Methods for Monitoring Milling Reactions and Mechanistic Studies of Mechanochemistry: A Primer

Crystal Growth & Design, Год журнала: 2022, Номер 22(9), С. 5726 - 5754

Опубликована: Авг. 21, 2022

Mechanochemistry by ball milling is garnering significant attention as an efficient and versatile means of chemical synthesis which minimizes the need for solvents reduces amount energy required to conduct many molecular transformations. Understanding reactions often requires monitoring reaction solid forms, with little or ideally no disruption process. Herein, we provide a broad but succinct summary how different ex situ more recently developed in techniques have been applied monitor mechanochemical reactions, revealing pathways mechanisms driving solid-state materials transformations milling. The rapidly evolving field has already revolutionized our understanding complex self-assembled phases intermediates catalytic other types through multitude reported investigating are touched upon this summary, promise dramatically increase pace development chemistry.

Язык: Английский

---

Direct mechanocatalysis by resonant acoustic mixing (RAM)

Chemical Science, Год журнала: 2023, Номер 14(27), С. 7475 - 7481

Опубликована: Янв. 1, 2023

We demonstrate the use of a metal surface to directly catalyse copper-catalysed alkyne-azide click-coupling (CuAAC) reactions under conditions Resonant Acoustic Mixing (RAM) - recently introduced and scalable mechanochemical methodology that uniquely eliminates need for bulk solvent, as well milling media. By using simple copper coil catalyst, this work shows direct mechanocatalysis can occur in an impact-free environment, relying solely on high-speed mixing reagents against surface, without specially designed containers introducing experimental setup enables real-time Raman spectroscopy monitoring RAM processes, we 0th-order reaction kinetics several selected CuAAC reactions, supporting surface-based catalysis. The herein presented RAM-based is simple, effective one-pot, two-step synthesis triazoles

Язык: Английский

---

Mechanochemical Deracemization: A Sustainable Approach to Enantiopurity

Chemistry - A European Journal, Год журнала: 2025, Номер unknown

Опубликована: Янв. 3, 2025

Abstract We introduce mechanochemical deracemization (MCDR) as a novel strategy for obtaining enantiopure compounds. This study demonstrates the successful transposition of six archetypical reactions from solvent‐based to solvent‐minimized ball milling environment. The scope includes ketone, isoindolinones, imines, an ester, and inorganic compound, all which deracemized successfully. Key parameters such material, number size, use bulk material liquid‐assisted grinding (LAG) were systematically investigated, revealing their crucial role. Quantitative enantiomeric excesses (ee) achieved, while reaction times reduced by up 97 % solvent consumption much 100 %. work establishes MCDR versatile, sustainable pathway By highlighting generalizability this approach its huge potential minimizing waste, provides foundation future advancements in deracemization.

Язык: Английский

---

Resonant acoustic mixing (RAM) for efficient mechanoredox catalysis without grinding or impact media

Chemical Communications, Год журнала: 2022, Номер 59(8), С. 1010 - 1013

Опубликована: Дек. 12, 2022

Resonant acoustic mixing (RAM) enables mechanoredox catalysis with BaTiO3 as the piezoelectric catalyst on model diazonium coupling reactions. RAM proceeds without formal grinding or impact media, is faster than analogous ball-milling strategy, and readily scalable. X-ray diffraction spectroscopy indicate that reusability of a under might be limited by boration.

Язык: Английский

---

Optimizing the Green Synthesis of ZIF-8 by Reactive Extrusion Using In Situ Raman Spectroscopy

ACS Sustainable Chemistry & Engineering, Год журнала: 2023, Номер 11(13), С. 5175 - 5183

Опубликована: Март 21, 2023

We report the scale-up of a batch solid synthesis zeolitic imidazolate framework-8 (ZIF-8) for reactive extrusion. The crystalline product forms in extruder directly under mixture 2-methylimidazole and basic zinc carbonate presence catalytic amount liquid. process parameters such as temperature, liquid type, feeding rate, linker excess were optimized using setup specifically designed situ Raman spectroscopy. Highly ZIF-8 with Brunauer–Emmett–Teller (BET) surface area 1816 m2 g–1 was quantitatively prepared at mild temperature ethanol small linker. Finally, we developed simple comprehensive approach to evaluating environmental friendliness scalability metal–organic framework (MOF) syntheses view their large-scale production.

