trans-1,2-bis(4-methoxyphenyl)cyclobutane | 52498-15-4

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 二苯乙烯类
• 英文名称: trans-1,2-bis(4-methoxyphenyl)cyclobutane
• 英文别名: 1,2-bis(4-methoxyphenyl)cyclobutane；1-methoxy-4-[(1S,2S)-2-(4-methoxyphenyl)cyclobutyl]benzene
• CAS: 52498-15-4
• 化学式: C₁₈H₂₀O₂
• 分子量: 268.356
• InChiKey: CDDDOGRTOBBYHR-QZTJIDSGSA-N

物化性质

• 沸点：
  385.4±42.0 °C(predicted)
• 密度：
  1.084±0.06 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.5
• 重原子数：
  20
• 可旋转键数：
  4
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  18.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  trans-1,2-bis(4-methoxyphenyl)cyclobutane 以 乙腈 为溶剂， 生成 7-甲氧基-1-(4-甲氧基苯基)-1,2-二氢萘
  参考文献：
  名称：

  Nanosecond and Picosecond Dynamics of the Radical Cation Mediated Dimerization of 4-Methoxystyrene

  摘要：

  The addition of the 4-methoxystyrene radical cation to neutral 4-methoxystyrene and the cleavage reactions of the 1,2-bis(4-methoxyphenyl)cyclobutane radical cation in acetonitrile have been studied by product analysis and by nanosecond and picosecond transient absorption spectroscopy. The main product upon radical cation mediated dimerization of 4-methoxystyrene using chloranil as the electron transfer sensitizer is a substituted dihydronaphthalene, 1,2-dihydro-7-methoxy-1-(4'-methoxyphenyl)naphthalene, at low concentrations of 4-methoxystyrene. At higher concentrations, the main product is 1,2-bis(4-methoxyphenyl)cyclobutane. Cleavage of the cyclobutane radical cation is found to give 4-methoxystyrene and the dihydronaphthalene in a 1:3 ratio. In the time-resolved experiments, the radical cations are generated from 4-methoxystyrene and 1,2-bis(4-methoxyphenyl)cyclobutane by 266-nm photoionization or by 355-nm photoinduced electron transfer using triplet chloranil as the sensitizer. A transient with an absorption maximum at 500 nm is observed as a short-lived intermediate in both the radical cation mediated 4-methoxystyrene dimerization and the cyclobutane radical cation cleavage experiments. Spectroscopic and kinetic considerations lead to the conclusion that this transient is a substituted hexatriene radical cation produced as an intermediate in the conversion of the 1,2-bis(4-methoxyphenyl)cyclobutane radical cation to the dihydronaphthalene. Observed rate constants for the decay of the 4-methoxystyrene radical cation measured at 4-methoxystyrene concentrations of 0.0001 to 0.015 M increase in a linear fashion with concentration, while at concentrations >0.2 M, the observed rate constant is found to be independent of concentration. Analysis of the kinetic data according to a rate law derived from a concerted [2 + 1] mechanism leads to the following rate constants: k(1) = 1.4 X 10(9) M(-1) s(-1) for the addition reaction, k(-1) = 8 x 10(7) s(-1) for the cycloreversion reaction, k(2) = 2.5 X 10(8) s(-1) for the rearrangement of the cyclobutane radical cation, and k(3) = 1.5 X 10(10) M(-1) s(-1) for the reduction of the cyclobutane radical cation by neutral 4-methoxystyrene. Monitoring the kinetics of the reactions of the cyclobutane radical cation gives the same values for the rate constants k(2) and k(-1).

  DOI：

  10.1021/ja00094a049
• 作为产物：
  描述：

  3-(4-甲氧苯基)-3-氧代丙酸乙酯 在 palladium on activated charcoal 盐酸 、 sodium tetrahydroborate 、 potassium tert-butylate 、 氨 、 氢气 、 sodium amide 作用下， 以 1,4-二氧六环 、 溶剂黄146 、 二甲基亚砜 为溶剂， 生成 trans-1,2-bis(4-methoxyphenyl)cyclobutane
  参考文献：
  名称：

  己烯雌酚的二芳基环丁烷类似物。

  摘要：

  DOI：

  10.1021/jm00250a001

文献信息

• Visible-Light-Mediated [4+2] Cycloaddition of Styrenes: Synthesis of Tetralin Derivatives
  作者：Leifeng Wang、Fengjin Wu、Jiean Chen、David A. Nicewicz、Yong Huang

  DOI：10.1002/anie.201702940

  日期：2017.6.6

  We report a formal [4+2] cycloaddition reaction of styrenes under visible‐light catalysis. Two styrene molecules with different electronic or steric properties were found to react with each other in good yield and excellent chemo‐ and regioselectivity. This reaction provides direct access to polysubstituted tetralin scaffolds from readily available styrenes. Sophisticated tricyclic and tetracyclic

