Biasing Divergent Polycyclic Aromatic Hydrocarbon Oxidation Pathway by Solvent-Free Mechanochemistry DOI
Hao Luo,

Fang‐Zi Liu,

Yan Liu

и другие.

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(28), С. 15118 - 15127

Опубликована: Июль 10, 2023

Precise control in reaction selectivity is the goal modern organic synthesis, and it has been widely studied throughout synthetic community. In comparison, of divergent reactivity a given reagent under different conditions relatively less explored aspect chemical selectivity. We herein report an unusual between polycyclic aromatic hydrocarbons periodic acid H5IO6 (1), where product outcome dictated by choice conditions. That is, reactions solution-based condition give preferentially C-H iodination products, while solvent-free mechanochemical provide oxidation quinone products. Control experiments further indicated that not intermediate toward vice versa. Mechanistic studies unveiled situ crystalline-to-crystalline phase change 2 during ball-milling treatment, we assigned as polymeric hydrogen-bond network 1. believe this crystalline shields more embedded electrophilic I═O group 1 from bias pathway (with I═O) solid state. Collectively, work demonstrates mechanochemistry can be employed to completely switch unmask hidden reagents.

Язык: Английский

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

и другие.

ChemSusChem, Год журнала: 2022, Номер 15(17)

Опубликована: Июль 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.

Язык: Английский

Процитировано

188

Green metrics in mechanochemistry DOI Creative Commons

Nicolas Fantozzi,

Jean‐Noël Volle, Andrea Porcheddu

и другие.

Chemical Society Reviews, Год журнала: 2023, Номер 52(19), С. 6680 - 6714

Опубликована: Янв. 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.

Язык: Английский

Процитировано

89

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

Synthesis, Год журнала: 2023, Номер 55(16), С. 2439 - 2459

Опубликована: Май 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

Язык: Английский

Процитировано

52

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

и другие.

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(44)

Опубликована: Апрель 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.

Язык: Английский

Процитировано

51

Photoactive Fe3O4@Fe2O3 Synthesized from Industrial Iron Oxide Dust for Fenton-Free Degradation of Multiple Organic Dyes DOI
Jaidev Kaushik,

Twinkle,

Tisha

и другие.

Industrial & Engineering Chemistry Research, Год журнала: 2023, Номер 62(27), С. 10487 - 10497

Опубликована: Июнь 27, 2023

Herein, we described a cost-effective, viable methodology for using an iron-based industrial waste material known as iron oxide dust (IOD), also Hematite (α-Fe2O3) the synthesis of their chemically reduced magnetic version named r-IOD (Fe3O4@α-Fe2O3). showed its visible-light-promoted photoresponsive behavior photodegradation higher concentration (∼1000 mg L–1) five different model dyes (methyl orange (MO), metanil yellow (MY), Congo red (CR), methylene blue (MB), crystal violet (CV), and mixtures) in presence sunlight. Based on kinetic radical trapping experiments, mechanistic analysis supports significant involvement superoxide radicals responsible photodegradation. Moreover, soil samples were externally spiked with further analyzed similar set experiments to support viability reported procedure, concerning utilization materials.

Язык: Английский

Процитировано

27

3D Porous MoS2-Decorated Reduced Graphene Oxide Aerogel as a Heterogeneous Catalyst for Reductive Transformation Reactions DOI
Jaidev Kaushik, Charu Sharma, Nicky Kumar Lamba

и другие.

Langmuir, Год журнала: 2023, Номер 39(36), С. 12865 - 12877

Опубликована: Авг. 28, 2023

The MoS2-based reduced graphene oxide aerogel (MoS2-rGOA)-assisted organic transformation reactions are presented. MoS2-rGOA is used as a heterogeneous catalyst for the reduction of benzene derivatives such benzaldehyde, nitrobenzene, and benzonitrile to benzyl alcohol, aniline, benzamide their derivatives, respectively, in green solvents (water/methanol) reducing agents (hydrazine hydrate having N2 H2 byproducts). mechanistic features pathway, substrate scope, best suitable conditions by varying temperature, solvent, agent, loading, time, etc. optimized. All synthesized products obtained quantitative yield with purity well characterized based on nuclear magnetic resonance analysis. Further, it also observed that our efficiently recyclable works checked up 5 cycles.

