6-ethynyl-2,4-dihydroxy-3-methylbenzaldehyde | 915789-22-9

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 6-ethynyl-2,4-dihydroxy-3-methylbenzaldehyde
• CAS: 915789-22-9
• 化学式: C₁₀H₈O₃
• 分子量: 176.172
• InChiKey: JAAGPJFDPYJBBJ-UHFFFAOYSA-N

物化性质

• 熔点：
  165 °C (decomp)
• 沸点：
  367.1±27.0 °C(Predicted)
• 密度：
  1.34±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.8
• 重原子数：
  13
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.1
• 拓扑面积：
  57.5
• 氢给体数：
  2
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  6-ethynyl-2,4-dihydroxy-3-methylbenzaldehyde 在 4-二甲氨基吡啶 、 bis-triphenylphosphine-palladium(II) chloride 、 N-氯代丁二酰亚胺 、 copper(l) iodide 、 tetrakis(actonitrile)copper(I) hexafluorophosphate 、 氧气 、 三乙胺 、 N,N-二异丙基乙胺 、 (1R,2S,9S)-11-ethyl-7,11-diazatricyclo[7.3.1.0^2,7]tridecane 作用下， 以 四氢呋喃 、 二氯甲烷 、 乙腈 为溶剂， 反应 31.58h， 生成 (+)-N-methylsclerotiorinamine
  参考文献：
  名称：

  Synthesis of the Azaphilones (+)-Sclerotiorin and (+)-8-O-Methylsclerotiorinamine Utilizing (+)-Sparteine Surrogates in Copper-Mediated Oxidative Dearomatization

  摘要：

  Enantioselective syntheses of the azaphilone natural products (+)-sclerotiorin and (+)-8-O-methylsclerotiorinamine that possess the natural R-configuration at the quaternary center are reported. The syntheses were accomplished using copper-mediated asymmetric dearomatization employing bis-y-oxo copper complexes prepared from readily available (+)-sparteine surrogates. Of note, site-selective O-methylation of a vinylogous pyridone was used to access the isoquinolin-6(7H)-one core of (+)-8-O-methylsclerotiorinamine.

  DOI：

  10.1021/jo102448n
• 作为产物：
  描述：

  2,4-二甲氧基-3-甲基苯甲醛 在 bis-triphenylphosphine-palladium(II) chloride 、 copper(l) iodide 、 正丁基锂 、 1,2-二碘乙烷 、 三溴化硼 、 potassium carbonate 、 N,N,N'-三甲基乙二胺 、 二异丙胺 、 tri tert-butylphosphoniumtetrafluoroborate 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 31.0h， 生成 6-ethynyl-2,4-dihydroxy-3-methylbenzaldehyde
  参考文献：
  名称：

  Synthesis of the Azaphilones (+)-Sclerotiorin and (+)-8-O-Methylsclerotiorinamine Utilizing (+)-Sparteine Surrogates in Copper-Mediated Oxidative Dearomatization

  摘要：

  Enantioselective syntheses of the azaphilone natural products (+)-sclerotiorin and (+)-8-O-methylsclerotiorinamine that possess the natural R-configuration at the quaternary center are reported. The syntheses were accomplished using copper-mediated asymmetric dearomatization employing bis-y-oxo copper complexes prepared from readily available (+)-sparteine surrogates. Of note, site-selective O-methylation of a vinylogous pyridone was used to access the isoquinolin-6(7H)-one core of (+)-8-O-methylsclerotiorinamine.

  DOI：

  10.1021/jo102448n

文献信息

• Design, Synthesis and Fungicidal Activity of Novel Sclerotiorin Derivatives
  作者：Long Lin、Nick Mulholland、Shao-Wei Huang、David Beattie、Dianne Irwin、Yu-Cheng Gu、John Clough、Qiong-You Wu、Guang-Fu Yang

  DOI：10.1111/cbdd.12005

  日期：2012.11

  Sclerotiorin, a chlorine‐containing azaphilone‐type natural product, was first isolated from Penicillium sclerotiorum and has been reported to exhibit weak fungicidal activity. Optimization of the substituents at the 3‐ and 5‐positions of the sclerotiorin framework was investigated with the aim of discovering novel fungicides with improved activity. The design of sclerotiorin analogues involved replacing

  巩膜甲菌素是一种含氯的氮杂苯甲酮类天然产物，最初是从青霉菌中分离出来的，据报道其杀真菌活性较弱。为了发现具有改进活性的新型杀真菌剂，研究了硬化菌素骨架3和5位上取代基的优化。巩膜铁蛋白类似物的设计涉及用苯基或含芳族或杂芳族的脂族侧链取代二烯侧链。通过环异构化和随后氧化合适的2-炔基苯甲醛合成设计的化合物，其中使用Sonogashira偶联反应引入各种取代基。这些新制备的化合物的结构由1证实。H和13 C NMR光谱，HRMS和单晶X射线分析。评估了合成化合物对7种植物病原菌的抗真菌活性。化合物3，9克和9H中发现有杀真菌活性的广谱性，并且这些结构上简单的产品可以被识别为用于进一步优化铅化合物。
• Asymmetric Syntheses of (−)-Mitorubrin and Related Azaphilone Natural Products
  作者：Jianglong Zhu、John A. Porco

  DOI：10.1021/ol062233m

  日期：2006.10.1

  Asymmetric syntheses of (-)-mitorubrin and related azaphilone natural products are reported. Key steps involve copper-mediated, enantioselective oxidative dearomatization to prepare the azaphilone core and olefin cross-metathesis for side-chain installation. [reaction: see text]

  （-）-mitorubrin和相关的azaphilone天然产物的不对称合成的报告。关键步骤涉及铜介导的对映选择性氧化脱芳香化反应，以制备氮杂philone核和用于侧链安装的烯烃交叉复分解。[反应：看文字]
• Synthesis of the Azaphilones (+)-Sclerotiorin and (+)-8-<i>O</i>-Methylsclerotiorinamine Utilizing (+)-Sparteine Surrogates in Copper-Mediated Oxidative Dearomatization
  作者：Andrew R. Germain、Daniel M. Bruggemeyer、Jianglong Zhu、Cedric Genet、Peter O’Brien、John A. Porco

  DOI：10.1021/jo102448n

  日期：2011.4.15

  Enantioselective syntheses of the azaphilone natural products (+)-sclerotiorin and (+)-8-O-methylsclerotiorinamine that possess the natural R-configuration at the quaternary center are reported. The syntheses were accomplished using copper-mediated asymmetric dearomatization employing bis-y-oxo copper complexes prepared from readily available (+)-sparteine surrogates. Of note, site-selective O-methylation of a vinylogous pyridone was used to access the isoquinolin-6(7H)-one core of (+)-8-O-methylsclerotiorinamine.