(E)-4-(4-acetylphenyl)but-3-en-2-one | 115665-94-6

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (E)-4-(4-acetylphenyl)but-3-en-2-one
• 英文别名: (E)-4-acetylbenzalacetone；4-(4-acetyl-phenyl)-but-3t-en-2-one；4-(4-Acetyl-phenyl)-but-3t-en-2-on；(3E)-4-(4-Acetylphenyl)-3-buten-2-one
• CAS: 115665-94-6
• 化学式: C₁₂H₁₂O₂
• 分子量: 188.226
• InChiKey: XCFFGUOWJMOOEM-ONEGZZNKSA-N

物化性质

• 熔点：
  103 °C
• 沸点：
  357.5±25.0 °C(Predicted)
• 密度：
  1.072±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.1
• 重原子数：
  14
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.17
• 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：

  (E)-4-(4-acetylphenyl)but-3-en-2-one 在 三氟甲磺酸三甲基硅酯 、 三苯基膦 、 二异丁基氢化铝 、 potassium carbonate 作用下， 以 二氯甲烷 、 正己烷 、 甲醇 为溶剂， 反应 1.5h， 以82%的产率得到(E)-4-(4-(1-hydroxyethyl)phenyl)but-3-en-2-one
  参考文献：
  名称：

  Selective Transformations of Carbonyl Functions in the Presence of α,β-Unsaturated Ketones: Concise Asymmetric Total Synthesis of Decytospolides A and B

  摘要：

  Enones selectively react with a combination of PPh3 and TMSOTf to produce phosphonium silyl enol ethers, which work as protective groups of enones during the reduction of other carbonyl functions and can be easily deprotected to regenerate parent enones at workup. Furthermore, the first ketone selective alkylations in the presence of enones were also accomplished. This in situ protection method was applied to concise asymmetric total syntheses of decytospolides A and B.

  DOI：

  10.1021/ol501463p
• 作为产物：
  描述：

  邻氯乙苯 在 三氯化铝 、 三乙醇胺 、 水 作用下， 生成 (E)-4-(4-acetylphenyl)but-3-en-2-one
  参考文献：
  名称：

  Baddeley et al., Journal of the Chemical Society, 1953, p. 2110,2114

  摘要：

  DOI：

文献信息

• A Selective and Benign Synthesis of Functionalized Benzalacetones <i>via</i> Mizoroki–Heck Reaction Using Aryldiazonium Salts
  作者：Therese Stern、Sven Rückbrod、Constantin Czekelius、Constanze Donner、Heiko Brunner

  DOI：10.1002/adsc.200900868

  日期：2010.10.9

  Palladium-catalyzed Mizoroki–Heck reactions were carried out in the presence of calcium carbonate in alcoholic solvents. Under these conditions an efficient preparation of functionalized benzalacetones was developed. The reactions were carried out at room temperature and aerobic conditions, giving the products within several minutes in up to 95% isolated yields. Furthermore, some kinetic investigations

  钯催化的Mizoroki-Heck反应是在碳酸钙存在下于醇类溶剂中进行的。在这些条件下，开发了一种高效制备功能化苯并丙酮的方法。反应在室温和有氧条件下进行，数分钟内获得产物，分离产率高达95％。此外，还介绍了一些动力学研究，机理见解和注意事项。
• Regioselective Heck Vinylation of Electron-Rich Olefins with Vinyl Halides: Is the Neutral Pathway in Operation?
  作者：Matthew McConville、Ourida Saidi、John Blacker、Jianliang Xiao

  DOI：10.1021/jo802781m

  日期：2009.4.3

  Highly regioselective vinylation of electron-rich olefins by bromo- as well as chlorostyrenes is effected by palladium catalysis with either mono- or bidentate phosphines in a molecular solvent, with no need for halide scavengers, ionic liquids, or ionic additives. The use of the hemilabile 1,3-bis(diphenylphosphino)propane monoxide (dpppO) as a ligand led to faster reactions of more challenging 2-substituted

  溴和氯苯乙烯对富电子烯烃的高度区域选择性乙烯基化是通过在分子溶剂中用单或二齿膦进行钯催化来实现的，不需要卤化物清除剂，离子液体或离子添加剂。半不稳定的1,3-双（二苯基膦基）丙烷一氧化碳（dpppO）作为配体的使用导致更具挑战性的2-取代乙烯基醚的反应更快，并降低了Pd的负载量。与相关的芳基化反应相反，证据表明乙烯基化可能通过中性的Heck机制进行。
• Palladium-Catalysed Heck Reactions of Alk-1-en-3-ones with Aryl Bromides: A Very Simple Access to (<i>E</i>)-1-Arylalk-1-en-3-ones
  作者：Mhamed Lemhadri、Yacoub Fall、Henri Doucet、Maurice Santelli

