trans-4-methylphenyl 1-propenyl ether | 51896-42-5

• 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: trans-4-methylphenyl 1-propenyl ether
• 英文别名: 4-methyl phenyl-(E)-1-propenyl ether；E-p-Tolyl-1-propenylether；1-methyl-4-[(E)-prop-1-enoxy]benzene
• CAS: 51896-42-5
• 化学式: C₁₀H₁₂O
• 分子量: 148.205
• InChiKey: OCOXFBWYILKHEU-FPYGCLRLSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.4
• 重原子数：
  11
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.2
• 拓扑面积：
  9.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  trans-4-methylphenyl 1-propenyl ether 在 四氧化锇 、 N-甲基吲哚酮 作用下， 以 丙酮 为溶剂， 反应 18.0h， 以87%的产率得到对甲酚
  参考文献：
  名称：

  Study of metal and acid catalysed deprotection of propargyl ethers of alcohols via their allenyl ethers

  摘要：

  A new method for the deprotection of prop-2-ynyl ethers 1b-9b is described. Isomerisation of 1b-9b to O-allenyl ethers 1d-9d and deprotection by reaction with Hg(OCOCF3)(2), aq.HCl, aq.CF3CO2H and best by use of a catalytic amount of OsO4 is described to obtain the alcohols 1a-9a in good yield. Application of this method for the deprotection of prop-2-enyl ethers 7c,8c,10c-13c via their corresponding prop-1-enyl ethers 7e,8e,10e-13e to obtain the corresponding alcohols 7a,8a,10a-13a is also described, (C) 1999 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4020(99)00631-6
• 作为产物：
  描述：

  烯丙基对甲苯醚 在 potassium tert-butylate 作用下， 以 二甲基亚砜 为溶剂， 反应 9.0h， 以89%的产率得到trans-4-methylphenyl 1-propenyl ether
  参考文献：
  名称：

  Study of metal and acid catalysed deprotection of propargyl ethers of alcohols via their allenyl ethers

  摘要：

  A new method for the deprotection of prop-2-ynyl ethers 1b-9b is described. Isomerisation of 1b-9b to O-allenyl ethers 1d-9d and deprotection by reaction with Hg(OCOCF3)(2), aq.HCl, aq.CF3CO2H and best by use of a catalytic amount of OsO4 is described to obtain the alcohols 1a-9a in good yield. Application of this method for the deprotection of prop-2-enyl ethers 7c,8c,10c-13c via their corresponding prop-1-enyl ethers 7e,8e,10e-13e to obtain the corresponding alcohols 7a,8a,10a-13a is also described, (C) 1999 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4020(99)00631-6

文献信息

• Thermodynamic, spectroscopic, and density functional theory studies of allyl aryl and prop-1-enyl aryl ethers. Part 1. Thermodynamic data of isomerization
  作者：Esko Taskinen

  DOI：10.1039/b101837j

  日期：——

  A chemical equilibration study of the relative thermodynamic stabilities of seventy isomeric allyl aryl ethers (a) and (Z)-prop-1-enyl aryl ethers (b) in DMSO solution has been carried out. From the variation of the equilibrium constant with temperature the Gibbs energies, enthalpies, and entropies of isomerization at 298.15 K have been evaluated. Because of their low enthalpies, the (Z)-prop-1-enyl aryl ethers are strongly favored at equilibrium, the Gibbs energies of the a→b isomerization ranging from −12 to −23 kJ mol−1. The entropy contribution is negligible in most reactions, but occasionally small positive values less than +10 J K−1 mol−1 of the entropy of isomerization are found. The equilibration studies were also extended to involve two pairs of related isomeric ethers with a Me substituent on C(2) of the olefinic bond. The Me substituent was found to increase the relative thermodynamic stability of the allylic ethers by ca. 3.4 kJ mol−1.

  通过对70对异构化的烯丙基苯基醚（a）和（Z）-丙-1-烯基苯基醚（b）在DMSO溶液中的化学平衡研究，考察了它们相对热力学稳定性的变化。从平衡常数随温度的变化中，评估了在298.15 K下的异构化吉布斯自由能、焓和熵。由于其低焓值，（Z）-丙-1-烯基苯基醚在平衡状态下具有显著优势，a→b异构化的吉布斯自由能范围从-12至-23 kJ/mol。在大多数反应中，熵的贡献可以忽略不计，但偶尔会发现小于+10 J/K·mol的正值。平衡研究还扩展到涉及两对在烯键C(2)位置带有甲基取代基的相关异构化醚。甲基取代基可以增加烯丙基醚的相对热力学稳定性约3.4 kJ/mol。
• Ruthenium(IV)‐Catalyzed Isomerization of the CC Bond of<i>O</i>‐Allylic Substrates: A Theoretical and Experimental Study
  作者：Adrián Varela‐Álvarez、José A. Sordo、Estefanía Piedra、Noel Nebra、Victorio Cadierno、José Gimeno

  DOI：10.1002/chem.201101131

  日期：2011.9.12

  carried out in aqueous medium. The new mechanistic proposal helped to develop a new experimental procedure for isomerization of allyl ethers to 1‐propenyl ethers under neutral aqueous conditions. This process is an unique example of efficient and selective catalytic isomerization of allyl ethers in aqueous medium.

  一般机制来合理化茹IV催化的所述CC键的异构化在ö建议使用烯丙基底物。在MPWB1K / 6-311 + G（d，p）+ SDD的理论水平上进行了支持该机制的计算。可以根据新机理解释在不同溶剂（水和THF）和不同pH条件（中性和碱性）下的所有实验观察结果。从预催化剂到催化剂的转化的理论分析导致了在不同介质中活性物种的结构鉴定。实验观察到的诱导期与为该过程计算的能垒的大小有关。如实验观察到的，催化循环的理论能量分布需要施加相对较高的温度。当在水性介质中进行反应时，水分子参与反应坐标是机械上必不可少的。新的机理建议有助于开发一种新的实验程序，用于在中性水溶液条件下将烯丙基醚异构化为1-丙烯基醚。该方法是烯丙基醚在水性介质中有效和选择性催化异构化的独特实例。
• A two step, non-stereospecific cation radical Diels-Alder reaction
  作者：Nathan L. Bauld、Jingkui Yang

  DOI：10.1016/s0040-4039(99)01842-0

  日期：1999.12

  The cation radical Diels-Alder cycloadditions of cis- and trans-1-propenyl aryl ethers to 1,3-cyclopentadiene, catalyzed by tris(4-bromophenyl)aminium hexachloroantimonate in dichloromethane solution, are found to be non-stereospecific, in contrast to the stereospecificity observed in other cation radical Diels-Alder reactions previously studied. These and supporting experiments indicate that, in this

  与三（4-溴苯基）六氯锑酸铵在二氯甲烷溶液中催化的顺式和反式-1-丙烯基芳基醚的阳离子基团的狄尔斯-阿尔德环加成反应成1,3-环戊二烯是非立体特异性的，这与在先前研究的其他阳离子自由基Diels-Alder反应中观察到的立体特异性。这些和辅助实验表明，在该特定系统中，反应通过两步机理进行。