147045-24-7

Usage

Uses

Used in Organic Synthesis:
2,2,6,6-Tetramethyl-4-(2-propynyloxy)piperidine 1-Oxyl Free Radical is used as a catalyst for facilitating various chemical reactions in organic synthesis. Its nitroxide function and radical scavenging ability make it an efficient mediator, enhancing the reaction rates and selectivity.
Used in Polymer Chemistry:
In polymer chemistry, 2,2,6,6-Tetramethyl-4-(2-propynyloxy)piperidine 1-Oxyl Free Radical is used as a mediator to control the polymerization processes. Its ability to initiate or mediate controlled radical polymerization is crucial for the development of new materials with specific properties and structures.
Used in Material Development:
2,2,6,6-Tetramethyl-4-(2-propynyloxy)piperidine 1-Oxyl Free Radical is used as a key component in the development of new materials and coatings. Its role in controlled radical polymerization allows for the creation of materials with tailored properties, such as improved strength, flexibility, or resistance to environmental factors.
Used in Medical Research:
In the field of medicine, 2,2,6,6-Tetramethyl-4-(2-propynyloxy)piperidine 1-Oxyl Free Radical is used as a potential candidate in the development of new drugs and therapeutics. Its unique properties and reactivity may contribute to the discovery of novel treatments for various diseases and conditions.

Upstream product

• 45985-24-8 TEMPOL 
• 106-96-7 propargyl bromide 
• 2226-96-2 tempol 

Downstream Products

• 1255743-81-7 1-cyclohexyloxy-2,2,6,6-tetramethyl-4-prop-2-ynyloxypiperidine 
• 1061204-61-2 C₄₉H₅₄N₁₃O₅ 

Relevant academic research and scientific papers

Synthesis of thermal degradable poly(alkoxyamine) through a novel nitroxide radical coupling step growth polymerization mechanism

The thermal degradable poly(alkoxyamine) was synthesized through a novel nitroxide radical coupling step growth polymerization (NRC-SGP) mechanism. The monomers of 1,4-phenylene bis(2-bromo-2-methylpropanoate) (monomer 1) and 1,4-phenylene bis(2-bromopropanoate) (monomer 1) with two bromide groups and 1,6-di(4-(2,2,6,6-tetramethylpiperidine-1-oxyl))-hexa-2,4-diyne (monomer 2) with two nitroxide radicals were first designed and synthesized. Then the NRC-SGP mechanism was investigated in detail by optimizing the factors such as polymerization time, temperature, solvents, catalysts, ligand, monomer concentration, and structures connected to halogen groups. The results showed that the termination by disproportionation was the major side reaction in the NRC-SGP mechanism, and the lower temperature (25 °C) would favor an important contribution. The proper combination of all factors could lead to an ideal NRC-SGP procedure. Finally, the thermal stability of formed poly(alkoxyamine) was monitored by TG, DSC and SEC instruments, and the results showed that the poly(alkoxyamine) would suffer a severe thermal degradation at the elevated temperature above 140°C.

A biphasic oxidation of alcohols to aldehydes and ketones using a simplified packed-bed microreactor

We demonstrate the preparation and characterization of a simplified packed-bed microreactor using an immobilized TEMPO catalyst shown to oxidize primary and secondary alcohols via the biphasic Anelli-Montanari protocol. Oxidations occurred in high yields with great stability over time. We observed that plugs of aqueous oxidant and organic alcohol entered the reactor as plugs but merged into an emulsion on the packed-bed. The emulsion coalesced into larger plugs upon exiting the reactor, leaving the organic product separate from the aqueous by-products. Furthermore, the microreactor oxidized a wide range of alcohols and remained active in excess of 100 trials without showing any loss of catalytic activity.

Grafting nitroxide radicals on nanodiamond surface using click chemistry

We demonstrate grafting of nitroxide radicals on the surface of nanodiamonds (NDs). The surface of NDs is functionalized by azide groups. Nitroxide radicals are covalently bonded using Cu(I)-catalyzed azide/alkyne-click chemistry approach. The reaction is confirmed by infrared spectroscopy. The grafting of nitroxides is also verified by studying the rotational correlational time using electron paramagnetic resonance (EPR) spectroscopy. EPR study estimates that a few hundreds (tens) of nitroxide radicals are grafted on the surface of NDs with 100 nm (25 nm) of the average diameter.

TEMPO-functionalized mesoporous silica particles as heterogeneous oxidation catalysts in flow

