Browse
Submit Data
Databases
API
Help

Dataset Information

0 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Complementarity of solution and solid state mechanochemical reaction conditions demonstrated by 1,2-debromination of tricyclic imides.

ABSTRACT: The solution phase 1,2-debromination of polycyclic imides using the Zn/Ag couple was successfully transferred to solid state mechanochemical conditions. The Zn/Ag couple was replaced by the Zn/Cu couple which was prepared without any metal activation by in situ ball milling of zinc and copper dusts. The advantage of the ball milling process is that the whole procedure is operationally very simplified. The reactive alkene generated was trapped in situ by several dienes and the respective Diels-Alder cycloadducts were obtained. It was demonstrated that mechanochemical milling offers complementary conditions to solution (thermal) reaction by allowing chemical transformations to proceed which were not possible in solution and vice versa.

SUBMITTER: Strbac P

PROVIDER: S-EPMC9235900 | biostudies-literature | 2022

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

Complementarity of solution and solid state mechanochemical reaction conditions demonstrated by 1,2-debromination of tricyclic imides.

Štrbac Petar P Margetić Davor D

Beilstein journal of organic chemistry 20220624

The solution phase 1,2-debromination of polycyclic imides using the Zn/Ag couple was successfully transferred to solid state mechanochemical conditions. The Zn/Ag couple was replaced by the Zn/Cu couple which was prepared without any metal activation by in situ ball milling of zinc and copper dusts. The advantage of the ball milling process is that the whole procedure is operationally very simplified. The reactive alkene generated was trapped in situ by several dienes and the respective Diels-Al ...[more]

PMID: 35821693

Similar Datasets

Mechanochemical <i>N</i>-alkylation of imides.

Project description:The mechanochemical N-alkylation of imide derivatives was studied. Reactions under solvent-free conditions in a ball mill gave good yields and could be put in place of the classical solution conditions. The method is general and can be applied to various imides and alkyl halides. Phthalimides prepared under ball milling conditions were used in a mechanochemical Gabriel synthesis of amines by their reaction with 1,2-diaminoethane.

| S-EPMC5588455 | biostudies-literature

Optimizing Shape Complementarity Enables the Discovery of Potent Tricyclic BCL6 Inhibitors.

Project description:To identify new chemical series with enhanced binding affinity to the BTB domain of B-cell lymphoma 6 protein, we targeted a subpocket adjacent to Val18. With no opportunities for strong polar interactions, we focused on attaining close shape complementarity by ring fusion onto our quinolinone lead series. Following exploration of different sized rings, we identified a conformationally restricted core which optimally filled the available space, leading to potent BCL6 inhibitors. Through X-ray structure-guided design, combined with efficient synthetic chemistry to make the resulting novel core structures, a >300-fold improvement in activity was obtained by the addition of seven heavy atoms.

| S-EPMC9234963 | biostudies-literature

Mechanochemical Lignin-Mediated Strecker Reaction.

Project description:A mechanochemical Strecker reaction involving a wide range of aldehydes (aromatic, heteroaromatic and aliphatic), amines, and KCN afforded a library of α-aminonitriles upon mechanical activation. This multicomponent process was efficiently activated by lignocellulosic biomass as additives. Particularly, commercially available Kraft lignin was found to be the best activator for the addition of cyanide to the in situ formed imines. A comparative study of the 31P-NMR (Nuclear Magnetic Resonance) along with IR (Infrared) data analysis for the Kraft lignin and methylated Kraft lignin samples ascertained the importance of the free hydroxyl groups in the activation of the mechanochemical reaction. The solvent-free mechanochemical Strecker reaction was then coupled with a lactamization process leading to the formation of the N-benzylphthalimide (5a) and the isoindolinone derivative 6a.

| S-EPMC6155632 | biostudies-literature

Solution-phase synthesis of a tricyclic pyrrole-2-carboxamide discovery library applying a stetter-Paal-Knorr reaction sequence.

Project description:The solution-phase synthesis of a discovery library of 178 tricyclic pyrrole-2-carboxamides was accomplished in nine steps and seven purifications starting with three benzoyl-protected amino acid methyl esters. Further diversity was introduced by two glyoxaldehydes and 41 primary amines. The combination of Pauson-Khand, Stetter, and microwave-assisted Paal-Knorr reactions was applied as a key sequence. The discovery library was designed with the help of QikProp 2.1, and physicochemical data are presented for all pyrroles. Library members were synthesized and purified in parallel and analyzed by LC/MS. Selected compounds were fully characterized.

| S-EPMC3433767 | biostudies-literature

Mechanical gating of a mechanochemical reaction cascade.

Project description:Covalent polymer mechanochemistry offers promising opportunities for the control and engineering of reactivity. To date, covalent mechanochemistry has largely been limited to individual reactions, but it also presents potential for intricate reaction systems and feedback loops. Here we report a molecular architecture, in which a cyclobutane mechanophore functions as a gate to regulate the activation of a second mechanophore, dichlorocyclopropane, resulting in a mechanochemical cascade reaction. Single-molecule force spectroscopy, pulsed ultrasonication experiments and DFT-level calculations support gating and indicate that extra force of >0.5 nN needs to be applied to a polymer of gated gDCC than of free gDCC for the mechanochemical isomerization gDCC to proceed at equal rate. The gating concept provides a mechanism by which to regulate stress-responsive behaviours, such as load-strengthening and mechanochromism, in future materials designs.

| S-EPMC5116086 | biostudies-literature

Forcing the reversibility of a mechanochemical reaction.