  我们报告了可见光催化下苯乙烯的正式[4 + 2]环加成反应。发现具有不同电子或空间特性的两个苯乙烯分子可以以良好的收率，优异的化学和区域选择性相互反应。该反应提供了从容易获得的苯乙烯直接进入多取代的四氢萘骨架的途径。复杂的三环和四环四氢化萘类似物可从环状底物中以高收率和高达20/1的非对映选择性制备。
• Dye-Sensitized Oxygenation and Dimerization of 4-Methoxystyrene through Electron Transfer
  作者：Masanobu Kojima、Yasunao Kuriyama、Hirochika Sakuragi、Katsumi Tokumaru

  DOI：10.1246/bcsj.64.2724

  日期：1991.9

  corresponding dimers, cis- and trans-cyclobutanes in a ratio of cis/trans ca. 5/95. On the basis of quenching studies of fluorescence and T–T absorption of the dyes, the oxygenation and dimerization are proposed to proceed through an electron transfer from 1 to excited singlet dyes but not to involve generation of singlet oxygen.

  4-甲氧基苯乙烯 (1) 与染料（如 Acriflavine、罗丹明 6G 和亚甲蓝）在氧气中在甲醇中敏化的光反应得到 4-甲氧基苯甲醛、其二甲基乙缩醛和 2-甲氧基-2-（4-甲氧基苯基）乙醇作为氧化产物连同相应的二聚体，顺式和反式环丁烷，顺式/反式约。5/95。在对染料的荧光和 T-T 吸收的猝灭研究的基础上，提出氧化和二聚化是通过从 1 到激发的单线态染料的电子转移进行的，但不涉及单线态氧的产生。
• Photochemical Electron-transfer Reaction between Aromatic Olefins and Metal Ions. Dependence of the Reaction Course on the Structure of the Olefins
  作者：Masanobu Kojima、Hirochika Sakuragi、Katsumi Tokumaru

  DOI：10.1246/bcsj.58.521

  日期：1985.2

  To investigate the photochemical electron transfer from aromatic olefins to copper(II) or iron(III) ions, a series of substituted styrenes (1) was irradiated in the presence of copper(II) or iron(III) salts in methanol, which gave dimethoxylated monomers (2) and one or more of three types of dimethoxylated dimers [α,α- (3), α,β- (4), and β,β,-dimers (5)]. The formation of these products are reasonably

  为了研究从芳族烯烃到铜 (II) 或铁 (III) 离子的光化学电子转移，在甲醇中存在铜 (II) 或铁 (III) 盐的情况下照射一系列取代的苯乙烯 (1)，得到二甲氧基化单体(2)和三种二甲氧基化二聚体[α,α-(3)、α,β-(4)和β,β,-二聚体(5)]中的一种或多种。这些产物的形成合理地归因于通过电子从受激烯烃转移到金属离子而产生的烯烃的阳离子自由基的参与。发现底物上的取代基控制反应产物。
• Synthesis of cyclobutane lignans via an organic single electron oxidant–electron relay system
  作者：Michelle Riener、David A. Nicewicz

  DOI：10.1039/c3sc50643f

  日期：——

  A direct method to synthesize lignan cyclobutanes and analogs via photoinduced electron transfer is presented. A variety of oxygenated alkenes are employed to furnish terminal or substituted cyclobutane adducts with complete regiocontrol, yielding cycloadducts with trans stereochemistry. Key to minimizing competing cycloreversion is the inclusion of an aromatic electron relay (ER). This method has been adapted to the synthesis of the natural products magnosalin and pellucidin A.

  本文介绍了一种通过光诱导电子转移合成木质素环丁烷及其类似物的直接方法。该方法采用了多种含氧烯烃，以提供具有完全区域控制的末端或取代环丁烷加合物，从而产生具有反式立体化学性质的环加合物。将芳香族电子中继器（ER）的加入是最大限度地减少竞争性环化反应的关键。这种方法已用于合成天然产物木犀草素和佩鲁西丁 A。
• The role of oxygen as an electron acceptor in dimerization of some styrene derivatives
  作者：Masanobu Kojima、HiroXhika Sakuragi、Katsumi Tokumaru

  DOI：10.1016/s0040-4039(01)81778-0

  日期：1981.1

  Irradiation of the CT bands of p-methoxy- and p-methylstyrene with oxygen induced the dimerization of the olefins through their cation radicals generated by electron transfer on CT excitation.

  用氧辐照对甲氧基苯乙烯和对甲基苯乙烯的CT谱带，通过CT激发下电子转移产生的阳离子自由基使烯烃发生二聚。