3-oxo-7α,12α-diformoxy-5β-cholan-24-oic acid | 88674-52-6

• 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: 3-oxo-7α,12α-diformoxy-5β-cholan-24-oic acid
• 英文别名: 3-oxo-7α,12α-diformyloxy-5β-cholanic acid；7α.12α-diformyloxy-3-oxo-5β-cholanoic acid-(24)；7α.12α-Diformyloxy-3-oxo-5β-cholansaeure-(24)；3-Oxo-7a,12a-diformyloxy-5b-cholanic acid；(4R)-4-[(5R,7R,8R,9S,10S,12S,13R,14S,17R)-7,12-diformyloxy-10,13-dimethyl-3-oxo-1,2,4,5,6,7,8,9,11,12,14,15,16,17-tetradecahydrocyclopenta[a]phenanthren-17-yl]pentanoic acid
• CAS: 88674-52-6
• 化学式: C₂₆H₃₈O₇
• 分子量: 462.584
• InChiKey: VNTNGWSEKCSETL-VARWYLKQSA-N

物化性质

• 熔点：
  160-162 °C(Solv: ethanol (64-17-5); water (7732-18-5))
• 沸点：
  588.6±50.0 °C(Predicted)
• 密度：
  1.20±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.3
• 重原子数：
  33
• 可旋转键数：
  8
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.85
• 拓扑面积：
  107
• 氢给体数：
  1
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  3-oxo-7α,12α-diformoxy-5β-cholan-24-oic acid 在 溴 、 lithium carbonate 、 lithium bromide 作用下， 以 溶剂黄146 、 N,N-二甲基甲酰胺 为溶剂， 反应 1.5h， 生成 Chol-4-en-24-oic acid, 7,12-bis(formyloxy)-3-oxo-, (7α,12α)-
  参考文献：
  名称：

  Improved synthesis of 3-keto, 4-ene-3-keto, and 4,6-diene-3-keto bile acids

  摘要：

  Cholic and deoxycholic acids can be converted into 3-keto derivatives in 75-80% yield, by a four-step synthesis consisting of formylation, selective deformylation of the 3-formoxyl group, oxidation, then deformylation of the remaining formoxyl groups. The intermediate 3-keto formoxyl acids in this sequence were shown to be suitable starting compounds for the synthesis of 4-ene-3-keto acids, in 55-60% yield, via bromination, dehydrobromination, and deformylation. By extending the dehydrobromination reaction, the 7 alpha-formoxyl group of the intermediate 4-ene-3-keto-7 alpha,12 alpha-diformoxyl acid is also lost, hence providing a useful synthetic route to 4,6-diene-3-keto bile acids.

  DOI：

  10.1016/0039-128x(83)90087-9
• 作为产物：
  描述：

  cholic acid triformate 在 chromium(VI) oxide 、 sodium hydroxide 、 硫酸 作用下， 以 丙酮 为溶剂， 生成 3-oxo-7α,12α-diformoxy-5β-cholan-24-oic acid
  参考文献：
  名称：

  Improved synthesis of 3-keto, 4-ene-3-keto, and 4,6-diene-3-keto bile acids

  摘要：

  Cholic and deoxycholic acids can be converted into 3-keto derivatives in 75-80% yield, by a four-step synthesis consisting of formylation, selective deformylation of the 3-formoxyl group, oxidation, then deformylation of the remaining formoxyl groups. The intermediate 3-keto formoxyl acids in this sequence were shown to be suitable starting compounds for the synthesis of 4-ene-3-keto acids, in 55-60% yield, via bromination, dehydrobromination, and deformylation. By extending the dehydrobromination reaction, the 7 alpha-formoxyl group of the intermediate 4-ene-3-keto-7 alpha,12 alpha-diformoxyl acid is also lost, hence providing a useful synthetic route to 4,6-diene-3-keto bile acids.

