o-Xylol-hydroperoxid | 55765-61-2

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: o-Xylol-hydroperoxid
• 英文别名: 1-(hydroperoxymethyl)-2-methylbenzene；(2-Methylphenyl)methaneperoxol
• CAS: 55765-61-2
• 化学式: C₈H₁₀O₂
• 分子量: 138.166
• InChiKey: JTJQZHCBMBJJMV-UHFFFAOYSA-N

物化性质

• 沸点：
  58 °C(Press: 0.01 Torr)
• 密度：
  1.0840 g/cm3

计算性质

• 辛醇/水分配系数(LogP)：
  1.6
• 重原子数：
  10
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  29.5
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (5,15-bis(2-methoxyphenyl)-2,8,12,18-tetra-n-butyl-3,7,13,17-tetramethylporphyrinato)zinc 、 o-Xylol-hydroperoxid 生成
  参考文献：
  名称：

  Kinetics of Zn-5,15-di(ortho-methyloxyphenyl)-2,8,12,18-tetramethyl-3,7,13,17-tetrabutylporphyrin oxidation by organic peroxides in o-xylene

  摘要：

  A spectrophotometric and quantum chemical (PM3) study of the structure and properties of Zn-5,15-di(ortho-methyloxyphenyl)-2,8,12,18-tetramethyl-3,7,13,17- tetrabutylporphyrin (ZnP(I)) in its oxidation with organic peroxides in o-xylene at T = 295 K is presented. The kinetic parameters (k(app), k(v)) of this reaction are reported. The reactivities of strained zinc porphyrinates (ZnP(I), Zn-5,15-di(ortho-methyloxyphenyl)-2,3,7,8,12,13,17,18-octamethylporphyrin (ZnP(II)), and a zinc porphyrin with a 2,5-dimethoxyphenylene "cover" (ZnP(III))) are compared. The electronic and conformational properties of the macrocycle are significant factors in the interaction of the metalloporphyrins with the peroxides. The structures of the reactants and intermediates have been calculated by the PM3 method. The macrocycle of ZnP(I) has a distorted structure. The degree and type of distortion are estimated. When reacting with the peroxides, the metalloporphyrin changes its structure so that the macrocycle becomes still more strained, and this enhances its reactivity.

  DOI：

  10.1134/s0036023610060215
• 作为产物：
  描述：

  邻二甲苯 在 氧气 作用下， 171.84 ℃ 、240.0 kPa 条件下， 生成 o-Xylol-hydroperoxid
  参考文献：
  名称：

  Co and Mn polysiloxanes as unique initiator–catalyst-systems for the selective liquid phase oxidation of o-xylene

  摘要：

  钴和锰聚硅氧烷是一种独特的催化剂/引发剂体系，可用于邻二甲苯的液相氧化，其活性高于钴环烷酸盐，这与极性产物与疏水表面的弱相互作用以及没有羟基和周围的含氧化合物限制自由基淬灭有关。

  DOI：

  10.1039/c0cc05050d

文献信息

• Indium-Mediated Synthesis of Benzylic Hydroperoxides
  作者：Yuxuan Hou、Jinjin Hu、Ruigang Xu、Shulei Pan、Xiaofei Zeng、Guofu Zhong

  DOI：10.1021/acs.orglett.9b01070

  日期：2019.6.21

  An indium(0)-metal-mediated efficient synthesis of benzylic hydroperoxides is described. The reaction proceeds efficiently with a broad range of benzyl bromides under aerobic conditions at room temperature to afford benzyl hydroperoxides in good to excellent yields. In addition, the tandem hydroperoxidation-Michael addition of (E)-1-(bromomethyl)-2-(2-nitrovinyl)benzene was also demonstrated.