  DOI：10.1055/s-0028-1087976

  日期：——

  When appropriate reaction conditions are used, very high yields of (E)-1-arylalk-1-en-3-one derivatives can be obtained by palladium-catalysed reactions of alk-1-en-3-ones with aryl bromides. The tetraphosphine cis,cis,cis-1,2,3,4-tetrakis(diphenylphosphinomethyl)cyclopentane in combination with [Pd(C3H5)Cl]2 was found to be a very efficient catalyst for this reaction. In general, higher reaction rates were observed with electron-poor aryl bromides, but the electron-rich aryl bromides 1-bromo-4-(dimethylamino)benzene and 4-bromoanisole also led to the arylated enones in high yields. Even with sterically very congested aryl bromides such as 9-bromoanthracene, 1-bromo-2,4,6-trimethylbenzene or 1-bromo-2,4,6-triisopropylbenzene, the expected (E)-1-arylalk-1-en-3-ones were obtained in moderate to good yields. These enones appear to be unstable under the reaction conditions, and the addition of a small amount of hydroquinone to the reaction mixture was found to be crucial, especially for the vinylation of electron-deficient aryl bromides. A variety of alk-1-en-3-ones has been employed, and better results in terms of substrate/catalyst ratios were obtained when oct-1-en-3-one or hex-1-en-3-one was used than when but-1-en-3-one or pent-1-en-3-one was used. It should be noted that several reactions can be performed with as little as 0.1-0.001 mol% catalyst.

  在适当的反应条件下，通过钯催化的alk-1-en-3-ones与芳基溴化物的反应，可以获得高产率的(E)-1-芳基烯-1-烯-3-酮衍生物。铑催化剂中发现四膦配体顺，顺，顺-1,2,3,4-四(二苯膦甲基)环戊烷与[Pd(C3H5)Cl]2结合是一种非常高效的催化剂。通常情况下，电子贫乏的芳基溴化物显示出更高的反应速率，但电子富集的芳基溴化物1-溴-4-(二甲基氨基)苯和4-溴苯甲醚也能导致高产率的芳基化烯酮。即使在空间位阻很大的芳基溴化物如9-溴蒽、1-溴-2,4,6-三甲基苯或1-溴-2,4,6-三异丙基苯的情况下，期望的(E)-1-芳基烯-1-烯-3-酮也能在中等至良好的产率下获得。这些烯酮在反应条件下似乎是不稳定的，在反应混合物中加入少量的氢醌被发现是至关重要的，特别是对于电子缺乏的芳基溴化物的乙烯基化。已使用了多种alk-1-en-3-ones，当使用辛-1-烯-3-酮或己-1-烯-3-酮时，相对于底物/催化剂比例，得到了更好的结果，而不是丁-1-烯-3-酮或戊-1-烯-3-酮。值得注意的是，有几种反应可以在仅0.1-0.001 mol%催化剂的情况下进行。
• Use of functionalized onium salts as a soluble support for organic synthesis
  申请人：Vaultier Michel

  公开号：US20070043234A1

  公开（公告）日：2007-02-22

  The invention relates to the use of a onium salt functionalized by at least one organic function, as a soluble support, in the presence of at least one organic solvent, for organic synthesis of a molecule, in a homogenous phase, by at least one transformation of said organic function. The onium salt enables the synthesized molecule to be released. The onium salt is present in liquid or solid form at room temperature and corresponds to formula A 1 + , X 1 − , wherein A 1 + represents a cation and X 1 − represents an anion.

  该发明涉及使用至少一个有机功能官能化的离子盐作为可溶性支持体，在至少一个有机溶剂的存在下，用于在均相相中通过至少一个所述有机功能的转化对分子进行有机合成。该离子盐使合成的分子能够被释放。该离子盐在室温下以液态或固态形式存在，符合以下公式A1+，X1−，其中A1+代表阳离子，X1−代表阴离子。
• Heck-type coupling vs. conjugate addition in phosphine–rhodium catalyzed reactions of aryl boronic acids with α,β-unsaturated carbonyl compounds: a systematic investigation
  作者：Gang Zou、Jianping Guo、Zhiyong Wang、Wen Huang、Jie Tang

  DOI：10.1039/b615473e

  日期：——

  Heck-type coupling and conjugate addition by synergistically tuning the supporting ligand, the boronic acid to olefin ratio and other reaction conditions. Conjugate addition with selectivity >99% and Heck-type coupling with selectivity of up to 100%, 98% and 84% for acrylates, acrylamides and methyl vinyl ketone, respectively, could be achieved in the rhodium-catalyzed reactions of aryl boronic acids

  在甲苯-H（2）O双相系统中，已系统研究了膦-铑催化的芳基硼酸与α，β-不饱和羰基的反应中的Heck型偶联和共轭加成之间的竞争。除了铑的内在性质和羰基的烯醇化之外，发现铑上的膦支持配体，芳基硼酸与α，β-不饱和羰基的比例以及水相的pH值均显着影响竞争。因此，已经通过协同调节载体配体，硼酸与烯烃的比例和其他反应条件，开发了用于Heck型偶联和共轭物加成的高选择性铑基催化剂体系。共轭添加的选择性> 99％，Heck型偶联的选择性高达100％，