1,5-di-p-tolylpentane-1,5-dione | 5333-22-2

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 1,5-di-p-tolylpentane-1,5-dione
• 英文别名: 1,5-di-p-tolyl-pentane-1,5-dione；1,5-Di-p-tolyl-pentan-1,5-dion；1.5-Bis-p-tolyl-pentan-1.5-dion；1,5-Di-(p-tolyl)pentane-1,5-dione；1,5-bis(4-methylphenyl)pentane-1,5-dione
• CAS: 5333-22-2
• 化学式: C₁₉H₂₀O₂
• 分子量: 280.367
• InChiKey: HTENBIWOWMNNNY-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.9
• 重原子数：
  21
• 可旋转键数：
  6
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.26
• 拓扑面积：
  34.1
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  1,5-di-p-tolylpentane-1,5-dione 在 tetraphosphorus decasulfide 、 lithium perchlorate 作用下， 以 溶剂黄146 为溶剂， 反应 2.0h， 以85%的产率得到perchlorate de di-p-tolyl-2,6 thiopyrylium
  参考文献：
  名称：

  Gionis, V.; Strzelecka, H., Synthetic Communications, 1984, vol. 14, # 8, p. 775 - 778

  摘要：

  DOI：
• 作为产物：
  描述：

  2,6-Bis(4-methylphenyl)-1,6-heptadiene 在 2,4,6-triphenylpyrylium tetrafluoroborate 、 氧气 、 iron(II) bromide 作用下， 以 四氢呋喃 、 乙腈 为溶剂， 反应 4.33h， 生成 1,5-di-p-tolylpentane-1,5-dione
  参考文献：
  名称：

  Synthesis, Fe(II)-induced degradation, and antimalarial activities of 1,5-diaryl-6,7-dioxabicyclo[3.2.2]nonanes: direct evidence for nucleophilic O-1,2-aryl shifts

  摘要：

  1,5-Diaryt-6.7-dioxabicyclo[3.2.2]nonanes 1a-d (1a: Ar=p-FC6H4, 1b: Ar=Ph. 1e: Ar=p-MeC6H4. 1d: Ar=pMeOC(6)H(4)) were prepared by a modified method of photo-electron transfer oxygenation. and the reactions of 1 with FeBr2 were investigated under various conditions. The Fe(Il)-induced degradation of 1 afforded various rearrangement products and fragmentation products through competitive single electron transfer (SET) and Lewis acid pathways. Direct evidence for the O-1,2-aryl shift was obtained by the isolation of rearrangement products. 1-aryloxy-5-aryl-8-oxabicyclo[3.2.1]octanes 8. The degradation mechanism was proposed and the in vitro antimalarial activities were also evaluated. (C) 2002 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4039(02)00166-1

文献信息

• Cobalt(II)-Catalyzed Stereoselective Olefin Isomerization: Facile Access to Acyclic Trisubstituted Alkenes
  作者：Sheng Zhang、Deepika Bedi、Lu Cheng、Daniel K. Unruh、Guigen Li、Michael Findlater

  DOI：10.1021/jacs.0c02101

  日期：2020.5.13

  Stereoselective synthesis of trisubstituted alkenes is a long-standing challenge in organic chemistry, due to the small energy differences between E and Z isomers of trisubstituted alkenes (compared with 1,2-disubstituted alkenes). Transition metal-catalyzed isomerization of 1,1-disubstituted alkene can serve as an alternative approach to trisubsti-tuted alkenes, but it remains underdeveloped owing

  三取代烯烃的立体选择性合成是有机化学中长期存在的挑战，因为三取代烯烃的 E 和 Z 异构体之间的能量差异很小（与 1,2-二取代烯烃相比）。1,1-二取代烯烃的过渡金属催化异构化可以作为三取代烯烃的替代方法，但由于与反应效率和立体选择性有关的问题，它仍然不发达。在这里，我们展示了一种新型钴催化剂可以克服这些挑战，为获得广泛的三取代烯烃提供有效和立体选择性的途径。该协议与单烯和二烯兼容，并表现出良好的官能团耐受性和可扩展性。而且，它已被证明是构建有机发光体和氘代三取代烯烃的有用工具。对该机制的初步研究表明，该反应涉及钴氢化物途径。该反应的高立体选择性归因于 π-π 堆积效应和底物和催化剂之间的空间位阻。
• One-Pot Synthesis of O-Heterocycles or Aryl Ketones Using an InCl₃/Et₃SiH System by Switching the Solvent
  作者：Wenqiang Jia、Qiumu Xi、Tianqi Liu、Minjian Yang、Yonghui Chen、Dali Yin、Xiaojian Wang

  DOI：10.1021/acs.joc.9b00140

  日期：2019.5.3

  An efficient one-pot synthesis of O-heterocycles or aryl ketones has been achieved using Et3SiH in the presence of InCl3 via a sequential ionic hydrogenation reaction by switching the solvent. This methodology can be used to construct C–O bonds and to prepare conjugate reduction products, including chromans, tetrahydrofurans, tetrahydropyrans, dihydroisobenzofurans, dihydrochalcones, and 1,4-diones