  描述了铟（0）-金属介导的苄基氢过氧化物的有效合成。在室温下，在有氧条件下，反应可与多种苄基溴有效地进行，从而以良好或优异的收率得到氢过氧化苄基。另外，还证实了串联的（E）-1-（溴甲基）-2-（2-硝基乙烯基）苯的加氢过氧化-迈克尔加成。
• Enantioselective Peroxidation of <i>C</i>-alkynyl imines enabled by chiral BINOL calcium phosphate
  作者：Zhongwen Sun、Lijun Chen、Kaixiong Qiu、Bo Liu、Hongtao Li、Fang Yu

  DOI：10.1039/d1cc07156d

  日期：——

  Herein, we report a catalytic enantioselective addition of C-alkynyl imines with hydroperoxides catalyzed by chiral BINOL calcium phosphate, affording a broad range of enantioenriched α-peroxy propargylamines in good yields (80–99%) with high enantioselectivities (up to 94% ee). The protocol is characterized by mild conditions, easy accessibility and good practicability.

  在此，我们报道了由手性 BINOL 磷酸钙催化的C-炔基亚胺与氢过氧化物的催化对映选择性加成，以良好的收率（80-99%）和高对映选择性（高达 94% ee）提供范围广泛的对映富集的 α-过氧炔丙基胺）。该协议具有条件温和、易于获取、实用性强的特点。
• NUCLEOSIDE ANALOGS FOR ANTIVIRAL TREATMENT
  申请人：Chen James M.

  公开号：US20100104532A1

  公开（公告）日：2010-04-29

  The invention provides unsaturated phosphonates of Formula I or a tautomer or pharmaceutically accepatble salt thereof, as described herein, as well as pharmaceutical compositions comprising the compounds, and therapeutic methods comprising administering the compounds. The compounds have anti-viral properties and are useful for treating viral infections (e.g. HCV) in animals (e.g. humans).

  本发明提供了公式I或其互变异构体或药学上可接受的盐的不饱和膦酸酯，以及包含这些化合物的制药组合物和包括给予这些化合物的治疗方法。这些化合物具有抗病毒性质，适用于治疗动物（如人类）的病毒感染（例如HCV）。
• Optimized liquid-phase oxidation
  申请人：Wonders George Alan

  公开号：US20060047145A1

  公开（公告）日：2006-03-02

  Disclosed is an optimized process and apparatus for more efficiently and economically carrying out the liquid-phase oxidation of an oxidizable compound. Such liquid-phase oxidation is carried out in a bubble column reactor that provides for a highly efficient reaction at relatively low temperatures. When the oxidized compound is para-xylene and the product from the oxidation reaction is crude terephthalic acid (CTA), such CTA product can be purified and separated by more economical techniques than could be employed if the CTA were formed by a conventional high-temperature oxidation process.

  公开了一种优化的工艺和装置，用于更有效和经济地进行可氧化化合物的液相氧化。这种液相氧化是在气泡柱反应器中进行的，可以在相对较低的温度下提供高效的反应。当被氧化的化合物是对二甲苯，氧化反应的产物是粗对苯二甲酸（CTA）时，这种CTA产物可以通过比传统高温氧化工艺更经济的技术进行纯化和分离。
• Selective liquid phase oxidation of o-xylene with gaseous oxygen by transition metal containing polysiloxane initiator/catalyst systems
  作者：Tobias Förster、Stephan A. Schunk、Andreas Jentys、Johannes A. Lercher

  DOI：10.1016/j.jcat.2011.06.019

  日期：2011.10

  The selective liquid phase oxidation of o-xylene over hydrophobic porous Co2+ and Mn3+ containing polysiloxane catalysts showed that both catalysts had higher activity than the homogeneous benchmark system Co naphthenate. The solid catalyst/initiator systems accelerate the radical initiation and the hydroperoxide decomposition. 2-Methylbenzyl hydroperoxide plays a key role in the reaction network as

  的选择性液相氧化ö二甲苯过疏水性多孔钴2+和Mn 3+的含聚硅氧烷的催化剂表明，两种催化剂具有比齐基准系统环烷酸钴更高的活性。固体催化剂/引发剂体系促进自由基引发和氢过氧化物分解。2-甲基苄基氢过氧化物在反应网络中起关键作用，因为它是第一个被观察到的中间体，并被催化剂有效地分解。通过选择过渡金属可以在一定程度上控制氢过氧化物分解的选择性。Co 2+增强邻甲苯甲醛的形成，而Mn 3+增加了2-甲基苄醇形成的趋势。疏水性表现为弱吸附水，从而阻碍了与极性反应产物的相互作用并使其快速解吸，这反过来又是导致高催化活性的主要原因。