3,3,5-三甲基环己基2-氧亚基-2-苯基醋酸盐 | 16623-22-6

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 中文名称: 3,3,5-三甲基环己基2-氧亚基-2-苯基醋酸盐
• 英文名称: 3,3,5-trimethylcyclohexyl 2-oxo-2-phenylacetate
• 英文别名: (3,3,5-trimethylcyclohexyl) 2-oxo-2-phenylacetate
• CAS: 16623-22-6
• 化学式: C₁₇H₂₂O₃
• 分子量: 274.36
• InChiKey: XTWPDGJQEPUEIH-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.7
• 重原子数：
  20
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.53
• 拓扑面积：
  43.4
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  3,3,5-三甲基环己基2-氧亚基-2-苯基醋酸盐 在 水 、 sodium acetate 、 双二苯基膦甲烷 、 cobalt(II) iodide 、 锌 作用下， 以 乙腈 为溶剂， 反应 12.0h， 以91%的产率得到环扁桃酯
  参考文献：
  名称：

  以H2O为氢源的α-酮酸酯和N-环硫磺酰亚胺的钴催化转移加氢

  摘要：

  描述了一种以安全和环境友好的H 2 O作为氢源对各种α-酮酸酯和N-环磺酰亚胺的共催化有效转移加氢方法。该反应使用容易获得并且易于处理锌金属作为还原剂。有趣的是，催化体系不需要用于还原N-环磺酰亚胺的配体。

  DOI：

  10.1002/adsc.201900636
• 作为产物：
  描述：

  环扁桃酯 在 戴斯-马丁氧化剂 作用下， 以 二氯甲烷 为溶剂， 反应 2.0h， 以86%的产率得到3,3,5-三甲基环己基2-氧亚基-2-苯基醋酸盐
  参考文献：
  名称：

  Enrichment of Relevant Oxidative Degradation Products in Pharmaceuticals With Targeted Chemoselective Oxidation

  摘要：

  The ability to produce and isolate relatively pure amounts of relevant degradation products is key to several aspects of drug product development: (a) aid in the unambiguous structural identification of such degradation products, fulfilling regulatory requirements to develop safe formulations (International Conference on Harmonization Q3B and M7); (b) pursue as appropriate safety evaluations with such material, such as chronic toxicology or Ames testing; (c) for a specified degradation product in a late-stage regulatory filing, use pure and well-characterized material as the analytical standard. Producing such materials is often a resource-and time-intensive activity, either relying on the isolation of slowly formed degradation products from stressed drug product or by re-purposing the drug substance synthetic route. This problem is exacerbated if the material of interest is an oxidative degradation product, because typical oxidative stressing (H2O2 and radical initiators) tends to produce a myriad of irrelevant species beyond a certain stress threshold, greatly complicating attempts for isolating the relevant degradation product. In this article, we present reagents and methods that may allow the rapid and selective enrichment of active pharmaceutical ingredient with the desired oxidative degradation product, which can then be isolated and used for purposes described above. (c) 2019 American Pharmacists Association (R). Published by Elsevier Inc. All rights reserved.

  DOI：

  10.1016/j.xphs.2018.10.059

文献信息

• Electrochemical two-electron oxygen reduction reaction (ORR) induced aerobic oxidation of α-diazoesters
  作者：Mengyao Ruan、Liang Chen、Ziyang Wen、Fan Yang、Chao Ma、Cuifen Lu、Guichun Yang、Meng Gao

  DOI：10.1039/d1cc06945d

  日期：——

  Electrochemical oxygen reduction reaction (ORR) is a powerful tool for introducing oxygen functional groups in synthetic chemistry. However, compared with the well-developed one-electron oxygen reduction process, the applications of two-electron oxygen reduction in electrochemical synthesis have been seldom studied. We present herein our recent progress in the oxidation of α-diazoesters to α-ketoesters

  电化学氧还原反应 (ORR) 是在合成化学中引入氧官能团的有力工具。然而，与成熟的单电子氧还原工艺相比，双电子氧还原在电化学合成中的应用研究较少。我们在此介绍了我们在通过双电子氧还原方法原位产生的过氧化氢将 α-重氮酯氧化为 α-酮酯方面的最新进展。在无外源氧化剂和无金属催化剂的电化学条件下，以中等至高产率获得了多种有价值的 α-酮酯产物。
• Rongalite-Mediated Transition Metal- and Hydride-Free Chemoselective Reduction of α-Keto Esters and α-Keto Amides
  作者：Sivaparwathi Golla、Hari Prasad Kokatla

