scholarly journals Mechanochemical Friedel–Crafts acylations

2019 ◽  
Vol 15 ◽  
pp. 1313-1320 ◽  
Author(s):  
Mateja Đud ◽  
Anamarija Briš ◽  
Iva Jušinski ◽  
Davor Gracin ◽  
Davor Margetić

Friedel–Crafts (FC) acylation reactions were exploited in the preparation of ketone-functionalized aromatics. Environmentally more friendly, solvent-free mechanochemical reaction conditions of this industrially important reaction were developed. Reaction parameters such as FC catalyst, time, ratio of reagents and milling support were studied to establish the optimal reaction conditions. The scope of the reaction was explored by employment of different aromatic hydrocarbons in conjunction with anhydrides and acylation reagents. It was shown that certain FC-reactive aromatics could be effectively functionalized by FC acylations carried out under ball-milling conditions without the presence of a solvent. The reaction mechanism was studied by in situ Raman and ex situ IR spectroscopy.

Crystals ◽  
2020 ◽  
Vol 10 (6) ◽  
pp. 482
Author(s):  
Richard Chen ◽  
Mehmet Kerem Gokus ◽  
Silvina Pagola

This report describes aspects of our previous studies of the mechanochemical synthesis of charge transfer complexes of the electron donor tetrathiafulvalene, which are relevant to the use of laboratory X-ray powder diffraction for ex situ monitoring of mechanochemical reactions toward investigating their mechanisms. In particular, the reaction of tetrathiafulvalene and chloranil was studied under neat mechanochemical conditions and liquid-assisted grinding with diethyl ether (1 μL/mg). The product in both cases is the green tetrathiafulvalene chloranil polymorph and the mechanism of the redox reaction is presumably the same. However, while the kinetic profile of the neat mechanochemical synthesis was fitted with a second-order rate law, that of the overall faster liquid-assisted grinding reaction was fitted with the Ginstling-Brounshtein 3D diffusion-controlled model. Hence, the diffusional processes and mass transfer bringing the reactants together and separating them from products must be different. Diffraction measurements sensitive to crystalline phases and amorphous material, combined with in situ monitoring by spectroscopic techniques, will ultimately afford a better understanding of mechanochemical reaction mechanisms, a hot topic in mechanochemistry.


2019 ◽  
Author(s):  
Patrick Julien ◽  
Luzia S. Germann ◽  
Hatem M. Titi ◽  
Martin Etter ◽  
Robert E. Dinnebier ◽  
...  

Using the mechanosynthesis of the calcium phosphate and urea fertilizer cocrystal as a model, we provide the first in situ investigation of autocatalysis in a mechanochemical reaction. The application of in situ Raman spectroscopy and synchrotron X-ray diffraction provided the first direct evidence of a mechanochemical system in which a reaction product (water) mediates the rate of transformation and underpins positive feedback kinetics.


2002 ◽  
Vol 56 (8) ◽  
pp. 1013-1020
Author(s):  
Robert J. Forrest ◽  
Robin Devonshire ◽  
Chakrapani V. Varanasi ◽  
Timothy R. Brumleve

Raman microscopy has been used to investigate the reactions between the chemical dosants in scandium metal halide discharge lamps and their silica lamp envelopes; such lamps are typically dosed with Hg, NaI, ScI3, and sometimes, additionally, excess Sc metal. Raman measurements were made both on operated lamps and dosed silica ampoules that had been furnace heat-treated. The ampoules mimic closely the dose–envelope interactions of lamps in a convenient manner while avoiding the obscuring and complicating effects in whole-lamp studies resulting from the reactions and mobility of electrode materials. In situ Raman analyses of deposits in the envelopes and ampoules, supported by an extensive database of the Raman spectra of lamp materials, and ex situ X-ray diffraction (XRD) analyses of refractory deposits to confirm independently the Raman assignments, have demonstrated that: (1) Sc metal reacts with envelope silica to produce Sc2O3 and elemental Si; (2) Sc metal in the presence of ScI3 reacts with the envelope silica to produce Sc2Si2O7; and (3) Sc metal reacts with envelope silica in the presence of NaI alone to produce Sc2O3 and not Sc2Si2O7. The results confirm and extend previous studies and demonstrate the value of Raman microscopy as a nondestructive investigative tool for lamp chemistry.