Язык: Английский

Процитировано

26

Recent Highlights in Micellar Catalysis: An Industrial Outlook DOI
Tharique N. Ansari, Guolin Xu, Andrew Z. Preston

и другие.

Organic Process Research & Development, Год журнала: 2024, Номер 28(4), С. 816 - 830

Опубликована: Март 14, 2024

From the context of sustainability, contemporary synthetic organic chemistry practices require significant transformation, as indicated by various sustainability matrices like atom economy, process mass intensity (PMI), E-factor, and DOZN. These factors have evidently unveiled inherent inefficiencies intrinsic to conventional protocols identified solvents principal causative agent. In response, utilization water a primary reaction medium for transformations has emerged an appealing alternative. This approach flourished with emergence micellar catalysis, where amphiphilic molecules alter bulk aqueous medium's solvation properties promote desired chemical transformation under milder sustainable conditions. After 2010, this technology gained considerable momentum established foundational framework performing reactions conditions, consequently mitigating dependency on hazardous solvents. perspective, recent advances in field catalysis will be discussed industrial applications, along future directions challenges associated regime.

Язык: Английский

Процитировано

11

Moving mechanochemistry forward DOI Creative Commons
James D. Batteas, Kerstin G. Blank, Evelina Colacino

и другие.

RSC Mechanochemistry, Год журнала: 2025, Номер unknown

Опубликована: Янв. 1, 2025

James Batteas, et al. , introduce the field of mechanochemistry in “Moving forward”.

Язык: Английский

Процитировано

1

Fe3O4 Nanoparticles Synthesized from Waste Iron Dust for Sunlight-Boosted Photodegradation of Nitrophenols and Their Mixtures DOI

Twinkle Twinkle,

Jaidev Kaushik,

Tisha Singla

и другие.

Industrial & Engineering Chemistry Research, Год журнала: 2023, Номер 62(23), С. 9091 - 9103

Опубликована: Июнь 1, 2023

Here, we describe a simpler-sustainable approach for fabricating photo-active magnetite nanoparticles (Fe3O4-NPs) using an almost inert waste material known as red-colored iron oxide dust (IOD). The synthesized heterogeneous catalyst Fe3O4-NPs showed photoactivity in the presence of sunlight and was used photodegradation higher concentration (∼1000 mg L–1) noxious nitrophenols their mixtures aqueous medium. Kinetic studies, including control tests, have been performed to compare photocatalytic performance vs IOD artificial bulb light. half-life percentage strongly suggest that influences faster rate mixtures. Radical trapping experiments were identify reactive active species responsible photodegradation, results support significant involvement hydroxyl radicals along with holes. Further, real-life assessment photocatalyst explored by checking its capability industrial wastewater soil samples via external spiking nitrophenols. Moreover, are compared two commercially available Fe3O4, which comparable results, case trinitrophenol (TNP) mixture, slightly better results. quantitative studies green chemistry metrics DOZN software-based calculations supported greener more sustainable process present method synthesis Fe3O4-NPs.

Язык: Английский

Процитировано

18

Opportunities and Challenges in Applying Solid‐State NMR Spectroscopy in Organic Mechanochemistry DOI Creative Commons
Igor d’Anciães Almeida Silva, Ettore Bartalucci, Carsten Bolm

и другие.

Advanced Materials, Год журнала: 2023, Номер 35(52)

Опубликована: Июль 5, 2023

In recent years it is shown that mechanochemical strategies can be beneficial in directed conversions of organic compounds. Finding new reactions proved difficult, and due to the lack mechanistic understanding reaction events, respective efforts have mostly remained empirical. Spectroscopic techniques are crucial shedding light on these questions. this overview, opportunities challenges solid-state nuclear magnetic resonance (NMR) spectroscopy field mechanochemistry discussed. After a brief discussion basics high-resolution NMR under magic-angle spinning (MAS) conditions, seven for presented, ranging from ex situ approaches structurally elucidated products obtained by milling potential limitations approaches. Particular strengths NMR, instance differentiating polymorphs, NMR-crystallographic structure-determination protocols, or detecting weak noncovalent interactions molecular-recognition events employing proton-detected experiments at fast MAS frequencies,

Язык: Английский

Процитировано

18