  DOI：10.1021/acs.joc.2c00936

  日期：2022.8.5

  metal- and hydride-free protocol has been developed for the chemoselective reduction of α-keto esters and α-keto amides using rongalite as a reducing agent. Here, rongalite acts as a hydride-free reducing agent via a radical mechanism. This protocol offers the synthesis of a wide range of α-hydroxy esters and α-hydroxy amides with 85–98% yields. This chemoselective method is compatible with other reducible

  已经开发了一种无过渡金属和无氢化物的方案，用于使用雕白粉作为还原剂对 α-酮酯和 α-酮酰胺进行化学选择性还原。在这里，雕白粉通过自由基机制充当无氢化物的还原剂。该协议提供了多种 α-羟基酯和 α-羟基酰胺的合成，产率为 85-98%。这种化学选择性方法与其他可还原的官能团兼容，例如卤化物、烯烃、酰胺和腈。使用廉价的雕白粉（约0.03 美元/1 g）、温和的反应条件和克级合成是该方法的一些关键特征。此外，已以 79% 的产率合成了克级规模的血管扩张药物 cyclandelate。
• FUNCKE; REKKER; ERNSTING, Arzneimittel-Forschung/Drug Research, 1956, vol. 6, # 2, p. 60 - 61
  作者：FUNCKE、REKKER、ERNSTING、NAUTA

  DOI：——

  日期：——
• Cobalt‐Catalyzed Transfer Hydrogenation of α‐Ketoesters and <i>N</i> ‐Cyclicsulfonylimides Using H ₂ O as Hydrogen Source
  作者：Yang Gao、Xuexin Zhang、Ronibala Devi Laishram、Jingchao Chen、Kangkui Li、Keyang Zhang、Guangzhi Zeng、Baomin Fan

  DOI：10.1002/adsc.201900636

  日期：2019.9.3

  A Co‐catalyzed effective transfer hydrogenation of various α‐ketoesters and N‐cyclicsulfonylimides by safe and environmentally benign H2O as hydrogen source is described. The reaction used easily available and easy to handle zinc metal as a reductant. Interestingly, the catalytic system does not require ligand for reduction of N‐cyclicsulfonylimides.

  描述了一种以安全和环境友好的H 2 O作为氢源对各种α-酮酸酯和N-环磺酰亚胺的共催化有效转移加氢方法。该反应使用容易获得并且易于处理锌金属作为还原剂。有趣的是，催化体系不需要用于还原N-环磺酰亚胺的配体。
• Enrichment of Relevant Oxidative Degradation Products in Pharmaceuticals With Targeted Chemoselective Oxidation
  作者：Kausik K. Nanda、Olivier Mozziconacci、James Small、Leonardo R. Allain、Roy Helmy、W. Peter Wuelfing

  DOI：10.1016/j.xphs.2018.10.059

  日期：2019.4

  The ability to produce and isolate relatively pure amounts of relevant degradation products is key to several aspects of drug product development: (a) aid in the unambiguous structural identification of such degradation products, fulfilling regulatory requirements to develop safe formulations (International Conference on Harmonization Q3B and M7); (b) pursue as appropriate safety evaluations with such material, such as chronic toxicology or Ames testing; (c) for a specified degradation product in a late-stage regulatory filing, use pure and well-characterized material as the analytical standard. Producing such materials is often a resource-and time-intensive activity, either relying on the isolation of slowly formed degradation products from stressed drug product or by re-purposing the drug substance synthetic route. This problem is exacerbated if the material of interest is an oxidative degradation product, because typical oxidative stressing (H2O2 and radical initiators) tends to produce a myriad of irrelevant species beyond a certain stress threshold, greatly complicating attempts for isolating the relevant degradation product. In this article, we present reagents and methods that may allow the rapid and selective enrichment of active pharmaceutical ingredient with the desired oxidative degradation product, which can then be isolated and used for purposes described above. (c) 2019 American Pharmacists Association (R). Published by Elsevier Inc. All rights reserved.