1-hydroperoxy-16-oxabicyclo[10.4.0]hexadecane | 174390-08-0

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 氧烷类
• 英文名称: 1-hydroperoxy-16-oxabicyclo[10.4.0]hexadecane
• 英文别名: Hydroperoxide, (4aR,14aR)-tetradecahydro-14aH-cyclododeca(b)pyran-14a-yl, rel-；14a-hydroperoxy-2,3,4,4a,5,6,7,8,9,10,11,12,13,14-tetradecahydrocyclododeca[b]pyran
• CAS: 174390-08-0
• 化学式: C₁₅H₂₈O₃
• 分子量: 256.386
• InChiKey: QJOTXZRMMLQXTG-UHFFFAOYSA-N

物化性质

• 沸点：
  388.6±21.0 °C(Predicted)
• 密度：
  1.02±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.8
• 重原子数：
  18
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  38.7
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  1-hydroperoxy-16-oxabicyclo[10.4.0]hexadecane 在 copper diacetate 作用下， 以 正丁醇 为溶剂， 反应 2.0h， 以10%的产率得到环十五内酯
  参考文献：
  名称：

  Ring-expansion reaction of 1-hydroperoxy-16-oxabicyclo[10.4.0]hexadecane catalyzed by copper ions: use in the synthesis of 15-pentadecanolide

  摘要：

  A catalytic procedure has been developed for the synthesis of 15-pentadecanolide (1) from readily available 1-hydroperoxy-16-oxabicyclo[10.4.0]hexadecane (2). The method is based on the reaction of hydroperoxide 2 with copper acetate (0.15-5 mol.%). Ring expansion occurred as a result of generation of tertiary bicyclohexadecyloxyl radicals 4 from hydroperoxide 2 under the action of Cu-I ions, beta-scission of the radicals accompanied by regioselective cleavage of the bridge bond to form macrocyclic C-centered radicals 5, and their oxidation by Cu-II ions to (E)-11- and (E)-12-pentadecen-15-olides (6). The products obtained were converted into 15-pentadecanolide by subsequent catalytic hydrogenation over a Pd catalyst in a yield of more than 90% with respect to hydroperoxide 2.

  DOI：

  10.1007/bf02503491
• 作为产物：
  描述：

  2-(3-hydroxypropyl)cyclododecanone 在 硫酸 、 双氧水 、 对甲苯磺酸 作用下， 以 水 、 溶剂黄146 为溶剂， 115.0 ℃ 、5.33 kPa 条件下， 反应 1.75h， 生成 1-hydroperoxy-16-oxabicyclo[10.4.0]hexadecane
  参考文献：
  名称：

  Ring-expansion reaction of 1-hydroperoxy-16-oxabicyclo[10.4.0]hexadecane catalyzed by copper ions: use in the synthesis of 15-pentadecanolide

  摘要：

  A catalytic procedure has been developed for the synthesis of 15-pentadecanolide (1) from readily available 1-hydroperoxy-16-oxabicyclo[10.4.0]hexadecane (2). The method is based on the reaction of hydroperoxide 2 with copper acetate (0.15-5 mol.%). Ring expansion occurred as a result of generation of tertiary bicyclohexadecyloxyl radicals 4 from hydroperoxide 2 under the action of Cu-I ions, beta-scission of the radicals accompanied by regioselective cleavage of the bridge bond to form macrocyclic C-centered radicals 5, and their oxidation by Cu-II ions to (E)-11- and (E)-12-pentadecen-15-olides (6). The products obtained were converted into 15-pentadecanolide by subsequent catalytic hydrogenation over a Pd catalyst in a yield of more than 90% with respect to hydroperoxide 2.

  DOI：

  10.1007/bf02503491

文献信息

• A rearrangement of 1-hydroperoxy-2-oxabicycloalkanes into lactones of ω-acyloxy-(ω-3)-hydroxyalkanoic acids related to the Criegee reaction
  作者：Yuri N Ogibin、Alexandre O Terent'ev、Alexandre V Kutkin、Gennady I Nikishin

  DOI：10.1016/s0040-4039(01)02368-1

  日期：2002.2

  1-Hydroperoxy-2-oxabicyclo[n.4.0]alkanes (n=3, 4, 5 and 10) on heating with formic or acetic acid containing a catalytic amount of sulfuric acid undergo a rearrangement into lactones of ω-acyloxy-(ω-3)-hydroxyalkanoic acids by a mechanism related to the Criegee reaction.

  在与含有催化量硫酸的甲酸或乙酸加热下，将1-羟过氧-2-氧杂双环[ n .4.0]烷烃（n = 3、4、5和10）进行重排，使其成为ω-酰氧基-（ω -3）-羟基链烷酸是通过与Criegee反应有关的机理而形成的。
• Process for the preparation of 1-hydroperoxy-16-oxabicyclo[10.4.0]hexadecane
  申请人：Lambrecht Stefan

  公开号：US20050085536A1

  公开（公告）日：2005-04-21

  Process for the preparation of 1-hydroperoxy-16-oxabicyclo[10.4.0]hexadecane (DDP-OOH), wherein 13-oxabicyclo[10.4.0]hexadec-1(12)-ene (DDP) and hydrogen peroxide are reacted in a diluent in the presence of a strong acid, the diluent has a pKa value of greater than or equal to 4.5 and the strong acid has a pKa value of less than or equal to 1.5, wherein after the reaction has taken place, the strong acid is neutralized with at least 0.9 molar equivalent of a base.

