N-(1,1-dimethyl-2-[tert-butyldimethylsilanyloxy]propyl)-N-(2-methyl-1-phenylpropyl)-N-oxyl | 270901-81-0

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: N-(1,1-dimethyl-2-[tert-butyldimethylsilanyloxy]propyl)-N-(2-methyl-1-phenylpropyl)-N-oxyl
• CAS: 270901-81-0
• 化学式: C₂₀H₃₆NO₂Si
• 分子量: 350.597
• InChiKey: UQGLRZSASGGBHL-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.83
• 重原子数：
  24
• 可旋转键数：
  8
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.7
• 拓扑面积：
  13.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  N-(1,1-dimethyl-2-[tert-butyldimethylsilanyloxy]propyl)-N-(2-methyl-1-phenylpropyl)-N-oxyl 在 四丁基氟化铵 、 三乙胺 作用下， 以 四氢呋喃 、 二氯甲烷 、 乙腈 为溶剂， 反应 20.33h， 生成 2-isopropylcarbamoyl-1,1-dimethylethyl 2-methyl-1-phenylpropyl nitroxide
  参考文献：
  名称：

  Nitroxide Bound β-Cyclodextrin:  Is There an Inclusion Complex?

  摘要：

  236CDTIPNO, a derivative of the persistent free radical TIPNO (1,1-dimethylethyl 2-methyl-1-phenylpropyl nitroxide) covalently bound to a permethylated-beta-cyclodextrin, was prepared. Self-association of 236CDTIPNO in water was proved by solvent- and competition-dependent EPR spectroscopy experiments with 2,6-di-O-Me-beta-cyclodextrin (DIMEB) and permethylated-beta-cyclodextrin (TRIMEB) as external hosts competing for accommodation of the TIPNO moiety. Temperature-dependent EPR spectra were simulated with a novel two-dimensional (field-temperature) EPR simulation program that afforded a full determination of the thermodynamic parameters characterizing the rate constants of the self-inclusion reaction derived from Arrhenius and Eyring models. This method allows separating the line broadening effects due to relaxation from a chemical exchange, even if only the fast exchange regime is accessible experimentally. The activation parameters for the forward and backward steps were consistent with an equilibrium between a nonassociated form and a weakly associated form, with activation free enthalpies for each reaction of around 34 kJ center dot mol(-1).

  DOI：

  10.1021/jo061194p
• 作为产物：
  描述：

  N-[1-[tert-butyl(dimethyl)silyl]oxy-2-methylpropan-2-yl]-1-phenylmethanimine oxide 在 ammonium hydroxide 、 copper diacetate 、 氧气 作用下， 以 四氢呋喃 、 甲醇 为溶剂， 生成 N-(1,1-dimethyl-2-[tert-butyldimethylsilanyloxy]propyl)-N-(2-methyl-1-phenylpropyl)-N-oxyl
  参考文献：
  名称：

  Nitroxide Bound β-Cyclodextrin:  Is There an Inclusion Complex?

  摘要：

  236CDTIPNO, a derivative of the persistent free radical TIPNO (1,1-dimethylethyl 2-methyl-1-phenylpropyl nitroxide) covalently bound to a permethylated-beta-cyclodextrin, was prepared. Self-association of 236CDTIPNO in water was proved by solvent- and competition-dependent EPR spectroscopy experiments with 2,6-di-O-Me-beta-cyclodextrin (DIMEB) and permethylated-beta-cyclodextrin (TRIMEB) as external hosts competing for accommodation of the TIPNO moiety. Temperature-dependent EPR spectra were simulated with a novel two-dimensional (field-temperature) EPR simulation program that afforded a full determination of the thermodynamic parameters characterizing the rate constants of the self-inclusion reaction derived from Arrhenius and Eyring models. This method allows separating the line broadening effects due to relaxation from a chemical exchange, even if only the fast exchange regime is accessible experimentally. The activation parameters for the forward and backward steps were consistent with an equilibrium between a nonassociated form and a weakly associated form, with activation free enthalpies for each reaction of around 34 kJ center dot mol(-1).

  DOI：

  10.1021/jo061194p

文献信息

• Factors Influencing the C−O Bond Homolysis of Alkoxyamines:  Effects of H−Bonding and Polar Substituents
  作者：Sylvain Marque、Hanns Fischer、Elisabeth Baier、Armido Studer

  DOI：10.1021/jo001190z

  日期：2001.2.1

  discussed. A correlation by which the rate constant for the C-O bond cleavage of TEMPO-derived alkoxyamines can be predicted from the C-H BDEs of the corresponding alkanes is presented. Solvent effects as well as the effect of camphorsulfonic acid on the rate of the C-O bond homolysis are discussed. Finally, EPR and kinetic evidence show that alkoxyamines derived from nitroxides which are capable of intramolecular

  描述了各种新的三烷基羟胺的合成。已经测量了这些新的烷氧基胺的CO键裂解的速率常数。例如，一系列对位取代的TEMPO-苯乙烯基化合物TEMPO-CH（CH3）C6H5X 1a（p-MeO），1b（p-Me），1d（pH），1e（p-Br）的CO键均质速率，并显示1f（p-MeO2C）。此外，讨论了α-杂芳基取代的仲烷氧基胺的CO键裂解的速率常数。提出了一种相关性，通过该相关性，可以从相应烷烃的CH BDE预测TEMPO衍生的烷氧基胺的CO键裂解速率常数。讨论了溶剂效应以及樟脑磺酸对CO键均质分解速率的影响。最后，
• Nitroxide Bound β-Cyclodextrin:  Is There an Inclusion Complex?
  作者：David Bardelang、Antal Rockenbauer、Laszlo Jicsinszky、Jean-Pierre Finet、Hakim Karoui、Sandrine Lambert、Sylvain R. A. Marque、Paul Tordo

  DOI：10.1021/jo061194p

  日期：2006.9.1

  236CDTIPNO, a derivative of the persistent free radical TIPNO (1,1-dimethylethyl 2-methyl-1-phenylpropyl nitroxide) covalently bound to a permethylated-beta-cyclodextrin, was prepared. Self-association of 236CDTIPNO in water was proved by solvent- and competition-dependent EPR spectroscopy experiments with 2,6-di-O-Me-beta-cyclodextrin (DIMEB) and permethylated-beta-cyclodextrin (TRIMEB) as external hosts competing for accommodation of the TIPNO moiety. Temperature-dependent EPR spectra were simulated with a novel two-dimensional (field-temperature) EPR simulation program that afforded a full determination of the thermodynamic parameters characterizing the rate constants of the self-inclusion reaction derived from Arrhenius and Eyring models. This method allows separating the line broadening effects due to relaxation from a chemical exchange, even if only the fast exchange regime is accessible experimentally. The activation parameters for the forward and backward steps were consistent with an equilibrium between a nonassociated form and a weakly associated form, with activation free enthalpies for each reaction of around 34 kJ center dot mol(-1).