The “η-sweet-spot” (ηmax) in liquid-assisted mechanochemistry: polymorph control and the role of a liquid additive as either a catalyst or an inhibitor in resonant acoustic mixing (RAM) DOI
Lori Gonnet,

Tristan H. Borchers,

Cameron B. Lennox

et al.

Faraday Discussions, Journal Year: 2022, Volume and Issue: 241, P. 128 - 149

Published: Aug. 8, 2022

Resonant acoustic mixing (RAM) offers a simple, efficient route for mechanochemical synthesis in the absence of milling media or bulk solvents. Here, we show use RAM to conduct copper-catalysed coupling sulfonamides and carbodiimides. This was previously reported take place only by ball milling, while conventional solution environments it is not efficient, does at all. The results demonstrate as suitable methodology reactions accessed provide detailed, systematic overview how amount liquid additive, measured ratio volume weight reactants (η, μL mg-1), can affect course reaction polymorphic composition its product. Switching from allowed discovery new polymorph model sulfonylguanidine obtained catalytic di(cyclohexyl)carbodiimide (DCC) p-toluenesulfonamide, ability control temperature enabled situ behaviour this nascent We that conversion given time change monotonically but, instead, achieves maximum well-defined η-value. "η-sweet-spot" herein designated ηmax. explored sensitivity η on order 0.01 mg-1, which corresponds an additive below 5 mol% compared reactants, least one two orders magnitude lower than η-value typically considered design liquid-assisted reactions. Such suggests strategies optimise should systematically evaluate η-values increments even finer. At other ηmax drops off, demonstrating same act either catalyst inhibitor reaction, depending amount.

Language: Английский

Mechanochemistry: New Tools to Navigate the Uncharted Territory of “Impossible” Reactions DOI Creative Commons
Federico Cuccu, Lidia De Luca, Francesco Delogu

et al.

ChemSusChem, Journal Year: 2022, Volume and Issue: 15(17)

Published: July 21, 2022

Mechanochemical transformations have made chemists enter unknown territories, forcing a different chemistry perspective. While questioning or revisiting familiar concepts belonging to solution chemistry, mechanochemistry has broken new ground, especially in the panorama of organic synthesis. Not only does it foster "thinking outside box", but also opened reaction paths, allowing overcome weaknesses traditional exactly where use well-established solution-based methodologies rules out progress. In this Review, reader is introduced an intriguing research subject not yet fully explored and waiting for improved understanding. Indeed, study mainly focused on that, although impossible solution, become possible under mechanochemical processing conditions, simultaneously entailing innovation expanding chemical space.

Language: Английский

Citations

184
Green metrics in mechanochemistry DOI Creative Commons

Nicolas Fantozzi,

Jean‐Noël Volle, Andrea Porcheddu

et al.

Chemical Society Reviews, Journal Year: 2023, Volume and Issue: 52(19), P. 6680 - 6714

Published: Jan. 1, 2023

The quantitative assessment of the greenness mechanochemical processes for green metrics were calculated is herein reported. A general introduction to topic, variables influencing reaction outcome and, an outlook are also provided.

Language: Английский

Citations

81
Salient Achievements in Synthetic Organic Chemistry Enabled by Mechanochemical Activation DOI
Eusebio Juaristi, C.G. Ávila-Ortíz

Synthesis, Journal Year: 2023, Volume and Issue: 55(16), P. 2439 - 2459

Published: May 3, 2023

Abstract Although known for millennia, it is only recently that mechanochemistry has received serious attention by chemists. Indeed, during the past 15 years an extraordinary number of reports concerning solid-state chemical transformations through grinding and milling techniques have been recorded. This short review discusses circumstances led this renaissance, highlighting present intense interest in so-called green chemistry, enabling capacity to handle insoluble substrates, identification profound influence additives can on mechanochemically activated reactions. The core account focuses salient developments synthetic organic especially amino acid peptide­ mechanosynthesis, successful employment mechanochemical activation combination with asymmetric organocatalysis, promising enzymatic whole cell biocatalysis, remarkable achievement multicomponent selective reactions via complex, multistep reaction pathways, mechanosynthesis representative heterocycles. final section comments some pending tasks area, such as scaling-up processes be practical use industry, requirement easier more efficient control parameters monitoring devices, consequently careful analysis additional procedures a proper understanding phenomena. 1 Introduction 2 Brief History Mechanochemistry 3 Milling Equipment Reaction Parameters 4 Attributes That Propelled Its Present Renaissance 4.1 Enormous Attention Being Presently Paid Sustainable Chemistry 4.2 Reduced Energy Consumption 4.3 Additive-Based 4.4 Handling Insoluble Reactants 4.5 ‘Impossible’ Reactions Are Successful 4.6 Air- Water-Sensitive Reagents Ball 5 Salient Developments Mechanochemical Activation Synthetic Organic 5.1 Amino Acid Peptide Mechanosynthesis 5.2 Asymmetric Synthesis Organocatalysis under Ball-Milling Conditions 5.3 Mechanoenzymology 5.4 Multicomponent Activated 5.5 Heterocycles Modification 6 Future Directions 6.1 Scaling-Up Protocols 6.2 Temperature-Controlled 6.3 Understanding Transformations 6.4 Emerging Techniques 7 Conclusions

Language: Английский

Citations

52
Principles and theories of green chemistry for corrosion science and engineering: design and application DOI
Chandrabhan Verma, Dheeraj Singh Chauhan, Ruby Aslam

et al.

