7-hydroperoxycholesterol | 86900-29-0

• 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: 7-hydroperoxycholesterol
• 英文别名: (3S,8S,9S,10R,13R,14S,17R)-7-hydroperoxy-10,13-dimethyl-17-[(2R)-6-methylheptan-2-yl]-2,3,4,7,8,9,11,12,14,15,16,17-dodecahydro-1H-cyclopenta[a]phenanthren-3-ol
• CAS: 86900-29-0
• 化学式: C₂₇H₄₆O₃
• 分子量: 418.66
• InChiKey: KJIGLXGIVLBXCF-UOQFGJKXSA-N

物化性质

• 沸点：
  534.2±39.0 °C(Predicted)
• 密度：
  1.05±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  7.5
• 重原子数：
  30
• 可旋转键数：
  6
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.93
• 拓扑面积：
  49.7
• 氢给体数：
  2
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  7-hydroperoxycholesterol 在 十二烷醇 、 氧气 作用下， 以 乙醇 为溶剂， 生成 5-胆甾烯-3β-醇-7-酮
  参考文献：
  名称：

  Kinetic Model for Studying the Effect of Quercetin on Cholesterol Oxidation during Heating

  摘要：

  Inhibition of the heat-induced cholesterol oxidation at 150 degrees C by incorporation of quercetin was kinetically studied. Results showed that without quercetin, the cholesterol oxidation products (COPs) concentration increased with increasing heating time. A low amount (0.002%, w/w) of quercetin was effective in inhibiting the formation of COPs during the initial heating period (<= 30 min) at 150 degrees C. However, after prolonged heating (30-120 min), a low antioxiclant activity was observed because of the degradation of quercetin. When using nonlinear regression models for kinetic study of cholesterol oxidation in the absence of quercetin, the epoxidation showed the highest rate constant (h(-1) = 683.1), followed by free radical chain reaction (h(-1) = 453.5), reduction (h(-1) = 290.3), dehydration (h(-1) = 155.5), triol dehydrogenation (h(-1) = 5.35), dehydrogenation (h(-1) = 0.68), thermal degradation (h(-1) = 0.66), and triol formation (h(-1) = 0.38). However, in the presence of quercetin, the reaction rate constants (h(-1)) for epoxidation (551.4), free radical chain reaction (111.7), and thermal degradation (0.28) were reduced greatly. The kinetic model developed in this study can be used to predict the inhibition of COPs by quercetin during the heating of cholesterol.

  DOI：

  10.1021/jf052529r
• 作为产物：
  描述：

  胆固醇 7-氢过氧化物 生成 7-hydroperoxycholesterol
  参考文献：
  名称：

  烯丙基氢过氧化物重排的机理

  摘要：

  3β羟基5α过氧化氢基Δ的suprafacial重排6 -cholestene到7α过氧化氢基Δ 5异构体不涉及的O-交换2与大气，这表明它进入由非离解性机制; 在另一方面，7α-Δ的较慢随后的重排5氢过氧化物的7β-Δ 5氢过氧化物易于交换，并跟随离解机制。

  DOI：

  10.1039/c39880000475

文献信息

• Allylic Oxidations Catalyzed by Dirhodium Catalysts under Aqueous Conditions
  申请人：Doyle Michael P.

  公开号：US20090093638A1

  公开（公告）日：2009-04-09

  The present invention relates to compositions and methods for achieving the efficient allylic oxidation of organic molecules, especially olefins and steroids, under aqueous conditions. The invention concerns the use of dirhodium (II,II) “paddlewheel complexes, and in particular, dirhodium carboximate and tert-butyl hydroperoxide as catalysts for the reaction. The use of aqueous conditions is particularly advantageous in the allylic oxidation of 7-keto steroids, which could not be effectively oxidized using anhydrous methods, and in extending allylic oxidation to enamides and enol ethers.

  本发明涉及在水相条件下实现有机分子的高效烯丙基氧化的组合物和方法，特别是烯烃和类固醇。该发明涉及使用二铑（II,II）“桨轮”配合物，特别是二铑羧酸酯和叔丁基过氧化氢作为催化剂进行反应。在烯丙基氧化7-酮类固醇中使用水相条件特别有优势，无法使用无水方法有效氧化，以及将烯丙基氧化扩展到烯酰胺和烯醇醚。
• Mass Spectrometry Characterization of the 5α-, 7α-, and 7β-Hydroxy Derivatives of β-Sitosterol, Campesterol, Stigmasterol, and Brassicasterol
  作者：Renzo Bortolomeazzi、Michela De Zan、Lorena Pizzale、Lanfranco S. Conte

  DOI：10.1021/jf9812580

  日期：1999.8.1

  chromatography mobilities, specific color reactions, and mass spectral data with those of the corresponding hydroxy derivatives of cholesterol, which were synthesized in the same manner. The phytosterols had the same behavior to photooxidation as cholesterol and, moreover, the different phytosterols photooxidized at about the same rate. The mass spectra of the trimethylsilyl ethers of the hydroxy derivatives

