synthesis of novel isoindoline nitroxides bearing water-solubilising functionality

A range of novel tetramethyl- and tetraethylisoindolinenitroxides, possessing aryl-linked carboxylic acids, amines, alcohols and phosphonic acids were prepared. Notably, the chemistry established for the aromatic dibromination of the tetramethylisoindolines was not easily transferred to the corresponding tetraethylisoindoline system. Instead, various tetraethylisoindoline analogues were accessed by the oxidation of methyl groups attached to the aromatic ring to give the carboxylic acids. The increased steric bulk of the tetraethyl structures should limit bio-reduction and these compounds may have potential as antioxidants.