bis-(tert-butyl-(2,2,6,6-tetramethyl-benzo[1,2-d;4,5-d']bis[1,3]dithiol-4-ylmethyl)-amine)-(2,2,6,6-tetramethyl-benzo[1,2-d;4,5-d']bis[1,3]dithiole-4-carboxylic acid ethyl ester)-methanol | 1039055-77-0

• 分子结构分类: 有机化合物 - 有机硫化合物 - 硫醚类
• 英文名称: bis-(tert-butyl-(2,2,6,6-tetramethyl-benzo[1,2-d;4,5-d']bis[1,3]dithiol-4-ylmethyl)-amine)-(2,2,6,6-tetramethyl-benzo[1,2-d;4,5-d']bis[1,3]dithiole-4-carboxylic acid ethyl ester)-methanol
• CAS: 1039055-77-0
• 化学式: C₅₀H₆₆N₂O₃S₁₂
• 分子量: 1127.88
• InChiKey: IUEZVUMEACMNAD-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  17.53
• 重原子数：
  67.0
• 可旋转键数：
  9.0
• 环数：
  9.0
• sp3杂化的碳原子比例：
  0.62
• 拓扑面积：
  70.59
• 氢给体数：
  3.0
• 氢受体数：
  17.0

反应信息

• 作为反应物：
  描述：

  bis-(tert-butyl-(2,2,6,6-tetramethyl-benzo[1,2-d;4,5-d']bis[1,3]dithiol-4-ylmethyl)-amine)-(2,2,6,6-tetramethyl-benzo[1,2-d;4,5-d']bis[1,3]dithiole-4-carboxylic acid ethyl ester)-methanol 在 氢氧化钾 、 三氟乙酸 作用下， 以 1,4-二氧六环 、 水 为溶剂， 反应 8.0h， 以50%的产率得到bis(tert-butyl-(2,2,6,6-tetramethyl-benzo[1,2-d;4,5-d']bis[1,3]dithiol-4-ylmethyl)-amine)-(tetramethyl-benzo[1,2-d;4,5-d']bis[1,3]dithiole-4-carboxylic acid)-methane radical
  参考文献：
  名称：

  Synthesis and Characterization of Amino Derivatives of Persistent Trityl Radicals as Dual Function pH and Oxygen Paramagnetic Probes

  摘要：

  Triarylmethyl radicals, TAMs, are useful soluble paramagnetic probes for EPR spectroscopic and imaging applications because of their extraordinary stability in living tissues, narrow line width, high analytical resolution at micromolar concentrations and enhanced sensitivity to molecular oxygen. Recently we proposed the concept of dual function pH and oxygen TAM probes based on the incorporation of ionizable groups into the TAM structure (J. Am. Chem. Soc. 2007, 129 (23), 7240-7241). In this paper we report the synthesis of TAM derivatives containing amino groups. The synthesized TAMs combine stability with oxygen and pH sensitivity, in the range of pH from 6.8 to 9.0. To decrease the number of spectral components and improve probe solubility at physiological pH, asymmetric TAM derivatives containing both carboxyl and amino functions were synthesized. The presence of nitrogen and hydrogen atoms in direct proximity to protonatable amino groups resulted in strong pH-induced changes to the corresponding hyperfine splittings, Delta hfs approximate to (300-1000) mG, comparable to the values of hfs themselves. Large pH-dependent lineshifts of individual spectral components, with narrow linewidths of (160-280) mG, allow for easy discrimination between the pH effect and the observed oxygen-dependent line broadening of about (6 0.5) mG per % oxygen. The synthesized TAM derivatives represent the first dual function pH and oxygen paramagnetic probes with reasonably valuable properties for biomedical research.

  DOI：

  10.1021/ja803083z
• 作为产物：
  描述：

  ethyl 8-(hydroxybis(8-(hydroxymethyl)-2,2,6,6-tetramethylbenzo[1,2-d:4,5-d']bis([1,3]dithiole)-4-yl)methyl)-2,2,6,6-tetramethylbenzo[1,2-d:4,5-d']bis([1,3]dithiole)-4-carboxylate 、 叔丁胺 在 甲基磺酰氯 、 三乙胺 作用下， 以 四氢呋喃 为溶剂， 反应 1.0h， 以60%的产率得到bis-(tert-butyl-(2,2,6,6-tetramethyl-benzo[1,2-d;4,5-d']bis[1,3]dithiol-4-ylmethyl)-amine)-(2,2,6,6-tetramethyl-benzo[1,2-d;4,5-d']bis[1,3]dithiole-4-carboxylic acid ethyl ester)-methanol
  参考文献：
  名称：

  Synthesis and Characterization of Amino Derivatives of Persistent Trityl Radicals as Dual Function pH and Oxygen Paramagnetic Probes

  摘要：

  Triarylmethyl radicals, TAMs, are useful soluble paramagnetic probes for EPR spectroscopic and imaging applications because of their extraordinary stability in living tissues, narrow line width, high analytical resolution at micromolar concentrations and enhanced sensitivity to molecular oxygen. Recently we proposed the concept of dual function pH and oxygen TAM probes based on the incorporation of ionizable groups into the TAM structure (J. Am. Chem. Soc. 2007, 129 (23), 7240-7241). In this paper we report the synthesis of TAM derivatives containing amino groups. The synthesized TAMs combine stability with oxygen and pH sensitivity, in the range of pH from 6.8 to 9.0. To decrease the number of spectral components and improve probe solubility at physiological pH, asymmetric TAM derivatives containing both carboxyl and amino functions were synthesized. The presence of nitrogen and hydrogen atoms in direct proximity to protonatable amino groups resulted in strong pH-induced changes to the corresponding hyperfine splittings, Delta hfs approximate to (300-1000) mG, comparable to the values of hfs themselves. Large pH-dependent lineshifts of individual spectral components, with narrow linewidths of (160-280) mG, allow for easy discrimination between the pH effect and the observed oxygen-dependent line broadening of about (6 0.5) mG per % oxygen. The synthesized TAM derivatives represent the first dual function pH and oxygen paramagnetic probes with reasonably valuable properties for biomedical research.

  DOI：

  10.1021/ja803083z