  DOI：

  10.1016/0039-128x(83)90087-9

文献信息

• Potential bile acid metabolites. 17. Synthesis of 2β-hydroxylated bile acids
  作者：Takashi Iida、Ichiro Komatsubara、Frederic C. Chang、Junichi Goto、Toshio Nambara

  DOI：10.1016/0039-128x(91)90060-9

  日期：1991.3

  rearrangement and substitution of the resulting 4 beta-bromo-3-oxo derivatives to the 2 beta-acetoxy-3-oxo compounds with potassium acetate, and (3) reduction to the 2 beta-acetoxy-3 alpha-hydroxy compounds with tert-butylamine-borane complex. As for the prepared 2 beta-hydroxylated bile acids with a diequatorial trans-glycol structure, proton and carbon-13 nuclear magnetic resonance spectroscopic and

  通过建立的方法，由各自的母体胆汁酸合成了石胆酸，鹅去氧胆酸，脱氧胆酸和胆酸的2β-羟基化衍生物。涉及的主要反应是（1）在N，N-二甲基甲酰胺中溴化3-氧代甲酰化胆汁酸，（2）重排并将所得的4个β-溴-3-氧代衍生物取代为2个β-乙酰氧基-3- （3）用叔丁胺-硼烷络合物还原为2个β-乙酰氧基-3α-羟基化合物。对于所制备的具有二水准反式-乙二醇结构的2-β-羟基胆汁酸，讨论了质子和碳-13核磁共振光谱以及气-液色谱/质谱性质。
• Synthesis and antitumor activity of alkylated bile acids and oxazolines
  作者：Srđan Bjedov、Dimitar Jakimov、Mihalj Poša、Olivera R. Klisurić、Marija Sakač

  DOI：10.1016/j.tet.2017.10.058

  日期：2017.12

  Bile acid derivatives with a free carboxylic group or an oxazoline ring in the side chain and with different lengths of alkyl chains on steroid skeleton were synthetized and their antitumor activity against six human cancer cell lines was investigated. Methyl, ethyl, butyl or octyl chains were introduced stereoselectively by Grignard reaction at C-7 of acid and oxazoline, and at C-12 of oxazoline.

  合成了在侧链上具有游离羧基或恶唑啉环且在甾族骨架上具有不同烷基链长度的胆汁酸衍生物，并研究了它们对六种人类癌细胞系的抗肿瘤活性。通过格氏反应在酸和恶唑啉的C-7和恶唑啉的C-12处立体选择性地引入甲基，乙基，丁基或辛基链。酸化合物C-12处的羰基仅与甲基格氏试剂产生加成产物，而产物与其他用过的试剂形成复杂混合物。由于烯醇化，C-3羰基不参与格氏反应。严格原因是这种化学行为的主要原因。在C-7位置带有丁基链的化合物显示出非常好的抗肿瘤活性，IC 50  <5μM。
• 461. Basic derivatives of steroids. 3-Amino-7 : 12-dihydroxy- and 3-amino-12-hydroxy-cholanic acid
  作者：A. S. Jones、M. Webb、F. Smith

  DOI：10.1039/jr9490002164

  日期：——
• KRAMER, WERNER;SCHNEIDER, STEPHAN, J. LIPID RES., 30,(1989) N, C. 1281-1288
  作者：KRAMER, WERNER、SCHNEIDER, STEPHAN

  DOI：——

  日期：——
• Improved synthesis of 3-keto, 4-ene-3-keto, and 4,6-diene-3-keto bile acids
  作者：Raymond A. Leppik

  DOI：10.1016/0039-128x(83)90087-9

  日期：1983.4

  Cholic and deoxycholic acids can be converted into 3-keto derivatives in 75-80% yield, by a four-step synthesis consisting of formylation, selective deformylation of the 3-formoxyl group, oxidation, then deformylation of the remaining formoxyl groups. The intermediate 3-keto formoxyl acids in this sequence were shown to be suitable starting compounds for the synthesis of 4-ene-3-keto acids, in 55-60% yield, via bromination, dehydrobromination, and deformylation. By extending the dehydrobromination reaction, the 7 alpha-formoxyl group of the intermediate 4-ene-3-keto-7 alpha,12 alpha-diformoxyl acid is also lost, hence providing a useful synthetic route to 4,6-diene-3-keto bile acids.