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
• Article Data: 75

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

• 2564-83-2 2,2,6,6-Tetramethyl-1-piperidinyloxy free radical 
• 1589-82-8 phenylmagnesium bromide 
• 108-88-3 toluene 
• 7031-93-8 2,2,6,6-tetramethylpiperidin-1-ol 
• 103-80-0 phenylacetyl chloride 
• 100-39-0 benzyl bromide 
• 270921-28-3 2-benzyloxy-2-methoxy-5,5-dimethyl-Δ³-1,3,4-oxadiazoline 
• 75-65-0 tert-butyl alcohol 
• 623-26-7 terephthalonitrile 
• 1539-57-7 diethyl 2,6-dimethyl-4-benzyl-1,4-dihydropyridine-3,5-dicarboxylate 
• 5802-60-8 N,N-dibenzylhydrazine 
• 62-53-3 aniline 
• 451-40-1 phenyl benzyl ketone 
• 6304-45-6 N′,N′-dibenzylbenzohydrazide 

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

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.

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

[VCl3(THF)3] reacted with the sodium salt of a tripodal diamine bisphenolate ligand precursor Na2L2 to give a paramagnetic d2 complex [V(L2)Cl] (2). The reaction of 2 with oxygen is strongly dependent on the experimental conditions, affording [VO(L2)Cl] (6) or [V(η2-O2)(L2)Cl] (7). The formation of 7 involves the direct addition of O2 to V(iii) in the solid state with oxidation to V(v) without significantly disturbing the structure of 2. DFT calculations showed that compound 7 is an intermediate in the formation of 6 from 2. The reaction involves the cleavage of the η1-O-O bond in a proposed dimeric species. The overall reaction of 2 moles of vanadium(iii), complex 2, and one mole of O2 to yield two moles of product 6 is a favourable process with ΔG298 = -38.3 kcal mol-1. 7 is the first non-oxido peroxidovanadium(v) complex obtained directly from the reaction of a crystal and the second example of a structurally characterized complex of that type. Reactions of V(L1)Cl (1) and V(L2)Cl (2) with one equivalent of the nitroxyl radical TEMPO in toluene also result in the formation of oxido V(v) complexes, VO(L1)Cl (5) and VO(L2)Cl (6). The reaction of VO(OiPr)3 with Na2L2 afforded [VO(L2)(OiPr)] (8) in high yield. A major isomer having the VO moiety in the equatorial plane was characterised by X-ray diffraction although solution NMR data showed the presence of a minor species with the oxido ligand trans to the tripodal nitrogen, as in 6. Complexes 6 and 8 are very active and selective sulfoxidation catalysts of thioanisole, but no enantiomeric excess was obtained.

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.

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

A rapid and highly efficient method for the radical formation using potassium alkylfluoroborates as radical precursor is devised and developed which conducts under relatively mild condition using silver(I) oxide as the oxidant. The observed silver mirror

Photochemical synthesis of TEMPO-capped initiators for 'living' free radical polymerization

Two photochemical routes to stoichiometric initiators used in living free radical polymerizations are presented. These routes offer the advantages of higher yields and allow for the preparation of initiators not accessible using current methodology. All initiators gave detectable carbon centered radicals (laser flash photolysis) and promoted the polymerization of styrene.

Evidence for Hydrogen Transfer in the Photochemistry of 2,2,6,6-Tetramethylpiperidine-N-oxyl

-

Transition Metal-Free sp3?sp3 Carbon-Carbon Coupling between Benzylboronic Esters and Alkyl Bromides

A transition metal-free coupling reaction of benzylboronic esters and alkyl halides has been developed. Both alkyl bromides and alkyl iodides were found to be competent substrates with the nucleophilic boronate intermediate generated from the combination of benzylboronic ester and an alkyllithium. Good chemoselectivity was observed for the reaction with the alkyl bromide in substrates with a second electrophile present. Both secondary and tertiary benzylboronic esters were effective nucleophiles in the reaction with primary alkyl halides. Mechanistic observations are consistent with a radical mechanism.

Asymmetric Synthesis of Homoallylic Alcohols Featuring Vicinal Tetrasubstituted Carbon Centers via Dual Pd/Photoredox Catalysis

Dual palladium/photoredox-catalysis provides an effective method for the decarboxylative asymmetric synthesis of vicinal α,β-tri/tetra- or α,β-tetrasubstituted homoallylic alcohols using Hantzsch-type esters as radical precursors. This mild methodology capitalizes on vinyl cyclic carbonates as accessible reagents providing the target molecules in appreciable to good yields, high branch selectivity, and enantiomeric ratios of up to 94:6, making it a rare example of using prochiral electrophiles for the creation of vicinal congested carbon centers.

Synthesis of 2-Benzyl-3,4-dihydronaphthalenes via Oxidative Radical Opening/Cyclization of Methylenecyclopropanes with Potassium Benzyltrifluoroborates

A Copper-catalyzed benzylation of methylenecyclopropanes with potassium benzyltrifluoroborate salts has been developed to produce 2-benzyl-3,4-dihydronaphthalenes in moderate to good yields. This oxidative cyclization reaction proceeds well via a sequence of radical addition, ring-opening, and cyclization. This protocol represents a new example of methylenecyclopropane oxidative cyclization and tolerates a diverse range of substrate.

Visible-Light-Promoted Cross-Coupling of N-Alkylpyridinium Salts and Nitrostyrenes

A stereoselective, denitrative cross-coupling of β-nitrostyrenes with N-alkylpyridinium salts for the preparation of functionalized styrenes has been developed. The visible-light-induced reaction proceeds without any catalyst at ambient temperature. Broad in scope and tolerant to multiple functional groups, the moderately yielding transformation is orthogonal to several traditional metal-catalyzed cross-couplings.