  制备1-过氧基-16-氧代-10.4.0]十六烷二醇（DDP-OOH）的过程，其中在稀释剂中，13-氧代-10.4.0]十六烷-1(12)-烯（DDP）和过氧化氢在强酸存在下发生反应，该稀释剂的pKa值大于或等于4.5，强酸的pKa值小于或等于1.5，在反应发生后，用至少0.9摩尔当量的碱中和强酸。
• Eine neuartige Fragmentierung bicyclischer Enoläther Verfahren zur Darstellung macrocyclischer Lactone
  作者：J. Becker、G. Ohloff

  DOI：10.1002/hlca.19710540854

  日期：1971.12.10

  Vicinal α-hydroperoxy-tetrahydropyranyl ethers annelated to cyclododecane are smoothly converted by homolytic fission in about 75% yield to a mixture of the macrocyclic lactones 3, 4, and 5. Based on this observation, an economically feasible synthesis of Exaltolide1 (>65% yield) has been developed. The mechanism of this new β-fragmentation reaction is discussed.

  稠合到环十二烷邻位α过氧化氢基四氢吡喃基醚平滑地通过均裂在约75％的产率转化为大环内酯类的混合物3，4，和5。基于这一观察，Exaltolide的经济上可行的合成1（> 65已开发出％（收率）。讨论了这种新的β片段化反应的机理。
• Iron-Catalyzed Alkoxyl Radical-Induced C–C Bond Cleavage/<i>gem</i>-Difluoroalkylation Cascade
  作者：Tian-Yu Zhang、Yong Wu、Shuai Liu、Jing-Qi Tao、Xu Yang、Xue-Qi Wang、Xin-Hua Duan、Li-Na Guo

  DOI：10.1021/acs.orglett.3c01427

  日期：2023.6.16

  An inexpensive iron-catalyzed alkoxyl radical-induced C–C bond cleavage/gem-difluoroalkylation cascade is presented. Regulated by the structure of alkoxyl radical precursors, fluorinated distal diketones were synthesized through a ring-opening strategy and difluoroalkylated medium-sized lactones and macrolactones were constructed via a ring-expansion strategy. Both protocols proceeded under mild and

  提出了一种廉价的铁催化的烷氧基自由基诱导的 C-C 键断裂/宝石-二氟烷基化级联反应。受烷氧基自由基前体结构的调控，通过开环策略合成了氟化远端二酮，并​​通过扩环策略构建了二氟烷基化中型内酯和大环内酯。两种方案均在温和和氧化还原中性条件下进行，具有广泛的底物范围和良好的官能团相容性。
• Verfahren zur Herstellung von 11(12)-Pentadecen-15-oliden und von 1-Hydroperoxy-16-oxabicyclo[10.4.0]hexadecan
  申请人：Symrise GmbH & Co. KG

  公开号：EP1690860A1

  公开（公告）日：2006-08-16

  Die Erfindung betrifft ein Verfahren zur Herstellung von 11(12)-Pentadecen-15-oliden ausgehend von 1-Hydroperoxy-16-oxabicyclo[10.4.0]hexadecan (DDP-OOH) in Gegenwart einer Cu-(II)-verbindung und eines Verdünnungsmittels, wobei während der Reaktion ein Azeotrop enthaltend Wasser und Verdünnungsmittel abdestilliert wird, und weiterhin ein Verfahren zur Herstellung von DDP-OOH ausgehend von 13-Oxabicyclo[10.4.0]hexadec-1(12)-en (DDP) und Wasserstoffperoxid in Gegenwart von Essigsäure und Schwefelsäure, worin die Umsetzung in Gegenwart von 0,05 bis 5 mol% H2SO4 bezogen auf DDP durchgeführt wird.

  本发明涉及一种 以 1-hydroperoxy-16-oxabicyclo[10.4.0]hexadecane (DDP-OOH)为原料，在 Cu-(II)化合物和稀释剂存在下制备 11(12)-pentadecene-15-olide的工艺，其中在反应过程中蒸馏掉含有水和稀释剂的共沸物，以及进一步以 13-oxabicyclo[10.4.0]hexadec-1(12)-ene (DDP)和过氧化氢为原料，在 Cu-(II)化合物和稀释剂存在下制备 DDP-OOH 的工艺。 以 13-氧杂双环[10.4.0]十六-1(12)-烯（DDP）和过氧化氢为原料，在醋酸和硫酸存在下制备 DDP-OOH 的工艺，其中反应是在相对于 DDP 0.05 至 5 摩尔%的 H2SO4 存在下进行的。 H2SO4 相对于 DDP 的情况下进行。