cis-3,5-bis(4-methoxyphenyl)-1,2-dioxolane | 86396-68-1

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 英文名称: cis-3,5-bis(4-methoxyphenyl)-1,2-dioxolane
• 英文别名: (3S,5R)-3,5-bis(4-methoxyphenyl)dioxolane
• CAS: 86396-68-1
• 化学式: C₁₇H₁₈O₄
• 分子量: 286.328
• InChiKey: BVEQKFFAVXURFC-CALCHBBNSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.3
• 重原子数：
  21
• 可旋转键数：
  4
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.29
• 拓扑面积：
  36.9
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为产物：
  描述：

  trans-1,2-di(4-methoxyphenyl)cyclopropane 在 magnesium(II) perchlorate 、 9,10-二氰基蒽 、 氧气 作用下， 以 乙腈 为溶剂， 反应 0.5h， 生成 cis-3,5-bis(4-methoxyphenyl)-1,2-dioxolane
  参考文献：
  名称：

  Salt effect on the 9,10-dicyanoanthracene-sensitized photooxygenation of 1,2-diarylcyclopropanes and the photodecomposition of 3,5-diaryl-1,2-dioxolanes

  摘要：

  The 9,10-dicyanoanthracene (DCA)-sensitized photooxygenation of less electron-rich 1,2-diarylcyclopropanes 1 such as 1,2-diphenylcyclopropanes and 1,2-bis(4-chlorophenyl)cyclopropanes in the presence of Mg(ClO4)2 gave cis- and trans-3,5-diaryl-1,2-dioxolanes as major products. However, in the absence of Mg(ClO4)2, the Photooxygenation did not afford 1,2-dioxolanes, but their decomposition products, 1,3-diaryl-1-hydroxypropan-3-ones 5, aryl aldehydes 6, and aryl methyl ketones 7. The DCA-sensitized photodecomposition of 1,2-dioxolanes also gave 5-7. This photoreaction was suppressed by the addition Of Mg(ClO4)2. The DCA-sensitized photooxygenation of 1 proceeds via radical cations that are generated by photoinduced electron-transfer from 1 to the excited singlet 1DCA*. The DCA-sensitized photodecomposition of 1,2-dioxolanes occurs via exciplexes that are formed between 1,2-dioxolanes and 1DCA* or energy-transfer from the excited triplet 3DCA* to 1,2-dioxolanes.

  DOI：

  10.1021/jo00046a014

文献信息

• Photo-oxygenation of 1,2-diarylcyclopropanes via electron transfer
  作者：Kazuhiko Mizuno、Nobuhiro Kamiyama、Nobuyuki Ichinose、Yoshio Otsuji

  DOI：10.1016/s0040-4020(01)96594-9

  日期：——

  aromatic hydrocarbons and metal salts, and are completely quenched by the addition of triethylamine and 1,4-diazabicyclo[2.2.2]octane. No photo-oxygenation takes place in non-polar solvents. The electron transfer mechanism is proposed for the photo-oxygenations, in which the cation radicals of 1,2- diarylcyclopropanes are involved as chain carriers.

  1,2- diarylcyclopropanes轴承给电子取代基在9,10-二氰基蒽的存在下光致氧化（DCA）的乙腈，得到的反式-和CIS以优良产率-3,5-二芳基-1,2-二氧戊环。较少电子富集的1,2-二芳基环丙烷的DCA增感光氧合可以低收率得到各种氧化产物。这些光反应通过添加某些芳族烃和金属盐而大大加速，并通过添加三乙胺和1,4-二氮杂双环[2.2.2]辛烷完全淬灭。在非极性溶剂中不会发生光氧合。提出了用于光氧合的电子转移机理，其中1,2-二芳基环丙烷的阳离子自由基作为链载体。
• PHOTOOXYGENATION OF 1,2-DIARYLCYCLOPROPANES: FORMATION OF 3,5-DIARYL-1,2-DIOXOLANES VIA PHOTOINDUCED ELECTRON TRANSFER
  作者：Kazuhiko Mizuno、Nobuhiro Kamiyama、Yoshio Otsuji

  DOI：10.1246/cl.1983.477

  日期：1983.4.5

  The photooxygenation of electron-rich 1,2-diarylcyclopropanes such as 1,2-bis(4-methoxyphenyl)cyclopropane and 1-(4-methoxyphenyl)-2-phenylcyclopropane in the presence of 9,10-dicyanoanthracene(DCA) as a sensitizer in acetonitrile affords trans- and cis-3,5-diaryl-1,2-dioxolanes in high yields. This photooxygenation is initiated by the electron transfer from 1,2-diarylcyclopropanes to the excited singlet

