1,1-dihydroperoxy-(4-tert-butyl)cyclohexane | 229323-96-0

• 分子结构分类: 有机化合物 - 有机氧化合物 - 有机氢过氧化物
• 英文名称: 1,1-dihydroperoxy-(4-tert-butyl)cyclohexane
• 英文别名: 1,1-bis(hydroperoxy)-4-tert-butylcyclohexane；4-tert-butylcyclohexane-1,1-diyl dihydroperoxide；4-(tert-butyl)-1,1-dihydroperoxycyclohexane；4-tert-Butylcyclohexane-1,1-diperoxol；4-tert-butyl-1,1-dihydroperoxycyclohexane
• CAS: 229323-96-0
• 化学式: C₁₀H₂₀O₄
• 分子量: 204.266
• InChiKey: LWGYYSIEPWXJMS-UHFFFAOYSA-N

物化性质

• 熔点：
  83-84 °C(Solv: ethyl ether (60-29-7); hexane (110-54-3))
• 沸点：
  329.0±12.0 °C(Predicted)
• 密度：
  1.10±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.1
• 重原子数：
  14
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  58.9
• 氢给体数：
  2
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  1,1-dihydroperoxy-(4-tert-butyl)cyclohexane 以 氘代氯仿 为溶剂， 反应 0.33h， 生成 4-叔丁基环己酮
  参考文献：
  名称：

  Nature Chooses Rings: Synthesis of Silicon-Containing Macrocyclic Peroxides

  摘要：

  The reactions of 1,2-bis(dimethylchlorosilyl)ethane (1), 1,2-bis(dimethylchlorosilyl)ethene (6), and 1,2-bis(dimethylchlorosilyl)ethyne (7) with gem-bis-(hydroperoxides) 2a-h and 1,1'-bis( hydroperoxy)bis-(cycloalkyl)peroxides 4a-c were found to proceed in an unusual way. Thus, the reactions do not give the expected polymeric peroxides; instead, they produce cyclic silicon-containing peroxides containing 2, 4, or 6 silicon atoms in the ring: 9- (3a-h), 12- (5a-c), 18- (8, 12), 24- (9, 10), 27- (13), and 36-membered (11) compounds. The size of the rings produced in the reactions increases in the series 1,2-bis(dimethylchlorosilyl)ethane < 1,2-bis(dimethylchlorosilyl)ethene < 1,2-bis(dimethylchlorosilyl)ethyne. The resulting 9- and 12-membered cyclic peroxides are stable under ambient conditions. These compounds were isolated by chromatography and characterized by H-1, C-13, and Si-29 NMR spectroscopy, X-ray diffraction, elemental analysis, and high-resolution mass spectrometry. The yields vary from 77 to 95%. Structures of the larger-size rings (18-, 24-, 27-, and 36-membered peroxides) were confirmed by H-1, C-13, and Si-29 NMR spectroscopy using 2D (COSY, HSQC, and HMBC), 2D DOSY H-1, 3D H-1-Si-29 HMBC-DOSY NMR experiments, and elemental analysis.

  DOI：

  10.1021/om500095x
• 作为产物：
  描述：

  4-叔丁基环己酮 在 硫酸 、 双氧水 作用下， 以 四氢呋喃 、 水 为溶剂， 反应 3.0h， 以95%的产率得到1,1-dihydroperoxy-(4-tert-butyl)cyclohexane
  参考文献：
  名称：

  通过酮与过氧化氢反应方便合成双氢过氧化物

  摘要：

  摘要 开发了一种通过硫酸催化酮与过氧化氢在 THF 中反应合成双氢过氧化物的简便方法。Gem-双氢过氧化物由五至七元环烷酮反应制备，无需额外纯化，产率 80-95%，纯度超过 95%；他们的无环类似物的产率为 43-72%。

  DOI：

  10.1080/00397910701226384

文献信息

• Generation of Singlet Oxygen from Fragmentation of Monoactivated 1,1-Dihydroperoxides
  作者：Jiliang Hang、Prasanta Ghorai、Solaire A. Finkenstaedt-Quinn、Ilhan Findik、Emily Sliz、Keith T. Kuwata、Patrick H. Dussault

  DOI：10.1021/jo202265j

  日期：2012.2.3

  short 1O2 lifetimes, and there is a need for oxygenations able to be conducted in organic solvents. We now report that monoactivated derivatives of 1,1-dihydroperoxides undergo a previously unobserved fragmentation to generate high yields of singlet molecular oxygen (1O2). The fragmentations, which can be conducted in a variety of organic solvents, require a geminal relationship between a peroxyanion and

