35814-33-6Relevant articles and documents
Synthesis of a Sterically Demanding Dispiropiperidine and Its Application in Monoamidodialkyl Zincate Complexes
Morisako, Shogo,Shang, Rong,Yamamoto, Yohsuke
supporting information, p. 10767 - 10773 (2016/10/26)
The new sterically hindered piperidine analog, dispiro[cyclohexane-2,2′-piperidine-6′,2″-cyclohexane] (CPC(H), 2), and its N-methylated derivative CPC(Me) (3) were synthesized from commercially available starting materials in short steps. The N-lithiated amide LiCPC (4) was also isolated from 2 as a cyclictrimer in single crystals and showed slightly larger steric hindrance than that of lithium 2,2,6,6-tetramethylpiperidide (LiTMP) in the competitive methylation reaction with methyl trifluoromethanesulfonate. In addition, the heterobimetallic heteroleptic zincate complexes [Li(μ-NR2)(μ-Et)Zn(Et)] (NR2 = CPC, 5, and NR2 = TMP, 6) were obtained as THF- and TMEDA-coordinated monomer 5·(THF)2, 6·(THF)2, 5·TMEDA, and 6·TMEDA (THF = tetrahydrofuran, TMEDA = N,N,N′,N′-tetramethylethylenediamine). These molecular structures bearing different amido ligands in single crystals showed little structural differences from crystallographic studies. Diffusion-ordered spectroscopy (DOSY) revealed that the solution structures of the zincate complexes 5·(THF)2 and 6·(THF)2 only differ in the number of coordination THF molecules. In the deprotonation reactions with tert-butyl 3-bromobenzoate, the zincate complexes containing the CPC ligand [Li(μ-CPC)(μ-R)Zn(R)] (R = Et (5), tBu) showed moderately improved regioselectivity for the 6 position in comparison to those containing the TMP ligand [Li(μ-TMP)(μ-R)Zn(R)] (R = Et (6), tBu).
A slowly relaxing rigid biradical for efficient dynamic nuclear polarization surface-enhanced NMR spectroscopy: Expeditious characterization of functional group manipulation in hybrid materials
Zagdoun, Alexandre,Casano, Gilles,Ouari, Olivier,Lapadula, Giuseppe,Rossini, Aaron J.,Lelli, Moreno,Baffert, Mathieu,Gajan, David,Veyre, Laurent,Maas, Werner E.,Rosay, Melanie,Weber, Ralph T.,Thieuleux, Chloe,Coperet, Christophe,Lesage, Anne,Tordo, Paul,Emsley, Lyndon
supporting information; experimental part, p. 2284 - 2291 (2012/03/10)
A new nitroxide-based biradical having a long electron spin-lattice relaxation time (T1e) has been developed as an exogenous polarization source for DNP solid-state NMR experiments. The performance of this new biradical is demonstrated on hybrid silica-based mesostructured materials impregnated with 1,1,2,2-tetrachloroethane radical containing solutions, as well as in frozen bulk solutions, yielding DNP enhancement factors (∈) of over 100 at a magnetic field of 9.4 T and sample temperatures of ~100 K. The effects of radical concentration on the DNP enhancement factors and on the overall sensitivity enhancements (σ?) are reported. The relatively high DNP efficiency of the biradical is attributed to an increased T1e, which enables more effective saturation of the electron resonance. This new biradical is shown to outperform the polarizing agents used so far in DNP surface-enhanced NMR spectroscopy of materials, yielding a 113-fold increase in overall sensitivity for silicon-29 CPMAS spectra as compared to conventional NMR experiments at room temperature. This results in a reduction in experimental times by a factor >12 700, making the acquisition of 13C and 15N one- and two-dimensional NMR spectra at natural isotopic abundance rapid (hours). It has been used here to monitor a series of chemical reactions carried out on the surface functionalities of a hybrid organic-silica material.
METHOD FOR SYNTHESIS OF NITROXYL RADICAL
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Page/Page column 20-21, (2009/12/23)
The problem to be solved by the present invention is to provide a highly-versatile method for producing a nitroxyl radical derivative, in which position-2 and position-6 in a TEMPO-based compound can be easily substituted, and further, a method for producing a nitroxyl radical derivative, in which a nitrogen nucleus is labeled with 15N. In the present invention, the above-described problem can be solved by reacting a triacetoneamine derivative with ketone or aldehyde in the presence of ammonium salt or a 15N-labeled compound thereof to obtain a 2,6-substituted-4-piperidone derivative.