1-methoxy-1-hydroperoxycyclohexane | 16580-35-1

• 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-methoxy-1-hydroperoxycyclohexane
• 英文别名: 1-methoxycyclohexyl-hydroperoxide；methoxycyclohexyl hydroperoxide；1-methoxy-cyclohexyl hydroperoxide；1-Methoxy-cyclohexylhydroperoxid；1-Methoxy-cyclohexyl-hydroperoxid；1-Methoxycyclohexylhydroperoxid；Hydroperoxide, 1-methoxycyclohexyl；1-hydroperoxy-1-methoxycyclohexane
• CAS: 16580-35-1
• 化学式: C₇H₁₄O₃
• 分子量: 146.186
• InChiKey: RUMUVYHILIPQLB-UHFFFAOYSA-N

物化性质

• 沸点：
  54.5-55 °C(Press: 0.02 Torr)
• 密度：
  1.07±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.2
• 重原子数：
  10
• 可旋转键数：
  2
• 环数：
  1.0
• 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-methoxy-1-hydroperoxycyclohexane 在 三乙烯二胺 、 iron(III) chloride 、 氯化铵 、 锌 作用下， 以 甲醇 、 二氯甲烷 、 水 、 二甲基亚砜 为溶剂， 反应 13.5h， 生成 6-羟基己酸甲酯
  参考文献：
  名称：

  通过从甲硅烷基过氧缩醛生成烷基自由基合成官能化脂肪酸酯

  摘要：

  描述了使用甲硅烷基过氧缩醛作为具有末端酯部分的烷基自由基前体获得官能化脂肪酸酯的催化方法。该反应通过烷基自由基的原位生成和随后的官能化进行，得到具有合成价值的脂肪酸衍生物。还开发了一种通过 CO 键形成过程合成羟基酸衍生物的新策略。

  DOI：

  10.1002/asia.202100723
• 作为产物：
  描述：

  亚甲基环己烷 在 臭氧 作用下， 以 甲醇 、 二氯甲烷 为溶剂， 以82%的产率得到1-methoxy-1-hydroperoxycyclohexane
  参考文献：
  名称：

  Spiro- and Dispiro-1,2-dioxolanes:  Contribution of Iron(II)-Mediated One-Electron vs Two-Electron Reduction to the Activity of Antimalarial Peroxides

  摘要：

  Fourteen spiro- and dispiro-1,2-dioxolanes were synthesized by peroxycarbenium ion annulations with alkenes in yields ranging from 30% to 94%. Peroxycarbenium ion precursors included triethylsilyldiperoxyketals and -acetals derived from geminal dihydroperoxides and from a new method employing triethylsilylperoxyketals and -acetals derived from ozonolysis of alkenes. The 1,2-dioxolanes were either inactive or orders of magnitude less potent than the corresponding 1,2,4-trioxolanes or artemisinin against P. falciparum in vitro and P. berghei in vivo. In reactions with iron(II), the predominant reaction course for 1,2-dioxolane 3a was two-electron reduction. In contrast, the corresponding 1,2,4-trioxolane 1 and the 1,2,4-trioxane artemisinin undergo primarily one-electron iron(II)-mediated reductions. The key structural element in the latter peroxides appears to be an oxygen atom attached to one or both of the peroxide-bearing carbon atoms that permits rapid beta-scission reactions (or H shifts) to form primary or secondary carbon-centered radicals rather than further reduction of the initially formed Fe(HI) complexed oxy radicals.

  DOI：

  10.1021/jm0707673

文献信息

• A Unified Catalytic Asymmetric (4+1) and (5+1) Annulation Strategy to Access Chiral Spirooxindole‐Fused Oxacycles
  作者：Min Gao、Yanshu Luo、Qianlan Xu、Yukun Zhao、Xiangnan Gong、Yuanzhi Xia、Lin Hu

  DOI：10.1002/anie.202105282

  日期：2021.9

  A unified catalytic asymmetric (N+1) (N=4, 5) annulation reaction of oxindoles with bifunctional peroxides has been achieved in the presence of a chiral phase-transfer catalyst (PTC). This general strategy utilizes peroxides as unique bielectrophilic four- or five-atom synthons to participate in the C−C and the subsequent umpolung C−O bond-forming reactions with one-carbon unit nucleophiles, thus providing