  分子氧 ( 1 O 2 )的第一个单线激发态是化学、生物学和医学中的重要氧化剂。1 O 2最常通过基态氧的光敏激发产生。1 O 2也可以通过过氧化氢和其他过氧化物的分解化学生成。然而，大多数这些“暗氧化”需要与短1 O 2相关的富水介质寿命，并且需要能够在有机溶剂中进行氧化。我们现在报告 1,1-二氢过氧化物的单活化衍生物经历了以前未观察到的碎裂，以产生高产率的单线态分子氧 ( 1 O 2 )。可以在多种有机溶剂中进行的断裂需要过氧阴离子和被激活以进行异裂裂解的过氧化物之间存在孪生关系。该反应适用于一系列骨架和活化基团，通过原位活化，可直接应用于 1,1-二氢过氧化物。我们的调查表明，碎裂涉及过氧阴离子的限速形成，过氧阴离子通过类似 Grob 的过程分解。
• Phosphomolybdic Acid Catalyzed Synthesis of 1,2,4,5-Tetraoxanes
  作者：Chunhua Qiao、Xing Yan、Jinglei Chen、Yun-Ting Zhu

  DOI：10.1055/s-0031-1289864

  日期：2011.12

  1,1-Dihydroperoxides were converted into 1,2,4,5-tetraoxanes through condensation with the corresponding ketones in 36-91% yields using phosphomolybdic acid as the catalyst and anhydrous MgSO4 as the water scavenger.

  将1,1-二氢过氧化物通过与相应酮进行缩合反应，以磷钼酸作为催化剂、无水硫酸镁作为水分捕获剂，在36-91%的产率下转化成1,2,4,5-四氧杂环己烷。
• Perhydrolysis in Ethereal H₂O₂ Mediated by MoO₂(acac)₂: Distinct Chemoselectivity between Ketones, Ketals, and Epoxides
  作者：Xiaosheng An、Qinghong Zha、Yikang Wu

  DOI：10.1021/acs.orglett.9b00425

  日期：2019.3.1

  Ketones, ketals, and epoxides were converted into corresponding hydroperoxides in high yields by reaction with ethereal H2O2 in the presence of a catalytic amount of MoO2(acac)2 with distinct (to date unattainable) chemoselectivity.

  在催化量的MoO 2（acac）2具有催化选择性（迄今为止无法实现）的条件下，通过与醚H 2 O 2反应，高产率地将酮，缩酮和环氧化物转化为相应的氢过氧化物。
• Synthesis, crystal structure and anti-malarial activity of novel spiro-1,2,4,5-tetraoxacycloalkanes
  作者：Kaoru Tsuchiya、Yoshiaki Hamada、Araki Masuyama、Masatomo Nojima、Kevin J McCullough、Hye-Sook Kim、Yasuharu Shibata、Yusuke Wataya

  DOI：10.1016/s0040-4039(99)00653-x

  日期：1999.5

  (Cycloalkylidene)bishydroperoxides 3 react with 1,n-dihaloalkanes (n = 3-6) in the presence of CsOH-H2O in DMF affording the corresponding spiro-1,2,4,5-tetraoxacycloalkanes 4 in moderate yields. Compound 4ba exhibits significant antimalarial activity in vitro against P, falciparum. (C) 1999 Elsevier Science Ltd. All rights reserved.

  （环亚烷基）双过氧化物 3 在 CsOH-H2O 存在下与 1,n-二卤代烷（n = 3-6）在 DMF 中反应，生成相应的 spiro-1,2,4,5-四氧杂环烷烃 4，产率中等。化合物 4ba 对恶性疟原虫（P. falciparum）表现出显著的抗疟活性（体外实验）。© 1999 Elsevier Science Ltd. 保留所有权利。
• Heteropoly acid/NaY zeolite as a reusable solid catalyst for highly efficient synthesis of gem-dihydroperoxides and 1,2,4,5-tetraoxanes
  作者：Kaveh Khosravi、Mojgan Zendehdel、Shirin Naserifar、Fatemeh Tavakoli、Kobra Khalaji、Atefeh Asgari

  DOI：10.3184/174751916x14792244600532

  日期：2016.12

  gem-Dihydroperoxides and 1,2,4,5-tetraoxanes were synthesised from aldehydes and ketones catalysed by heteropoly acid/NaY zeolite (HPA/NaY) as a new, effective and reusable solid catalyst using 30% aqueous hydrogen peroxide at room temperature. The reactions proceeded with high rates and excellent yields.

  在室温下，使用 30% 过氧化氢水溶液，在杂多酸/NaY 沸石 (HPA/NaY) 的催化下，合成了 gem-二氢过氧化物和 1,2,4,5-四恶烷，作为一种新型、有效且可重复使用的固体催化剂。反应以高速率和优异的产率进行。