Green Chemistry, Journal Year: 2024, Volume and Issue: 26(8), P. 4270 - 4357

Published: Jan. 1, 2024

Given the high toxicity of inorganic inhibitors, organic substances, primarily heterocycles, have been proven to be one most efficient, cost-effective, and practical alternatives.

Language: Английский

Citations

48
Tinkering with Mechanochemical Tools for Scale Up DOI Creative Commons
Javier F. Reynes, Valerio Isoni, Felipe Garcı́a

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(44)

Published: April 28, 2023

Mechanochemistry provides an environmentally benign platform to develop more sustainable chemical processes by limiting raw materials, energy use, and waste generation while using physically smaller equipment. A continuously growing research community has steadily showcased examples of beneficial mechanochemistry applications at both the laboratory preparative scale. In contrast solution-based chemistry, mechanochemical have not yet been standardized, thus scaling up is still a nascent discipline. The purpose this Minireview highlight similarities, differences challenges various approaches that successfully applied for range scales. We hope provide discussion starting point those interested in further developing commercial use and/or industrialisation.

Language: Английский

Citations

46
Mechanochemical Approach for Air‐Tolerant and Extremely Fast Lithium‐Based Birch Reductions in Minutes DOI
Yunpeng Gao, Koji Kubota, Hajime Ito

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(21)

Published: March 22, 2023

Birch reduction has been widely used in organic synthesis for over half a century as powerful method to dearomatize arenes into 1,4-cyclohexadiene derivatives. However, the conventional reaction using liquid ammonia requires laborious procedures ensure inert conditions and low temperatures. Although several ammonia-free modifications have reported, development of an operationally simple, efficient, scalable protocol remains challenge. Herein, we report lithium-based air without special operating ball-milling technique. This is characterized by its operational simplicity extremely short time (within 1 min), probably owing situ mechanical activation lithium metal, broad substrate scope, no requirement dry bulk solvents. The potential our flash also demonstrated efficient bioactive target molecules gram-scale synthesis.

Language: Английский

Citations

45
Chemical recycling of polycarbonate and polyester without solvent and catalyst: mechanochemical methanolysis DOI

Hyo Won Lee,

Kwangho Yoo,

Lars Borchardt

et al.

Green Chemistry, Journal Year: 2024, Volume and Issue: 26(4), P. 2087 - 2093

Published: Jan. 1, 2024

Mechanochemical methanolysis of polyester and polycarbonate eliminated catalyst solvent.

Language: Английский

Citations

21
MOF membranes for gas separations DOI
Yiming Zhang, Hang Yin,

Lingzhi Huang

et al.

Progress in Materials Science, Journal Year: 2025, Volume and Issue: unknown, P. 101432 - 101432

Published: Jan. 1, 2025

Citations

3
Toward Mechanistic Understanding of Mechanochemical Reactions Using Real-Time In Situ Monitoring DOI
Stipe Lukin, Luzia S. Germann, Tomislav Friščić

et al.

Accounts of Chemical Research, Journal Year: 2022, Volume and Issue: 55(9), P. 1262 - 1277

Published: April 21, 2022

The past two decades have witnessed a rapid emergence of interest in mechanochemistry-chemical and materials reactivity achieved or sustained by the action mechanical force-which has led to application mechanochemistry almost all areas modern chemical synthesis: from organic, inorganic, organometallic chemistry enzymatic reactions, formation metal-organic frameworks, hybrid perovskites, nanoparticle-based materials. recent success ball milling also raised questions about underlying mechanisms realization that rational development effective harnessing mechanochemical for cleaner more efficient manufacturing will critically depend on establishing mechanistic understanding these reactions. Despite their long history, such knowledge framework reactions is still incomplete. This part due the, until recently, unsurmountable challenge directly observing transformations taking place rapidly oscillating rotating vessel, with sample being under continuous impact media. A transformative change studies was recently introduced through first methodologies real-time situ monitoring based synchrotron powder X-ray diffraction Raman spectroscopy. Introduced 2013 2014, new techniques inspired period tremendous method development, resulting are temperature and/or pressure monitoring, extended fine structure (EXAFS), and, latest, nuclear magnetic resonance (NMR) technologies available now experimental strategies advanced data analysis approaches identification quantification short-lived reaction intermediates, models, as well complex three simultaneous approaches. use opportunities has, less than decade, enabled observations kinetics how presence additives, other means modifying reaction, influence rates pathways. These revealed multistep mechanisms, autocatalysis, identified molecules previously not been known even considered possible synthesize conventional Mechanistic (PXRD) spectroscopy highlighted supramolecular complexes (for example, cocrystals) critical intermediates organic synthesis combined isotope labeling provide deeper insight into atomic molecular dynamics conditions. Account provides an overview this exciting, evolving field presenting concepts behind outlining key advances mechanochemistry, selected important pushing forward boundaries measurement techniques, analysis, mapping mechanisms.

Language: Английский

Citations

59
Mechanochemical synthesis of biochar encapsulated FeMn nanoparticles with strong metal–carbon interactions for efficient degradation of tetracycline via activating peroxymonosulfate DOI
Yue Wang, Zhenglong Liu, Pan Huang

et al.

Chemical Engineering Journal, Journal Year: 2023, Volume and Issue: 479, P. 147525 - 147525

Published: Nov. 30, 2023

Language: Английский

Citations

40