  β-谷甾醇，菜油甾醇，豆甾醇和芸苔甾醇的5α-氢过氧化物是通过在吡啶并以血卟啉为敏化剂的条件下将各甾醇在吡啶中进行光氧化而获得的。氢过氧化物的还原得到相应的5α-羟基衍生物。通过使等分的5α-氢过氧化物异构化为7α-氢过氧化物而获得固醇的7α-氢过氧化物和7β-氢过氧化物，其继而异构化为7β-氢过氧化物。还原得到相应的7α-和7β-羟基衍生物。通过比较薄层色谱的迁移率，特定的颜色反应，确定了β-谷甾醇，菜油甾醇，豆甾醇和芸苔甾醇的5α-，7α-和7β-羟基衍生物。质谱数据与相应的胆固醇羟基衍生物的质谱数据相同。植物甾醇对光氧化的行为与胆固醇相同，而且，不同的植物甾醇以大约相同的速率光氧化。研究的植物甾醇的羟基衍生物的三甲基甲硅烷基醚和胆固醇的相应羟基衍生物的质谱具有相同的裂解模式和相似的相对离子丰度。
• Synthesis, Characterization, and Electrochemical Studies of New π-Extended Metalloporphyrins
  作者：Angel J. Jimenez、Christophe Jeandon、Jean-Paul Gisselbrecht、Romain Ruppert

  DOI：10.1002/ejoc.200900856

  日期：2009.11

  A doubly fused porphyrin has been synthesized by two successive cyclization reactions. The first meso-phenyl group was fused by an intramolecular Cadogan reaction leading to an enamine-functionalized porphyrin. After Vilsmeier–Haack formylation of the nickel enaminoporphyrin, an intramolecular Friedel–Crafts reaction followed by dehydration of the intermediate alcohol afforded the doubly fused aromatic

  通过两个连续的环化反应合成了双稠合卟啉。第一个中间苯基团通过分子内卡多根反应融合，产生烯胺功能化的卟啉。在对镍烯氨基卟啉进行 Vilsmeier-Haack 甲酰化后，通过分子内 Friedel-Crafts 反应，然后中间体醇脱水，得到双稠合的芳香镍卟啉，可以将其脱金属。游离碱以及铜和钯卟啉在 700-800 nm 范围内显示出极高的吸光度。钯配合物是用单线态氧氧化胆固醇的良好催化剂，这使得这种发色团成为光动力疗法的潜在候选者。（© Wiley-VCH Verlag GmbH & Co. KGaA，69451 Weinheim，德国，2009）
• Comparison of Photo-oxidation Reactions in Batch and a New Photosensitizer-Immobilized Microfluidic Device
  作者：Emily K. Lumley、Charlotte E. Dyer、Nicole Pamme、Ross W. Boyle

  DOI：10.1021/ol3023424

  日期：2012.11.16

  been functionalized with photoactive porphyrins for performing reactions which are mediated by singlet molecular oxygen. The resulting device was used to investigate the photochemical oxidation of cholesterol, α-terpinene, and citronellol under flow conditions, and the results were compared with similar batch reactions.

  玻璃微流体装置已经用光敏卟啉功能化，以进行由单线态分子氧介导的反应。所得装置用于研究流动条件下胆固醇，α-萜品烯和香茅醇的光化学氧化，并将结果与​​类似的间歇反应进行比较。
• Compositions and methods for treatment of neoplastic disease
  申请人：Terman S. David

  公开号：US20050112141A1

  公开（公告）日：2005-05-26

  The present invention comprises compositions and methods for treating a tumor or neoplastic disease in a host, The methods employ conjugates comprising superantigen polypeptides or nucleic acids with other structures that preferentially bind to tumor cells and are capable of inducing apoptosis. Also provided are superantigen-glycolipid conjugates and vesicles that are loaded onto antigen presenting cells to activate both T cells and NKT cells. Cell-based vaccines comprise tumor cells engineered to express a superantigen along with glycolipids products which, when expressed, render the cells capable of eliciting an effective anti-tumor immune response in a mammal into which these cells are introduced. Included among these compositions are tumor cells, hybrid cells of tumor cells and accessory cells, preferably dendritic cells. Also provided are T cells and NKT cells activated by the above compositions that can be administered for adoptive immunotherapy.

  本发明包括用于治疗宿主体内肿瘤或肿瘤性疾病的组合物和方法，这些方法采用了由超抗原多肽或核酸与其他结构组成的共轭物，它们优先与肿瘤细胞结合，并能够诱导细胞凋亡。此外，还提供了超抗原-糖脂共轭物和囊泡，将其装载到抗原呈递细胞上可激活 T 细胞和 NKT 细胞。以细胞为基础的疫苗由肿瘤细胞和糖脂产品组成，前者能表达超抗原，后者能使细胞在引入这些细胞的哺乳动物体内引起有效的抗肿瘤免疫反应。这些成分包括肿瘤细胞、肿瘤细胞的杂交细胞和辅助细胞，最好是树突状细胞。此外，还提供了由上述组合物激活的 T 细胞和 NKT 细胞，这些细胞可用于采纳性免疫疗法。