  使用Int 3 SiH的Et 3 SiH通过转换溶剂进行顺序离子氢化反应，可以在InCl 3存在下实现O-杂环或芳基酮的有效一锅合成。该方法可用于轻松构建C–O键并制备共轭物还原产物，包括苯并二氢吡喃，四氢呋喃，四氢吡喃，二氢异苯并呋喃，二氢查耳酮和1,4-二酮。另外，通过实验研究证实了涉及共轭物还原和串联还原性环化的新型合理机制。
• Base-Promoted/Gold-Catalyzed Intramolecular Highly Selective and Controllable Detosylative Cyclization
  作者：Chenghao Zhu、Lin Qiu、Guangyang Xu、Jian Li、Jiangtao Sun

  DOI：10.1002/chem.201502073

  日期：2015.9.7

  controllable and synthetically useful base‐promoted intramolecular detosylative cyclization of bis‐N‐tosylhydrazones has been achieved, affording N‐containing heterocycles and cyclic olefins under transition‐metal‐free or gold‐catalyzed procedures, respectively. Moreover, an effective and practical metal‐free or gold‐catalyzed approach to synthesize polycyclic aromatic compounds is also reported.

  已实现了对双N-甲苯磺酰hydr的高度选择性，可控和合成有用的碱促进的分子内去甲苯基化环化反应，分别在无过渡金属或金催化的程序下提供了含N的杂环和环烯烃。此外，还报道了一种有效且实用的无金属或金催化的合成多环芳族化合物的方法。
• Asymmetric hydrogenation of 1,4-diketones: facile synthesis of enantiopure 1,4-diarylbutane-1,4-diols
  作者：Jingyuan Song、Pan-Lin Shao、Jiang Wang、Fanping Huang、Xumu Zhang

  DOI：10.1039/d1cc05359k

  日期：——

  4-diarylbutane-1,4-diols and their derivatives, increasingly considerable attention has been paid to developing effective synthetic methods for chiral 1,4-diarylbutane-1,4-diols. We herein report an efficient asymmetric hydrogenation of 1,4-diaryldiketones catalyzed by a chiral iridium complex bearing f-amphox as ligand, furnishing a series of 1,4-diarylbutane-1,4-diols in excellent yields (up to >99%) with exceptional

  由于1,4-二芳基丁烷-1,4-二醇及其衍生物的生物学意义和巨大的合成价值，开发有效的手性1,4-二芳基丁烷-1,4-二醇的合成方法越来越受到重视。我们在此报告了由带有f- amphox 作为配体的手性铱配合物催化的 1,4-二芳基二酮的有效不对称氢化，以优异的产率提供了一系列 1,4-二芳基丁烷-1,4-二醇（高达 >99%） ) 具有出色的对映选择性（高达 >99.9% ee）和非对映选择性（高达 >100 : 1 dr）。
• Novel photo-rearrangement of 1,5-di(p-methoxyphenyl)-6,7-dioxabicyclo[3.2.2]nonane through an O-neophyl-type 1,2-aryl shift: evidence for a 1,6-dioxyl diradical intermediate
  作者：Masaki Kamata、Ken-ichi Komatsu

  DOI：10.1016/s0040-4039(01)01973-6

  日期：2001.12

  Photolysis and thermolysis of 1,5-diaryl-6,7-dioxabicyclo[3.2.2]nonane 1a–c (a: Ar=p-MeOC6H4, b: Ar=p-MeC6H4, c: Ar=Ph) were investigated. (p-Methoxyphenyl)-substituted 1a underwent a novel photo-initiated O-neophyl-type 1,2-aryl shift to afford 1-(p-methoxyphenyl)oxy-5-(p-methoxyphenyl)-8-oxabicyclo[3.2.1]octane 7a along with a small amount of 1-(p-methoxyphenyl)-3-(2-(4′-methoxyphenyl)tetrahydro

  1,5-二芳基-6,7-二氧杂双环[3.2.2]壬烷1a – c（a：Ar = p -MeOC 6 H 4，b：Ar = p -MeC 6 H 4，c：Ar的光解和热解= Ph）进行了调查。（对-甲氧基苯基）-取代的1a进行新的光引发的O-新叶型1,2-芳基转移，得到1-（对-甲氧基苯基）氧基-5-（对甲氧基苯基）-8-氧杂双环[3.2。 1]辛烷7a和少量1-（p-甲氧基苯基）-3-（2-（4'-甲氧基苯基）四氢呋喃-2-基）丙-1-酮4a通过1,6-二氧基双自由基中间体形成，而热解主要得到1,5-di（p -甲氧基苯基）戊-1,5-二酮5a和1,4-二（对甲氧基苯基）丁-1,4-二酮8a。