Язык: Английский

---

Boosting tribo-catalytic conversion of H ₂O and CO ₂ by Co ₃O ₄ nanoparticles through metallic coatings in reactors

Journal of Advanced Ceramics, Год журнала: 2023, Номер 12(10), С. 1833 - 1843

Опубликована: Июль 26, 2023

In recent years, more and metal oxides have been finding critical tribo-catalytic applications. Presently, we explored the conversion of H₂O CO₂ using Co₃O₄ nanoparticles obtained some surprising results. an as-received 150 mL glass reactor enclosed with 10 H₂O, 0.10 g nanoparticles, 1 atm CO₂, a Teflon magnetic rotary disk, observed production as much 57.41 µmol/L H₂, 0.15 CH₄, 0.21 CO after 5 h stirring. Metallic coatings Cu, Ni, SUS316, Ti, Nb, Mo, W were further introduced on bottoms separately. For those reduction was dramatically enhanced C₂₊ products C₂H₆ C₂H₄ observed. Especially for Ti coating, amounts H₂ CH₄ increased by 2 26 times from bottom, respectively, very impressive. proven chemically stable under stirring in water, hydroxyl radicals superoxide detected through fluorescence spectroscopy electron paramagnetic resonance analyses. These findings not only reveal outstanding capability to generate multicarbon tribo-catalysis but also highlight promising potential whole harness mechanical energy addressing shortages environmental pollution.

Язык: Английский

---

Milling Medium‐Free Suzuki Coupling by Direct Mechanocatalysis: From Mixer Mills to Resonant Acoustic Mixers**

Chemistry - A European Journal, Год журнала: 2023, Номер 29(65)

Опубликована: Июль 28, 2023

Here we describe the development of a sustainable and cost-effective approach for catalytic cross-coupling reactions in mechanochemistry. It is found that substrate's impact with vessel wall alone sufficient to initiate reaction, thus indicating milling balls function primarily as mixing agent direct mechanocatalytic Suzuki coupling. The absence can be offset by adjusting rheology using liquid-assisted grinding (LAG). LAG sweet spot 0.25 μL mg-1 confirmed both resonance acoustic mixers (RAMs) ball-free mixer mills, higher than presence balls. RAMs exhibit excellent performance achieving yields 90 % after 60 min complete conversion min. longevity significantly improved RAM, allowing at least 20 without deterioration.

Язык: Английский

---

Mechanochemical Deoxyfluorination of Carboxylic Acids to Acyl Fluorides and Successive Mechanochemical Amide Bond Formation

ACS Sustainable Chemistry & Engineering, Год журнала: 2024, Номер 12(9), С. 3565 - 3574

Опубликована: Фев. 16, 2024

Diverse methods have been reported for the synthesis of acyl fluorides; however, an environmentally benign method fluorides remains underdeveloped. In this study, we developed solvent-free mechanochemical deoxyfluorination carboxylic acids to mediated by 1,1,2,2-tetrafluoroethyl-N,N-dimethylamine (TFEDMA) using a ball mill. This facilitated high product yields in short reaction times even sterically challenged acids. We also realized coupling and amines as well TFEDMA-mediated direct with via sequential one-pot deoxyfluorination/coupling pathway. Furthermore, protocol was expanded include peptide synthesis. The efficiency protocol, terms speed, characteristics, favorable E-factor, aligns requirements current environmental policies.

Язык: Английский

---

Nickel-catalyzed cross-coupling aminations via high-throughput mechanochemistry enabled by resonant acoustic mixing

Green Chemistry, Год журнала: 2024, Номер 26(14), С. 8341 - 8347

Опубликована: Янв. 1, 2024

Resonant Acoustic Mixing (RAM) allows High Throughput Experimentation (HTE) using commercially available 96-well plates as exemplified by the nickel catalyzed C–N cross coupling of aryl halides with different amine and anilines.

Язык: Английский

---

Halogen-bonded cocrystals via resonant acoustic mixing

RSC Mechanochemistry, Год журнала: 2024, Номер 1(1), С. 50 - 62

Опубликована: Янв. 1, 2024

Resonant acoustic mixing (RAM) is shown to be an effective mechanochemical method for producing halogen-bonded cocrystals, characterized here by X-ray diffraction and solid-state NMR. An elusive stoichiomorph unobtainable milling found via RAM.

Язык: Английский

---