102261-92-7

Basic information

• Product Name: Piperidine, 2,2,6,6-tetramethyl-1-(phenylmethoxy)-
• CAS NO: 102261-92-7
• Molecular Formula: C16H25NO
• Molecular Weight: 247.381
• Mol File: 102261-92-7.mol

Chemical Properties

• CAS DataBase Reference: Piperidine, 2,2,6,6-tetramethyl-1-(phenylmethoxy)-(CAS DataBase Reference)
• NIST Chemistry Reference: Piperidine, 2,2,6,6-tetramethyl-1-(phenylmethoxy)-(102261-92-7)
• EPA Substance Registry System: Piperidine, 2,2,6,6-tetramethyl-1-(phenylmethoxy)-(102261-92-7)

Safety Data

• Hazardous Substances Data: 102261-92-7(Hazardous Substances Data)

Upstream product

• 7031-93-8 2,2,6,6-tetramethylpiperidin-1-ol 
• 100-39-0 benzyl bromide 
• 2564-83-2 2,2,6,6-Tetramethyl-1-piperidinyloxy free radical 
• 620-05-3 iodomethylbenzene 
• 108-88-3 toluene 
• 103-80-0 phenylacetyl chloride 
• 145178-53-6 2,3-bis(trimethylsilyl)-1,3-butadiene-1,4-dione 
• 401636-52-0 di-tert-butyl 4-benzyl-2,6-dimethyl-1,4-dihydropyridine-3,5-dicarboxylate 
• 10409-54-8 2-bromo-2-methyl-1-phenyl-propan-1-one 
• 611-70-1 phenyl isopropyl ketone 
• 1539-57-7 diethyl 2,6-dimethyl-4-benzyl-1,4-dihydropyridine-3,5-dicarboxylate 
• 62-53-3 aniline 
• 65-85-0 benzoic acid 
• 10364-94-0 1-benzoylimidazole 

Downstream Products

• 2564-83-2 2,2,6,6-Tetramethyl-1-piperidinyloxy free radical 
• 2154-56-5 benzyl radical 
• 103-29-7 1,1'-(1,2-ethanediyl)bisbenzene 

Relevant articles and documents

Alkylation Reactions of Azodicarboxylate Esters with 4-Alkyl-1,4-Dihydropyridines under Catalyst-Free Conditions

Introduction of alkyl groups on azodicarboxylate esters is an important method to prepare alkyl amine derivatives. Herein, we report reactions of 4-alkyl-1,4-dihydropyridines as alkylation reagents with di-tert-butyl azodicarboxylate to prepare alkyl amin

Magnetic Field Effects on the Dynamics of Nitroxide-Based Singlet Radical Pairs in Micelles

The nitroxide adduct 1-benzyloxy-2,2,6,6-tetramethylpiperidine (3) undergoes rapid photocleavage to yield 2,2,6,6-tetramethylpiperidine N-oxide and benzyl radicals.Laser excitation (248 nm) of 3 in aqueous micellar solution leads to the formation of singlet radical pairs which decay via a combination of separation and geminate processes.The singlet radical pair produced from 3 undergoes moderately slow recombination and as a result allows for the competition between spin evolution and radical escape.Application of an external magnetic field leads to an increase in the rate constant for the geminate radical reaction, reflecting that the magnetic field prevents the interconversion of the singlet radical pair to the unreactive T- and T+ triplet sublevels.In contrast, when the radicals are produced directly on the triplet surface by sensitization, application of a field leads to a slowdown of radical recombination, as normally observed for triplet radical pairs in heterogeneous media.The magnetic field effects are ascribed to the manifestation of the HFI mechanism.The kinetic analyses for the various cases possible are presented in detail.

Unprecedented and Reversible Cobalt-to-Carbon Alkyl Bond Rearrangement in the Coenzyme B12 Model Complex C6H5CH2CoIII[C 2(DO)(DOH)pn]I: Synthesis, Structural Characterization, and Mechanistic Studies

