1-methyl-1-cyclohexenyl 3-hydroperoxide | 56595-77-8

• 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-methyl-1-cyclohexenyl 3-hydroperoxide
• 英文别名: 3-methylcyclohex-2-enyl hydroperoxide；3-hydroperoxy-1-methylcyclohex-1-ene；3-Hydroperoxy-1-methylcyclohexene
• CAS: 56595-77-8
• 化学式: C₇H₁₂O₂
• 分子量: 128.171
• InChiKey: NWLMSTHNKFGMLH-UHFFFAOYSA-N

物化性质

• 沸点：
  213.9±20.0 °C(Predicted)
• 密度：
  1.03±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.9
• 重原子数：
  9
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.71
• 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：

  1-methyl-1-cyclohexenyl 3-hydroperoxide 、 sodium hydroxide 生成 3-甲基-2-环己烯-1-醇
  参考文献：
  名称：

  MUSAEV M. R.; SAFAROV A. S., MEHPYZHEHLEHR. AZSSR ELMLEHR AKAD., DOKL. AN AZSSR, 1978, 34, HO 10, 45-4+

  摘要：

  DOI：
• 作为产物：
  描述：

  3-甲基-1-环己烯 在 N-羟基邻苯二甲酰亚胺 、 1,8-naphthalicanhydride 、 氧气 作用下， 以 乙腈 为溶剂， 30.0~35.0 ℃ 、101.33 kPa 条件下， 生成 1-methyl-1-cyclohexenyl 3-hydroperoxide 、 3-hydroperoxy-3-methylcyclohex-1-ene
  参考文献：
  名称：

  萘酰亚胺介导的阳光诱导的N-羟基邻苯二甲酰亚胺的氧化光活化

  摘要：

  AbstractWe report the aerobic photoactivation of N‐hydroxyphthlimide (NHPI) to the phthalimido‐N‐oxyl (PINO) radical mediated by naphthalene monoimides (NI) for promoting the selective oxidation of alkylaromatics and allylic compounds to the corresponding hydroperoxides. In the absence of either NI or NHPI no oxidation was observed, meaning that the two molecules operate in a synergistic way. Sunlight as well as artificial UV‐light irradiation was necessary in order to perform the process at low temperature (30–35 °C). EPR spectroscopy confirmed the role of NI and oxygen in promoting the formation of the superoxide radicals O2.− which, in turn, increased the concentration of PINO radicals during the UV light irradiation of NI/NHPI mixtures in MeCN. The investigation was extended to NI bearing different substituents on the naphthalene moiety. Finally, the synthesis and application of a unique photocatalyst including the NI and NHPI moieties linked by a suitable spacer was also considered. In this case the photocatalyst showed a substrate‐dependent behaviour with some peculiarities in comparison to the system where NI and NHPI are independent units in the same reacting system. This photocatalytic system paves the way to a non‐thermal, metal‐free approach for CH bond activation towards aerobic oxidation under very mild conditions.magnified image

  DOI：

  10.1002/adsc.201300611

文献信息

• <i>Lone</i>Selectivity of the Decatungstate-Sensitized Photooxidation of 1-Substituted Cycloalkenes
  作者：Michael Orfanopoulos、Ioannis N. Lykakis

  DOI：10.1055/s-2004-832803

  日期：——

  Decatungstate-sensitized oxidation of alkyl and phenyl substituted cycloalkenes in the presence of molecular oxygen shows a general preference for hydrogen abstraction on the congested side of the double bond.

  在分子氧存在下，带有烷基和苯基取代的环烯烃通过十钨酸盐敏化的氧化反应，表现出一贯偏好从双键拥挤侧进行氢抽取的行为。
• Studies relating to the oxidative degradation of natural rubber. The autoxidation of 1-methylcyclohexene: primary product analysis, allylic hydroperoxide isolation, and regiochemistry of the initial events
  作者：John L. Courtneidge、Melanie Bush

  DOI：10.1039/c39890001227

  日期：——

  The autoxidation of 1-methylcyclohexene has been examined; the regiochemistry of the initial events has been defined by direct examination and isolation of the first-formed products and a synthetically useful method has been developed in which t-butyl hydroperoxide-loaded mixtures undergo rapid, low temperature autoxidation.

  已经研究了1-甲基环己烯的自氧化。通过直接检查和分离第一个形成的产物来定义初始事件的区域化学，并开发了一种合成上有用的方法，其中叔丁基过氧化氢负载的混合物会进行快速，低温自氧化。
• Initiated, tert-butyl hydroperoxide-loaded, low-temperature autoxidation of alkenes: a chemoselective synthesis of allylic hydroperoxides, allowing analysis of the regioselectivity of hydrogen atom abstraction from some unsymmetrically substituted substrates
  作者：John L. Courtneidge、Melanie Bush

  DOI：10.1039/p19920001531

  日期：——

  A method for the preparation of allylic hydroperoxides is introduced: the method involves the rapid, low-temperature, initiated autoxidation of an alkene (in these instances 1-methylcyclohexene and the isomeric 4-methyloct-4-enes) in the presence of tert-butyl hydroperoxide. The success of the method relies upon the selectivity of hydrogen atom abstraction from the substrate by the chain-carrying tert-butylperoxyl

  引入一种烯丙基氢过氧化物的制备方法：该方法包括在存在的快速，低温，烯烃的发起自动氧化（在这些情况下1-甲基环己烯和异构的4-甲基辛-4-烯类）叔-丁基过氧化氢。该方法的成功取决于携带链的叔丁基过氧自由基从底物中提取氢原子的选择性，这是根据形成最稳定的中间烯丙基自由基的偏好以及降低的链终止速率而决定的。这些相同的部首。该方法与Bolland法则的预测大致相符地给出了对进攻的区域选择性，并且对于烯丙基氢过氧化物的形成具有足够高的化学选择性，从而能够以良好的产率容易地分离这些产物。
• UV-laser photochemistry: diffusion-controlled trapping of cyclic 1,3-diradicals by molecular oxygen - conformational effects on triplet lifetimes
  作者：Waldemar Adam、Peter Hoessel、Walter Huemmer、Herbert Platsch、R. Marshall Wilson

  DOI：10.1021/ja00258a074

  日期：1987.11

  and hence it should have a relatively long triplet lifetime. In contrast, the rigid puckered bicyclo(2.2.1)hepta-2,7-diyl should be the most short-lived species of the three. The flexible twist-boat conformation of the cyclohexa-1,3-diyl possesses intermediate lifetime. Other than such conformational effects, it is difficult to rationalize the lifetimes of these rather similar 1,3-diradicals.

  为了探索甲基取代在自由基位点和环大小的影响，从各自的偶氮烷烃中生成 1,3-双自由基并定量测定氧捕获。分子力学计算表明，在最低能量构象中，轨道间角约为。1,3-双基分别为 0/sup 0/、45/sup 0/ 和 60/sup 0/。因此，对于平面 cyclopenta-1,3-diyl（平面性证实为 ESR）系统间交叉自旋轨道耦合应该是最困难的，因此它应该具有相对较长的三重态寿命。相比之下，刚性褶皱双环（2.2.1）hepta-2,7-diyl 应该是三者中寿命最短的物种。cyclohexa-1,3-diyl 的灵活扭船构象具有中等寿命。除了这种构象效应，
• Courtneidge, John L.; Bush, Melanie; Loh, Lay-See, Journal of the Chemical Society. Perkin transactions I, 1992, # 12, p. 1539 - 1548
  作者：Courtneidge, John L.、Bush, Melanie、Loh, Lay-See

  DOI：——

  日期：——