  在 9,10-二氰基蒽 (DCA) 存在下，富电子 1,2-二芳基环丙烷如 1,2-双（4-甲氧基苯基）环丙烷和 1-（4-甲氧基苯基）-2-苯基环丙烷的光氧化反应乙腈中的敏化剂以高产率提供反式和顺式 3,5-二芳基-1,2-二氧戊环。这种光氧化是由电子从 1,2-二芳基环丙烷转移到激发的单线态 DCA 引发的，涉及环丙烷的阳离子自由基作为关键中间体。
• CIS-TRANS PHOTOISOMERIZATION AND PHOTOOXYGENATION OF 1,2-DIARYLCYCLOPROPANES, SALT EFFECTS ON THE PHOTOINDUCED ELECTRON TRANSFER REACTIONS
  作者：Kazuhiko Mizuno、Nobuyuki Ichinose、Yoshio Otsuji

  DOI：10.1246/cl.1985.455

  日期：1985.4.5

  The efficiencies of the 9,10-dicyanoanthracene (DCA)-sensitized cis-trans photoisomerization and photooxygenation of cis- and trans-1,2-bis(4-methoxyphenyl)cyclopropanes (c-CP and t-CP) in CH3CN were remarkably enhanced by the addition of inorganic salts such as LiBF4 and Mg(ClO4)2. The mechanistic implication of the salt effects on these photoreactions was discussed.

  9,10-二氰基蒽 (DCA) 敏化的顺反光异构化和顺式和反式 1,2-双（4-甲氧基苯基）环丙烷（c-CP 和 t-CP）在 CH3CN 中的光氧化效率显着通过添加无机盐如 LiBF4 和 Mg(ClO4)2 来增强。讨论了盐效应对这些光反应的机理影响。
• Generation of Polyphenylene Radical Cations and Their Cosensitization Ability in the 9,10-Dicyanoanthracene-Sensitized Photochemical Chain Reactions of 1,2-Bis(4-methoxyphenyl)cyclopropane
  作者：Toshiyuki Tamai、Nobuyuki Ichinose、Tomoko Tanaka、Tsuneo Sasuga、Isao Hashida、Kazuhiko Mizuno

  DOI：10.1021/jo971649y

  日期：1998.5.1

  Cosensitization effects of polyphenylene compounds (PP) such as biphenyl (BP) terphenyls (o-, m-, p-TP), and phenanthrene (Phen) in photoinduced electron-transfer reactions were examined. The 9,10-dicyanoanthracene (DCA)-sensitized cis-trans photoisomerization of 1,2-bis(4-methoxyphenyl)-cyclopropane (CP), which proceeds in a chain reaction via free radical cation of CP (CP.+) as a chain carrier, was accelerated by adding PP, particularly by TP. A similar accelerating effect was observed in the DCA-sensitized photooxygenation of CP as another example. BP and TP were more stable under the oxygenation condition than phenanthrene and naphthalene, which also accelerate the photooxygenation CP. CP.+ is generated by the direct electron transfer from CP to the excited singlet state of DCA ((1)DCA*) and also by the secondary electron transfer from CP to PP.+, which is generated by the primary electron transfer from PP to (1)DCA* The laser flash photolysis study revealed that the quantum yield for the formation of free CP.+ in the direct electron transfer from CP to (1)DCA* (Phi(CP.+) approximate to 0.1) was smaller than that in the presence of PP. This is due to the high yield of free PP.+ generation by the primary electron transfer and the efficient secondary electron transfer from CP to PP.+. The secondary electron transfers were found to take place in nearly diffusion-controlled rates (0.9-1.5 x 10(10) M-1 s(-1)). The high yield of PP.+ as free radical ions does not seem to be the sole factor of the cosensitization of PP for the DCA-sensitized photoreactions of CP. The ratio of the quantum yields of the photoreactions to that of the initial CP.+ formation (turnover) also increased by the addition of PP from 3 (isomerization) and 15 (oxygenation) to 32-90 for both reactions. The second-order rate constant for the decay of CP.+ in aerated acetonitrile was decreased by a factor of 0.5-0.8 by the addition of PP. We concluded that the cosensitization effect in the photoreaction involves pi-complex formation between CP.+ and PP assisting the chain reaction as well as initial CP.+ formation.