Organocatalysts immobilized on inorganic porous substrates possess fundamental benefits, e.g., a high catalyst/reactant ratio, easy scalability as well as work-up, and continuous processing. Here we report the development of a heterogeneous (2,2,6,6-tetramethylpiperidin-1-yl)oxyl (TEMPO) catalyst immobilized on mesoporous SiO2 and demonstrate its feasibility in the oxidation of benzyl alcohol to benzaldehyde. Our catalyst system is based on commercially available mesoporous silica particles that are optimized for flow applications (LiChrospher Si 100 from Merck). The transition from well-known silica materials like MCM-41 and SBA-15 to specialized high-performance materials such as the used LiChrospher particles is of great value for getting closer to industrial applications on large scale. We functionalized the material by applying click-chemistry and employed a packed HPLC column for the investigation of the catalyst performance and stability in continuous flow. The material shows the best performance with low catalyst loadings. The catalytic activity can be improved significantly by conversion of the TEMPO radical to an oxoammonium salt prior to the reaction. The material is well suited for applications in continuous flow syntheses, as the spherical shape of the particles results in low back pressures. The organic catalyst produces yields up to 89% with a flow rate of 0.05 mL min-1. The mild reaction conditions allow the use of the material in multi-step reactions. This option was demonstrated by combining the TEMPO-functionalized column with an aminopropyl-functionalized column and performing a TEMPO-mediated oxidation followed by a Knoevenagel condensation in a continuous flow setup for the first time. Long-term tests and post-catalytic analysis show a previously neglected decomposition pathway of TEMPO due to the co-catalyst.

Radical-Enhanced Intersystem Crossing in New Bodipy Derivatives and Application for Efficient Triplet-Triplet Annihilation Upconversion

A long-lived triplet excited state of the well-known fluorophore boron dipyrromethene (Bodipy) was observed for the first time via efficient radical-enhanced intersystem crossing (EISC). The triplet state has been obtained in two dyads in which the Bodipy

A TEMPO-Functionalized Ordered Mesoporous Polymer as a Highly Active and Reusable Organocatalyst

The properties of high stability, periodic porosity, and tunable nature of ordered mesoporous polymers make these materials ideal catalytic nanoreactors. However, their application in organocatalysis has been rarely explored. We report herein for the first time the incorporation of a versatile organocatalyst, 2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO), into the pores of an FDU-type mesoporous polymer via a pore surface engineering strategy. The resulting FDU-15-TEMPO possesses a highly ordered mesoporous organic framework and enhanced stability, and shows excellent catalytic activity in the selective oxidation of alcohols and aerobic oxidative synthesis of 2-substituted benzoxazoles, benzimidazoles and benzothiazoles. Moreover, the catalyst can be easily recovered and reused for up to 7 consecutive cycles.

Fluorescent and Water Dispersible Single-Chain Nanoparticles: Core–Shell Structured Compartmentation

Single-chain nanoparticles (SCNPs) are highly versatile structures resembling proteins, able to function as catalysts or biomedical delivery systems. Based on their synthesis by single-chain collapse into nanoparticular systems, their internal structure is complex, resulting in nanosized domains preformed during the crosslinking process. In this study we present proof of such nanocompartments within SCNPs via a combination of electron paramagnetic resonance (EPR) and fluorescence spectroscopy. A novel strategy to encapsulate labels within these water dispersible SCNPs with hydrodynamic radii of ≈5 nm is presented, based on amphiphilic polymers with additional covalently bound labels, attached via the copper catalyzed azide/alkyne “click” reaction (CuAAC). A detailed profile of the interior of the SCNPs and the labels’ microenvironment was obtained via electron paramagnetic resonance (EPR) experiments, followed by an assessment of their photophysical properties.

Site-Selective Modification of Peptides and Proteins via Interception of Free-Radical-Mediated Dechalcogenation

The development of site-selective chemistry targeting the canonical amino acids enables the controlled installation of desired functionalities into native peptides and proteins. Such techniques facilitate the development of polypeptide conjugates to advance therapeutics, diagnostics, and fundamental science. We report a versatile and selective method to functionalize peptides and proteins through free-radical-mediated dechalcogenation. By exploiting phosphine-induced homolysis of the C?Se and C?S bonds of selenocysteine and cysteine, respectively, we demonstrate the site-selective installation of groups appended to a persistent radical trap. The reaction is rapid, operationally simple, and chemoselective. The resulting aminooxy linker is stable under a variety of conditions and selectively cleavable in the presence of a low-oxidation-state transition metal. We have explored the full scope of this reaction using complex peptide systems and a recombinantly expressed protein.

"Click Chemistry" Mediated Functional Microporous Organic Nanotube Networks for Heterogeneous Catalysis

The synthesis of azide functional microporous organic nanotube networks (N3-MONNs) via a Friedel-Crafts hyper-cross-linking reaction is reported. Subsequently, a general method for obtaining heterogeneous catalysts through a Cu-catalyzed alkyne-azide reaction is presented. The small-molecule catalysts such as 2,2,6,6,-tetramethylpiperidine-1-oyl and 4-(N,N-dimethylamino)pyridine can be anchored into the MONNs. Owing to the hierarchically porous structure and high surface area, these catalysts show high activity in selective oxidation of alcohols and acylation reaction, respectively.

STRUCTURED AND POROUS MATERIALS PARTICULARLY SUITABLE AS POLARIZING AGENTS IN DISSOLUTION DYNAMIC NUCLEAR POLARIZATION

The present invention concerns materials consisting in a porous and structured network, this network being at least in part formed by Si atoms, or Si atoms and metal atoms, linked to each other by oxy bridges, comprising organic molecules which include at least one nitroxyl radical -NO· and which are covalently bonded to the network via siloxy bonds, the amount of nitroxyl radical -NO· ranging from 30 to 120 nmol per square meter of material characterized in that : Q > 0.4 and 4s a b a * and T1b being obtained by the method defined in claim 1.