  在手性相转移催化剂 (PTC) 的存在下，已经实现了羟吲哚与双官能过氧化物的统一催化不对称 ( N +1) ( N =4, 5) 环化反应。这种通用策略利用过氧化物作为独特的双亲电四原子或五原子合成子参与 C−C 和随后与单碳单元亲核试剂的 umpolung C−O 键形成反应，从而提供了一种独特的方法来获得有价值的手性螺吲哚-四氢呋喃和-四氢吡喃在温和条件下具有良好的产率和高对映选择性。进行 DFT 计算以合理化高对映选择性的起源。还证明了所得产物的克级合成和合成效用。
• Organocatalytic Enantioselective Peroxidation of Ketimines Derived from Isatins
  作者：Shuichi Nakamura、Shun Takahashi

  DOI：10.1021/acs.orglett.5b00805

  日期：2015.6.5

  The first catalytic enantioselective addition of hydroperoxides to ketimines derived from isatins has been developed. Excellent yields and enantioselectivities were observed for the reaction of various ketimines with peroxides using a cinchona alkaloid sulfonamide catalyst. Both enantiomers of products could be obtained by using pseudoenantiomeric chiral catalysts. The obtained product can be converted

  已经开发了氢过氧化物向衍生自靛红的酮亚胺的第一催化对映选择性加成。使用金鸡纳生物碱磺酰胺催化剂，各种酮亚胺与过氧化物的反应观察到极佳的收率和对映选择性。产物的两种对映体都可以通过使用对映体手性催化剂来获得。所获得的产物可以转化为光学活性的α-氨基氢过氧化物。
• Nucleophilic character of alkyl radicals generated in redox processes—III
  作者：F. Minisci、P. Zammori、R. Bernardi、M. Cecere、R. Galli

  DOI：10.1016/s0040-4020(01)93057-1

  日期：1970.1

  α-chloromethyl, α-chloroethyl, γ-chloropropyl and 5-(methoxycarbonyl) pentyl radicals to pairs of conjugated olefins. The sources of the alkyl radicals were the redox systems: acyl peroxides/cuprous ion and 1-methoxycyclohexylhydroperoxide/ferrous ion. The relative reactivities of the above mentioned radicals towards butadiene, acrylonitrile, 2,3-dimethylbutadiene, methyl acrylate, methyl methacrylate, acrylic acid

  通过将乙基，正丙基，正丁基，仲丁基，环己基，α-氯甲基，α-氯乙基，γ-氯丙基和5-（甲氧羰基）戊基自由基交替加成自由基来进行新的合成烯烃。烷基的来源是氧化还原系统：酰基过氧化物/亚铜离子和1-甲氧基环己基氢过氧化物/亚铁离子。上述自由基对丁二烯，丙烯腈，2，3-二甲基丁二烯，丙烯酸甲酯，甲基丙烯酸甲酯，丙烯酸和马来酸酐的相对反应性是根据它们的亲核特性定量描述的。
• Use of hydroperoxides as regulators in polymerizations
  申请人：——

  公开号：US20020137882A1

  公开（公告）日：2002-09-26

  The invention provides for the use of non-copolymerizable hydroperoxides of the formula R—O—O—H as regulators in the free-radically initiated polymerization of ethylenically unsaturated monomers, where R is H, a C 1 -C 18 -alkyl radical, a C 7 -C 22 -aralkyl radical or a saturated or unsaturated carbocyclic or heterocyclic ring having from 3 to 18 carbon atoms, and may be substituted or unsubstituted.

  本发明提供了使用式为R—O—O—H的不可共聚的过氧化氢作为乙烯基不饱和单体自由基引发聚合的调节剂，其中R为H、C1-C18烷基、C7-C22-芳基烷基或具有3至18个碳原子的饱和或不饱和碳环或杂环，可以是取代或未取代的。
• Asymmetric Ketoalkylation/Rearrangement of Alkyenlfurans via Synergistic Photoredox/Brønsted Acid Catalysis
  作者：Jie Wei、Yurong Tang、Qian Yang、Hongxiang Li、Dongxian He、Yunfei Cai

  DOI：10.1021/acs.orglett.2c03040

  日期：2022.11.4

  An enantioselective three-component rearrangement of alkenylfurans with various cycloalkyl silyl peroxides and anilines has been developed by merging photoredox catalysis with chiral Brønsted acid catalysis. This protocol provides expedient access to a broad spectrum of ketoalkyl-functionalized 4-aminocyclopentenones in high yields with excellent enantio- and diastereoselectivities. Diverse functional

  通过将光氧化还原催化与手性布朗斯台德酸催化相结合，开发了烯基呋喃与各种环烷基过氧化硅和苯胺的对映选择性三组分重排。该协议以高产率和优异的对映选择性和非对映选择性方便地获得广谱的酮烷基官能化 4-氨基环戊烯酮。可以通过简单的产品衍生引入不同的官能团。