Project description:Mechanical force modifies the free-energy surface of chemical reactions, often enabling thermodynamically unfavoured reaction pathways. Most of our molecular understanding of force-induced reactivity is restricted to the irreversible homolytic scission of covalent bonds and ring-opening in polymer mechanophores. Whether mechanical force can by-pass thermodynamically locked reactivity in heterolytic bimolecular reactions and how this impacts the reaction reversibility remains poorly understood. Using single-molecule force-clamp spectroscopy, here we show that mechanical force promotes the thermodynamically disfavored SN2 cleavage of an individual protein disulfide bond by poor nucleophilic organic thiols. Upon force removal, the transition from the resulting high-energy unstable mixed disulfide product back to the initial, low-energy disulfide bond reactant becomes suddenly spontaneous, rendering the reaction fully reversible. By rationally varying the nucleophilicity of a series of small thiols, we demonstrate how force-regulated chemical kinetics can be finely coupled with thermodynamics to predict and modulate the reversibility of bimolecular mechanochemical reactions.

| S-EPMC6082871 | biostudies-literature

Synthesis of New Tricyclic 1,2-Thiazine Derivatives with Anti-Inflammatory Activity.

Project description:New, tricyclic compounds containing a sulfonyl moiety in their structure, as potential safer COX inhibitors, were designed and synthesized. New derivatives have three conjugated rings and a sulfonyl group. A third ring, i.e., an oxazine, oxazepine or oxazocin, has been added to the 1,2-benzothiazine skeleton. Their anti-COX-1/COX-2 and cytotoxic effects in vitro on NHDF cells, together with the ability to interact with model membranes and the influence on reactive oxygen species and nitric oxide, were studied. Additionally, a molecular docking study was performed to understand the binding interaction of the compounds with the active site of cyclooxygenases. For the abovementioned biological evaluation of new tricyclic 1,2-benzothiazine derivatives, the following techniques and procedures were employed: the differential scanning calorimetry, the COX colorimetric inhibitor screening assay, the MTT, DCF-DA and Griess assays. All of the compounds studied demonstrated preferential inhibition of COX-2 compared to COX-1. Moreover, all the examined tricyclic 1,2-thiazine derivatives interacted with the phospholipid model membranes. Finally, they neither have cytotoxic potency, nor demonstrate significant influence on the level of reactive oxygen species or nitric oxide. Overall, the tricyclic 1,2-thiazine derivatives are good starting points for future pharmacological tests as a group of new anti-inflammatory agents.

| S-EPMC8346139 | biostudies-literature

Chromium-ruthenium oxide solid solution electrocatalyst for highly efficient oxygen evolution reaction in acidic media.

Project description:The development of active, acid-stable and low-cost electrocatalysts for oxygen evolution reaction is urgent and challenging. Herein we report an Iridium-free and low ruthenium-content oxide material (Cr0.6Ru0.4O2) derived from metal-organic framework with remarkable oxygen evolution reaction performance in acidic condition. It shows a record low overpotential of 178 mV at 10 mA cm-2 and maintains the excellent performance throughout the 10 h chronopotentiometry test at a constant current of 10 mA cm-2 in 0.5 M H2SO4 solution. Density functional theory calculations further revealed the intrinsic mechanism for the exceptional oxygen evolution reaction performance, highlighting the influence of chromium promoter on the enhancement in both activity and stability.

| S-EPMC6329788 | biostudies-literature

PtFeCoNiCu high-entropy solid solution alloy as highly efficient electrocatalyst for the oxygen reduction reaction.

Project description:Searching for an efficient, durable, and low cost catalyst toward oxygen reduction reaction (ORR) is of paramount importance for the application of fuel cell technology. Herein, PtFeCoNiCu high-entropy alloy nanoparticles (PFCNC-HEA) is reported as electrocatalyst toward ORR. It shows remarkable ORR catalytic mass activity of 1.738 A mg-1 Pt at 0.90 V, which is 15.8 times higher than that of the state-of-art commercial Pt/C catalyst. It also exhibits outstanding stability with negligible voltage decay (3 mV) after 10k cycles accelerated durability test. High ORR activity is ascribed to the ligand effect caused by polymetallic elements, the optimization of the surface electronic structure, and the formation of multiple active sites on the surface. In the proton exchange membrane fuel cell setup, this cell delivers a power density of up to 1.380 W cm-2 with a cathodic Pt loading of 0.03 mgPt cm-2, demonstrating a promising catalyst design direction for highly efficient ORR.

| S-EPMC9860490 | biostudies-literature

Solid-state mechanochemical ω-functionalization of poly(ethylene glycol).

Project description:Poly(ethylene glycol) (PEG) is a linear polymer with a wide range of applications in chemical manufacturing, drug development and nanotechnology. PEG derivatives are being increasingly used to covalently modify small molecule and peptide drugs, as well as bioactive nanomaterials in order to improve solubility in biological serum, reduce immunogenicity, and enhance pharmacokinetic profiles. Herein we present the development of mechanochemical procedures for PEG functionalization without the need for bulk solvents, offering a cleaner and more sustainable alternative to existing solution-based PEG procedures. The herein presented mechanochemical procedures enable rapid and solvent-free derivatization of PEG with tosyl, bromide, thiol, carboxylic acid or amine functionalities in good to quantitative yields and with no polymer chain oligomerization, proving the versatility of the method.

| S-EPMC5629410 | biostudies-literature

OmicsDI is part of the ELIXIR infrastructure

OmicsDI is an Elixir interoperability service. Learn more ›

Tweets

OmicsDI Databases

PRIDE
PeptideAtlas
MassIVE
JPOST Repository
Physiome Model Repository

EGA
EVA
ENA
LINCS
PAXDB
Cell Collective

MetaboLights
Metabolomics Workbench
MetabolomeExpress
GNPS
BioModels
FAIRDOMHub

ArrayExpress
dbGaP
ExpressionAtlas
GEO
NODE

Information

Databases
Help
API
Contact us
Code on GitHub
Terms of use
Submit Data