p-methyl-α-methylstyrene oxide | 42432-27-9

• 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: p-methyl-α-methylstyrene oxide
• 英文别名: 2-methyl-2-(4-methylphenyl)oxirane；2-p-(methylphenyl)propylene oxide；p,α-dimethylstyrene oxide；2-methyl-2-(4-tolyl)oxirane；2-methyl-2-(p-tolyl)oxirane；2-methyl-2-p-tolyl-oxirane
• CAS: 42432-27-9
• 化学式: C₁₀H₁₂O
• mdl: MFCD11592331
• 分子量: 148.205
• InChiKey: LCEIWCJSIRHMNY-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.9
• 重原子数：
  11
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.4
• 拓扑面积：
  12.5
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  p-methyl-α-methylstyrene oxide 在 三氟化硼乙醚 作用下， 以 四氢呋喃 为溶剂， 反应 24.0h， 以60%的产率得到2-(对甲苯基)丙醛
  参考文献：
  名称：

  β-tert-Butyl aspartate as an organocatalyst for the asymmetric α-amination of α,α-disubstituted aldehydes

  摘要：

  The enantioselective alpha-amination reaction of alpha,alpha-disubstituted aldehydes can lead to a variety of enantioenriched amino aldehydes, amino alcohols, and amino acids. After screening a variety of amino acids and their derivatives, we identified a cheap, simple, commercially available aspartic acid derivative that can catalyze efficiently the reaction between alpha,alpha-disubstituted aldehydes and dialkyl azodicarboxylates. The reaction proceeds smoothly leading to the corresponding alpha-aminated adducts in moderate to quantitative yields and moderate to high enantioselectivities (up to 96% ee). Finally, the conversion of these adducts to alpha,alpha-disubstituted quaternary amino acids is also described. 2013 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2013.04.103
• 作为产物：
  描述：

  1-甲基-4-(1-甲基乙烯基)苯 在 叔丁基过氧化氢 、 双氧水 作用下， 以 癸烷 、 水 、 乙腈 为溶剂， 80.0 ℃ 、101.33 kPa 条件下， 反应 15.0h， 以58.6%的产率得到p-methyl-α-methylstyrene oxide
  参考文献：
  名称：

  钛酸钡纳米管上负载金对苯乙烯环氧化的光谱学和催化活性研究

  摘要：

  制备了负载在钛酸钡纳米管（Au / BaTNT）上的金（0.5-5 wt。％），并进行了表征，并首次进行了研究，将其用作用氧气（O 2或H 2  + O 2）和苯乙烯选择性氧化的催化剂。过氧化物（H 2 O 2或TBHP）。当在反应中将H 2共添加到O 2中时，苯乙烯的转化率提高。Au / BaTNT活化O 2和H 2并原位产生H 2 O 2 用于氧化。发现过氧化物比O 2更好的氧化剂。在最佳条件下，使用TBHP相对于Au（1 wt％）/ BaTNT，苯乙烯转化率为60.5 wt。％时，苯乙烯氧化物的选择性达到80.1 wt。％。金粒子（5.0–7.4 nm）分散并装饰在BaTNT的壁上。在苯乙烯氧化中，它们表现出优于已知Au催化剂的性能。在氧化反应过程中形成的活性氧具有原位光谱特征（漫反射紫外可见和傅立叶拉曼光谱）。Au / BaTNT可在四个循环中重复使用，催化活性几乎没有损失。

  DOI：

  10.1016/j.apcata.2016.05.014

文献信息

• Mild Iridium‐Catalysed Isomerization of Epoxides. Computational Insights and Application to the Synthesis of β‐Alkyl Amines
  作者：Albert Cabré、Juanjo Cabezas‐Giménez、Giuseppe Sciortino、Gregori Ujaque、Xavier Verdaguer、Agustí Lledós、Antoni Riera

  DOI：10.1002/adsc.201900372

  日期：2019.8.5

  The isomerization of epoxides to aldehydes using the readily available Crabtree's reagent is described. The aldehydes were transformed into synthetically useful amines by a one‐pot reductive amination using pyrrolidine as imine‐formation catalyst. The reactions worked with low catalyst loadings in very mild conditions. The procedure is operationally simple and tolerates a wide range of functional groups

