(E)-1-anthracen-9-ylpent-1-en-3-one

• 分子结构分类: 有机化合物 - 苯类化合物 - 蒽
• 英文名称: (E)-1-anthracen-9-ylpent-1-en-3-one
• 化学式: C₁₉H₁₆O
• 分子量: 260.335
• InChiKey: IBSFZIXOAIGZJG-VAWYXSNFSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.3
• 重原子数：
  20
• 可旋转键数：
  3
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.11
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为产物：
  描述：

  1-戊烯-3-酮 、 9-溴蒽 在 bis(η3-allyl-μ-chloropalladium(II)) 、 Tedicyp sodium acetate 、 对苯二酚 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 20.0h， 以89%的产率得到(E)-1-anthracen-9-ylpent-1-en-3-one
  参考文献：
  名称：

  Synthesis of (E)-1-Aryl Alk-1-en-3-ones by Tetraphosphine/Palladium-Catalysed Heck Reactions of Alk-1-en-3-ones with Aryl Bromides

  摘要：

  四膦cis,cis,cis-1,2,3,4-四(二苯膦甲基)环戊烷与[Pd(C3H5)Cl]2结合，可以有效地催化烯-1-烯-3-酮与芳基溴化物的赫克反应。如果使用适当的反应条件（以醋酸钠为碱，羟基苯作为稳定剂，DMF作为溶剂），可以获得高产率的（E）-1-芳基烯-1-烯-3-酮衍生物。一般来说，使用电子贫乏的芳基溴化物时反应速率较高，但电子丰富的芳基溴化物4-N,N-二甲基氨基溴苯和4-溴苯醚也能生成芳基化的烯酮。即使是非常拥挤的芳基溴化物，如9-溴芴、2,4,6-三甲基溴苯或2,4,6-三异丙基溴苯，预期的（E）-1-芳基烯-1-烯-3-酮也以中等到良好的产率获得。此外，几乎可以仅用0.1%的催化剂进行多次反应。

  DOI：

  10.1055/s-2006-948174

文献信息

• Synthesis of (<i>E</i>)-1-Aryl Alk-1-en-3-ones by Tetraphosphine/Palladium-Catalysed Heck Reactions of Alk-1-en-3-ones with Aryl Bromides
  作者：Henri Doucet、Maurice Santelli、Mhamed Lemhadri

  DOI：10.1055/s-2006-948174

  日期：2006.11

  The tetraphosphine cis,cis,cis-1,2,3,4-tetrakis(di­phenylphosphinomethyl)cyclopentane in combination with [Pd(C3H5)Cl]2 affords a very efficient catalyst for the Heck reaction of alk-1-en-3-ones with aryl bromides. If appropriate reaction ­conditions are used (NaOAc as base, hydroquinone as stabilising agent and DMF as solvent) high yields of (E)-1-aryl alk-1-en-3-one derivatives are obtained. In general, higher reaction rates were observed with electron-poor aryl bromides, but the electron-rich aryl bromides 4-N,N-dimethylaminobromobenzene and 4-bromoanisole also led to the arylated enones. Even with sterically very congested aryl bromides such as 9-bromoanthracene, 2,4,6-trimethylbromo­benzene or 2,4,6-triisopropylbromobenzene, the expected (E)-1-aryl alk-1-en-3-ones were obtained in moderate to good yields. Moreover, several reactions can be performed with as little as 0.1% catalyst.

  四膦cis,cis,cis-1,2,3,4-四(二苯膦甲基)环戊烷与[Pd(C3H5)Cl]2结合，可以有效地催化烯-1-烯-3-酮与芳基溴化物的赫克反应。如果使用适当的反应条件（以醋酸钠为碱，羟基苯作为稳定剂，DMF作为溶剂），可以获得高产率的（E）-1-芳基烯-1-烯-3-酮衍生物。一般来说，使用电子贫乏的芳基溴化物时反应速率较高，但电子丰富的芳基溴化物4-N,N-二甲基氨基溴苯和4-溴苯醚也能生成芳基化的烯酮。即使是非常拥挤的芳基溴化物，如9-溴芴、2,4,6-三甲基溴苯或2,4,6-三异丙基溴苯，预期的（E）-1-芳基烯-1-烯-3-酮也以中等到良好的产率获得。此外，几乎可以仅用0.1%的催化剂进行多次反应。
• 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。