cyclohexyl(3,2',2',5',5'-pentamethyl-1'-oxyl-4,5,2',5'-tetrahydro-3H,1'H-[1,4']biimidazolyl-2-ylidene)methylammonium methyl sulfate | 1006032-67-2

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 有机硫酸及其衍生物
• 英文名称: cyclohexyl(3,2',2',5',5'-pentamethyl-1'-oxyl-4,5,2',5'-tetrahydro-3H,1'H-[1,4']biimidazolyl-2-ylidene)methylammonium methyl sulfate
• CAS: 1006032-67-2
• 化学式: CH₃O₄S*C₁₈H₃₃N₅O
• 分子量: 446.591
• InChiKey: RTXFERLFKYPUJE-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  1.23
• 重原子数：
  30
• 可旋转键数：
  3
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.89
• 拓扑面积：
  101
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为产物：
  描述：

  、 硫酸二甲酯 以 乙醚 为溶剂， 反应 8.0h， 以0.12 g的产率得到cyclohexyl(3,2',2',5',5'-pentamethyl-1'-oxyl-4,5,2',5'-tetrahydro-3H,1'H-[1,4']biimidazolyl-2-ylidene)methylammonium methyl sulfate
  参考文献：
  名称：

  Studies toward the Synthesis of 4-(2-R-ethyl)amino-2,2,5,5-tetramethyl-3-imidazoline 1-Oxyls. Nucleophilic Substitution of Bromide in the N-Alkyl Chain of the 1,2,4-Oxadiazol-2-one Precursor

  摘要：

  [GRAPHICS]A synthetic approach to access the new nitroxides of the amidine type exhibiting pH-dependent EPR spectra through substitution of a halide in the exo-N-halogenoalkyl chain of 1-(2-bromoethyl)-6-oxyl-5,5,7,7-tetramethyltetrahydroimidazo[1,5-b][1,2,4]oxadiazol-2-one is reported. In this approach, an oxycarbonyl moiety of the oxadiazolone heterocycle plays the role of a "protecting group" for the amidine functionality. A nucleophilic cleavage of the oxadiazolone heterocycle under mild nonbasic conditions, applicable to substrates bearing substituents vulnerable to attack by strong basic nucleophiles, is elaborated. The approach allows for the new amidine nitroxides bearing various functional groups (e.g., such as CN, N-3, NH2, COOEt) to be synthesized. A series of nitroxides obtained through the Staudinger/intermolecular aza-Wittig reaction of the azido derivative is also described. The nitroxides synthesized here were found to have pfl-dependent two-component EPR spectra indicative of a slow, on the EPR time scale, R-center dot reversible arrow (RH+)-H-center dot chemical exchange, and pK(a) values ranging from 2.8 to 12.5 units. The guanidine derivatives synthesized in this work show the highest pK(a) values (pK(a) = 10.2 and 12.5, respectively) ever reported for the nitroxide pH-probes of a "basic type".

  DOI：

  10.1021/jo701803a

文献信息

• Studies toward the Synthesis of 4-(2-R-ethyl)amino-2,2,5,5-tetramethyl-3-imidazoline 1-Oxyls. Nucleophilic Substitution of Bromide in the <i>N</i>-Alkyl Chain of the 1,2,4-Oxadiazol-2-one Precursor
  作者：Julya F. Polienko、Thomas Schanding、Yury V. Gatilov、Igor A. Grigor'ev、Maxim A. Voinov

  DOI：10.1021/jo701803a

  日期：2008.1.1

  [GRAPHICS]A synthetic approach to access the new nitroxides of the amidine type exhibiting pH-dependent EPR spectra through substitution of a halide in the exo-N-halogenoalkyl chain of 1-(2-bromoethyl)-6-oxyl-5,5,7,7-tetramethyltetrahydroimidazo[1,5-b][1,2,4]oxadiazol-2-one is reported. In this approach, an oxycarbonyl moiety of the oxadiazolone heterocycle plays the role of a "protecting group" for the amidine functionality. A nucleophilic cleavage of the oxadiazolone heterocycle under mild nonbasic conditions, applicable to substrates bearing substituents vulnerable to attack by strong basic nucleophiles, is elaborated. The approach allows for the new amidine nitroxides bearing various functional groups (e.g., such as CN, N-3, NH2, COOEt) to be synthesized. A series of nitroxides obtained through the Staudinger/intermolecular aza-Wittig reaction of the azido derivative is also described. The nitroxides synthesized here were found to have pfl-dependent two-component EPR spectra indicative of a slow, on the EPR time scale, R-center dot reversible arrow (RH+)-H-center dot chemical exchange, and pK(a) values ranging from 2.8 to 12.5 units. The guanidine derivatives synthesized in this work show the highest pK(a) values (pK(a) = 10.2 and 12.5, respectively) ever reported for the nitroxide pH-probes of a "basic type".