2021 ◽  
Author(s):  
◽  
Thomas Wade Nilsson

<p>Gold nanoparticles are known for their remarkable optical properties; they exhibit localised surface plasmon resonance bands in the visible region of the electromagnetic spectrum. This has led to their use as luxury dyes for the colouring of wool fibres. Gold is associated with wealth and desire, and as such, gold nanoparticle-wool fibre composites may be fabricated into high-quality garments, apparel, textiles and carpets for international markets.  Novel proprietary approaches for the laboratory-scale synthesis of gold nanoparticle-wool fibre composites have previously been developed by Professor James Johnston and Dr Kerstin Lucas. The innovative nanotechnology utilises the affinity of gold for sulfur-containing cystine residues in wool fibres, to attract and bind the gold nanoparticles. One approach involves the absorption of gold ions by wool fibres and the nucleation of gold nanoparticles in-situ. In an alternative method, gold nanoparticle colloids are synthesised ex-situ, and are then used to colour wool fibres.  The reaction conditions of the in-situ and ex-situ approaches were optimised with respect to cost-effectiveness and scalability. The gold content of the in-situ composites was minimised, and the range of possible colours widened, via the use of heat and external reducing agents. In the ex-situ process, the formation and stability of the gold nanoparticle colloids was studied, and the reaction conditions of the synthesis were optimised. The rate of uptake of gold nanoparticles to wool was controlled by manipulating the pH, concentration, volume, and wool to liquor ratio of the gold colloids, and by introducing auxiliary agents into the dyeing reactions. A range of chemical treatments and alternative stabilising agents were investigated to improve the washfastness properties of ex-situ gold nanoparticle-wool fibre composites.  There are numerous size-controllable syntheses of gold nanoparticle colloids at the laboratory-scale. However, when the process is scaled-up, gold nanoparticle synthesis is no longer trivial. A barrel reactor with a high velocity mixer was utilised to achieve uniform mixing and heating in the synthesis of gold nanoparticle colloids of up to 90 L in volume. The ratios of gold to stabilising agents in the colloidal gold syntheses were optimised to result in more stable and reproducible gold colloids for subsequent dyeing reactions.  The uniform colouring of small quantities of wool is easily achieved in the laboratory, but preventing colour variation across a kilogram of wool is a significant challenge. Initial kilogram-scale dyeing reactions in static tank reactors resulted in unevenly coloured gold nanoparticle-wool fibre composites. To overcome this, conventional hank dyeing equipment was used to colour felted merino yarn, in collaboration with the wool dyeing industry. Modified hank dyeing procedures were recreated in the laboratory, and composites with remarkable colour uniformity were produced. Industrial package dyeing reactors were then used to colour fine merino yarn with gold nanoparticle colloids. The uptake of gold nanoparticles was controlled by manipulating the owrates, ow direction and amounts of auxiliary agents that were employed in the dyeing reactions.  Based upon the success of the industrial dyeing reactions, novel dyeing reactors were developed for the colouring of hanks of wool fibres and yarns in the laboratory. These reactors utilised rapid dye circulation and pressure to produce gold nanoparticle-wool fibre composites with remarkable colour uniformity. The composites were used to fabricate luxury apparel and carpets for international trade expositions.  The pathway from synthesis in the laboratory to pilot-scale production of gold nanoparticle-wool fibre composites is presented. The PhD research was an integral step in the successful commercialisation of this innovative nanotechnology, and will assist in scaling-up the synthesis of metal nanoparticle colloids and nanocomposites in the future.</p>


Sign in / Sign up

Export Citation Format

Share Document