cholest-5-en-3-yl 4-[(E)-(4-methoxyphenyl)diazenyl]benzoate | 139879-15-5

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 类固醇和类固醇衍生物
• 英文名称: cholest-5-en-3-yl 4-[(E)-(4-methoxyphenyl)diazenyl]benzoate
• 英文别名: cholest-6-en-3-yl 4-[(E)-(4-methoxyphenyl)diazenyl]benzoate；trans-4-methoxy-4'-((cholesteryloxy)carbonyl)azobenzene
• CAS: 139879-15-5
• 化学式: C₄₁H₅₆N₂O₃
• 分子量: 624.907
• InChiKey: POJWZJZVGUAABU-XLTGEJAASA-N

计算性质

• 辛醇/水分配系数(LogP)：
  11.68
• 重原子数：
  46.0
• 可旋转键数：
  10.0
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.63
• 拓扑面积：
  60.25
• 氢给体数：
  0.0
• 氢受体数：
  5.0

反应信息

• 作为反应物：
  描述：

  cholest-5-en-3-yl 4-[(E)-(4-methoxyphenyl)diazenyl]benzoate 以 正丁醇 为溶剂， 生成 cis-4-methoxy-4'-((cholesteryloxy)carbonyl)azobenzene
  参考文献：
  名称：

  通过圆二色性检测开关功能化胆固醇的溶胶-凝胶相变

  摘要：

  含有偶氮苯部分的胆固醇衍生物与甾体部分的 C3 偶联，在某些有机溶剂中显示出可逆的溶胶-凝胶相变。凝胶相中出现强 ICD 光谱，而溶胶相中 ICD 消失。伴随着剧烈的 ICD 光谱变化的溶胶-凝胶相变是由偶氮苯部分的光介导的顺反异构同步诱导的。

  DOI：

  10.1246/cl.1992.739
• 作为产物：
  描述：

  4-[2-(4-hydroxyphenyl)diazen-1-yl]benzoic acid 在 4-二甲氨基吡啶 、 potassium carbonate 、 N,N'-二环己基碳二亚胺 作用下， 以 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 20.0h， 生成 cholest-5-en-3-yl 4-[(E)-(4-methoxyphenyl)diazenyl]benzoate
  参考文献：
  名称：

  Thermal and Light Control of the Sol-Gel Phase Transition in Cholesterol-Based Organic Gels. Novel Helical Aggregation Modes As Detected by Circular Dichroism and Electron Microscopic Observation

  摘要：

  Nineteen cholesterol derivatives containing a variety of azobenzene moieties coupled to C-3 of a steroidal moiety through an ester linkage were synthesized. We employed two different esterification methods by which cholesterol derivatives with the natural (S)-configuration at C-3 and those with the inverted (R)-configuration at C-3 were obtained (the latter derivatives are indicated by a prime). Among them, cholesterol derivatives bearing a p-alkoxyazobenzene moiety (2R and 2R') acted as excellent thermally-reversible gelators of various organic fluids, but the gelation ability is fairly different between 2R and 2R': 2R could gelatinize hydrocarbons such as n-hexane, n-octane, and toluene, halogen solvents such as 1,2-dichloroethane and dichloromethane, ether solvents such as diethyl ether and THF, and alcohols such as ethanol and I-butanol whereas 2R' could gelatinize ketones, methanol, and polysiloxanes. In general, the solubility of 2R' in apolar solvents is superior to that of 2R, so 2R is useful for gelation of apolar solvents whereas 2R' is useful for gelation of polar solvents. We found that the sol-gel phase transition is sensitively ''read-out'' by a change in the circular dichroism (CD) spectrum: the gel phase is CD-active whereas the sol phase is totally CD-silent. For example, the 2Me-1-butanol gel gave a positive exciton coupling band with (R)-chirality whereas the 2Et'-methanol gel gave a negative exciton coupling band with (S)-chirality. These results mean that dipoles in the azobenzene moiety are oriented in a clockwise (in (R)-chirality) or anticlockwise (in (S)-chirality) direction when they interact in the excited state. Strangely, we accidentally found that the CD sign of the gels prepared from 2Pr, 2Bu, and 3Me' (azobenzene-linked cholesterol derivative with p-NMe(2)) is frequently inverted. After careful examination of the gel preparation conditions, we found that inversion takes place only when the cooling speed is fast. The scanning electron microscopic studies established that gelators form three-dimensional networks with helical fibrils. Interestingly, we found that in the 3Me' gel prepared from cyclohexane the gel with (R)-chirality in CD possesses a right- handed helix whereas the gel with (S)-chirality in the CD possesses a left-handed helix. The sol-gel phase transition was also induced by photoresponsive cis-trans isomerism of the azobenzene moiety: the gel formed from the trans-isomer was efficiently converted to the sol when trans-to-cis isomerization was photochemically induced, and this process can be repeated reversibly. The photoinduced sol-gel phase transition was also ''read-out'' as a change in CD spectroscopy.

  DOI：

  10.1021/ja00094a023

文献信息

• Efficient Synthesis of Azo Dye Labeled Terpenes, Sugars, and Steroids Using N-(4-Arylazobenzoyl)-1H-benzotriazoles
  作者：Alan Katritzky、Srinivasa Tala、Nader Abo-Dya、Zakaria Abdel-Samii

  DOI：10.1055/s-0029-1216786

  日期：2009.5

  N-(4-Arylazobenzoyl)-1H-benzotriazoles react with hydroxyterpenes­, sugars, and steroids in the presence of 1,8-diaza­bicyclo[5.4.0]undec-7-ene (DBU) at room temperature in tetrahydrofuran to afford azo dye labeled terpenes, sugars, and steroids (45-82% yield).

  N-(4-芳偶氮苯甲酰基)-1H-苯并三氮唑在与羟基萜类、糖类和甾体的反应中，当存在1,8-二氮杂双环[5.4.0]十一碳-7-烯（DBU）于室温下四氢呋喃中时，能够得到偶氮染料标记的萜类、糖类和甾体化合物，产率范围为45-82%。