Photolysis of the coenzyme B12 model complex PhCH2Co[C2(DO)(DOH)pn]I (1) leads to a high-yield, efficient synthesis of an unprecedented cobalt-to-carbon alkyl rearrangement product Co[C2(DO)(DOH)pnCH2Ph]I (2), (Sf-5-15)-[2-[[3-[[2-(hydroxyamino)-l-methyl-2-(phenylmethyl)butylidene]amino] propyl]imino]-3-pentanone oximato(2-)-N,-N',N'',N"']iodocobalt. The novel product 2 is unequivocally characterized by X-ray crystallography, 1H NMR, visible, and mass spectroscopy, and an elemental analysis. With pure 2 available, a thermal equilibrium between 1 and 2, Keq = 1.5 ± 0.1 (69°C, benzene solvent), is shown to exist, thereby explaining the low (60%) yield of 2 from the thermolysis of 1 at 69 °C. Thermolysis of 2 in the presence of TEMPO free radical trap quantitatively yields trapped benzylTEMPO and ?CoII-[C2(DO)(DOH)pn]I. An Eyring plot of this reaction yields ΔH = 26 ± 2 kcal/mol, ΔS" = -6 ± 7 cal/(mol.K), or ΔG298 = 27 ±3 kcal/mol; the ΔH value plus appropriate corrections imply a low benzyl-carbon bond dissociation energy of 25 kcal/mol in 2. Also provided are a proposed mechanism for the formation of 2, a summary discussion detailing the significance of the results toward explaining a number of related, but poorly understood, literature reports, and a short list of some interesting but unanswered questions that form a basis for future research.

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Radical reactions of diamine bis(phenolate) vanadium(III) complexes. Solid state binding of O2 to form a vanadium(v) peroxo complex

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Electron-Rich, Diiron Bis(monothiolato) Carbonyls: C-S Bond Homolysis in a Mixed Valence Diiron Dithiolate

The synthesis and redox properties are presented for the electron-rich bis(monothiolate)s Fe2(SR)2(CO)2(dppv)2 for R = Me ([1]0), Ph ([2]0), CH2Ph ([3]0). Whereas related derivatives adopt C2-symmetric Fe2(CO)2P4 cores, [1]0-[3]0 have Cs symmetry resulting from the unsymmetrical steric properties of the axial vs equatorial R groups. Complexes [1]0-[3]0 undergo 1e- oxidation upon treatment with ferrocenium salts to give the mixed valence cations [Fe2(SR)2(CO)2(dppv)2]+. As established crystallographically, [3]+ adopts a rotated structure, characteristic of related mixed valence diiron complexes. Unlike [1]+ and [2]+ and many other [Fe2(SR)2L6]+ derivatives, [3]+ undergoes C-S bond homolysis, affording the diferrous sulfido-thiolate [Fe2(SCH2Ph)(S)(CO)2(dppv)2]+ ([4]+). According to X-ray crystallography, the first coordination spheres of [3]+ and [4]+ are similar, but the Fe-sulfido bonds are short in [4]+. The conversion of [3]+ to [4]+ follows first-order kinetics, with k = 2.3 × 10-6 s-1 (30 °C). When the conversion is conducted in THF, the organic products are toluene and dibenzyl. In the presence of TEMPO, the conversion of [3]+ to [4]+ is accelerated about 10×, the main organic product being TEMPO-CH2Ph. DFT calculations predict that the homolysis of a C-S bond is exergonic for [Fe2(SCH2Ph)2(CO)2(PR3)4]+ but endergonic for the neutral complex as well as less substituted cations. The unsaturated character of [4]+ is indicated by its double carbonylation to give [Fe2(SCH2Ph)(S)(CO)4(dppv)2]+ ([5]+), which adopts a bioctahedral structure.

Silicates as Latent Alkyl Radical Precursors: Visible-Light Photocatalytic Oxidation of Hypervalent Bis-Catecholato Silicon Compounds

This works introduces hypervalent bis-catecholato silicon compounds as versatile sources of alkyl radicals upon visible-light photocatalysis. Using Ir[(dF(CF3)ppy)2(bpy)](PF6) (dF(CF3)ppy=2-(2,4-difluorophenyl)-5-trifluoromethylpyridine, bpy=bipyridine) as catalytic photooxidant, a series of alkyl radicals, including highly reactive primary ones can be generated and engaged in various intermolecular homolytic reactions. Based on cyclic voltammetry, Stern-Volmer studies, and supported by calculations, a mechanism involving a single-electron transfer from the silicate to the photoactivated iridium complex has been proposed. This oxidative photocatalyzed process can be efficiently merged with nickel-catalyzed Csp2-Csp3 cross-coupling reactions.

Facial strategy for radical species through Ag(I)-mediated oxidation of the alkyl trifluoroborates

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C-N Bond Activation of N, N′-Dialkylacylhydrazines Mediated by β-Fragmentation of Nitrogen-Centered Radical

In the presence of tert-butylnitrite and dioxygen, the C-N bond activation of N,N′-dialkylacylhydrazines was realized, providing a series of N-nitrosoacylhydrazines in high yields. Different from transition-metal and other radical catalysis, this reaction is mediated by a nitrogen-centered radical of the corresponding N,N′-dialkylacylhydrazine and further β-fragmentation, which was supported by the mechanistic study.