  描述了使用容易获得的Crabtree试剂将环氧化物异构化为醛的方法。使用吡咯烷作为亚胺形成催化剂，通过一锅还原胺化将醛转化为合成有用的胺。该反应在非常温和的条件下以较低的催化剂负载量进行。该过程操作简单，并且可以接受各种功能组。DFT对其机理的研究表明，异构化是通过具有低能垒的氢化铱机理进行的，与温和的反应条件相符。
• Continuous Flow Synthesis of Terminal Epoxides from Ketones Using in Situ Generated Bromomethyl Lithium
  作者：Timo von Keutz、David Cantillo、C. Oliver Kappe

  DOI：10.1021/acs.orglett.9b04072

  日期：2019.12.20

  preparation of epoxides from ketones has been developed. The method is based on the carefully controlled generation of (bromomethyl)lithium (LiCH2Br) from inexpensive CH2Br2 and MeLi in a continuous flow reactor. The reaction has shown excellent selectivity for a variety of substrates, including α-chloroketones, which typically fail under classic Corey-Chaykovsky conditions. This advantage has been used to develop

  已经开发了从酮直接制备环氧化物的可扩展程序。该方法基于在连续流反应器中从廉价的CH2Br2和MeLi中精心控制的（溴甲基）锂（LiCH2Br）生成。该反应对多种底物（包括α-氯酮）表现出出色的选择性，这些底物通常在经典的Corey-Chaykovsky条件下失效。这一优势已被用于开发一种新的药物氟康唑的途径。
• Facile synthesis of libraries of functionalized cyclopropanes and oxiranes using ionic liquids – A new approach to the classical Corey-Chaykovsky reaction
  作者：Shruti S. Malunavar、Suraj M. Sutar、Pavankumar Prabhala、Hemantkumar M. Savanur、Rajesh G. Kalkhambkar、Gopalakrishnan Aridoss、Kenneth K. Laali

  DOI：10.1016/j.tetlet.2021.153339

  日期：2021.9

  [PAIM][NTf]/BMIM-ILs as a base/solvent in the Corey-Chaykovsky reaction is demonstrated by the facile synthesis of libraries of functionalized cyclopropanes from enones and oxiranes from aldehydes and ketones, at room temperature in respectable isolated yields. To demonstrate their application, the synthesized epoxides were employed as substrates for the synthesis of a library of 2,3-disubstituted quinolines, using

  [PAIM][NTf]/BMIM-IL 在 Corey-Chaykovsky 反应中作为碱/溶剂的潜力通过在室温下以相当高的分离度从烯酮和环氧乙烷轻松合成官能化环丙烷库来证明。产量。为了证明其应用，合成的环氧化物被用作合成 2,3-二取代喹啉库的底物，使用 [BMIM(SOH)][OTf]/[BMIM][PF] 作为催化剂/溶剂。还探讨了离子液体溶剂回收/再利用的潜力。
• Efficient Catalytic Corey–Chaykovsky Reactions Involving Ketone Substrates
  作者：Sarah A. Kavanagh、Alessandro Piccinini、Stephen J. Connon

  DOI：10.1002/adsc.201000255

  日期：2010.10.9

  demonstrated for the first time that a sulfide catalyst, utilised at 20 mol% loading, can promote methylene transfer to ketones in the presence of methyl triflate and an organic base. This metal-free methodology is of broad scope – both aliphatic and aromatic ketones (including trifluoromethyl ketones) can be converted to synthetically useful terminal epoxides in excellent yields at room temperature.

  首次证明，在三氟甲磺酸甲酯和有机碱的存在下，以20摩尔％的载量使用的硫化物催化剂可促进亚甲基向酮的转移。这种无金属的方法具有广泛的应用范围-脂肪族和芳香族酮（包括三氟甲基酮）都可以在室温下以优异的产率转化为合成有用的末端环氧化物。
• Asymmetric rearrangement of racemic epoxides catalyzed by chiral Brønsted acids
  作者：Minyang Zhuang、Haifeng Du

  DOI：10.1039/c3ob27285k

  日期：——

  This paper describes a chiral Brønsted acid catalyzed asymmetric 1,2-rearrangement of racemic epoxides via a hydrogen-shift process for the synthesis of chiral aldehydes, and, followed by a reduction, a variety of optically active alcohols can be furnished in moderate yields with up to 50% ee. Especially, a facile one-pot synthesis of chiral alcohols directly from simple alkenes by a sequential epoxidation

  本文描述了一种手性布朗斯台德酸通过氢转移工艺催化外消旋环氧化物的不对称1,2-重排合成手性醛，然后进行还原反应，可以以适度的收率提供各种旋光性醇，高达50％ee。特别地，还已经实现了通过连续的环氧化，重排和还原直接从简单的烯烃简单地一锅法合成手性醇。