1,2-二乙炔基-3-甲氧基苯 | 412041-47-5

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 中文名称: 1,2-二乙炔基-3-甲氧基苯
• 英文名称: 1,2-diethynyl-3-methoxybenzene
• 英文别名: 2,3-diethynyl-1-methoxybenzene；2,3-diethynylanisole
• CAS: 412041-47-5
• 化学式: C₁₁H₈O
• 分子量: 156.184
• InChiKey: RHRJXRZLWDMUTC-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.4
• 重原子数：
  12
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.09
• 拓扑面积：
  9.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  1,2-二乙炔基-3-甲氧基苯 在 三甲基氯硅烷 、 1,4-环己二烯 作用下， 以 氯苯 为溶剂， 以67%的产率得到1-甲氧基萘
  参考文献：
  名称：

  具有邻位取代基的苯甲酰化二炔的伯格曼环化的调谐速率。

  摘要：

  [反应：见正文]苯甲酰化二炔的Bergman环化对邻位取代非常敏感。这一发现为合理设计构象特异性和pH依赖性DNA切割剂提供了可能性。

  DOI：

  10.1021/ol0255054
• 作为产物：
  描述：

  2,3-bis(trifluoromethanesulfonyloxy)anisole 在 bis-triphenylphosphine-palladium(II) chloride 、 copper(l) iodide 四丁基碘化铵 、 potassium carbonate 作用下， 以 甲醇 、 三乙胺 、 N,N-二甲基甲酰胺 为溶剂， 反应 11.0h， 生成 1,2-二乙炔基-3-甲氧基苯
  参考文献：
  名称：

  Reaction of ene-bis(phosphinylallenes): [2+2] versus [4+2] cycloaddition

  摘要：

  Reaction of ene-bis(phosphinylallenes), derived from ene-bis(propargyl alcohols) and chlorodiphenylphosphine, was investigated. Benzene-bridged bis(phosphinylallenes) exclusively gave intramolecular [2+2] cycloadducts in the presence of dimethyl fumarate in sharp contrast to the reaction of benzene-bridged bis(sulfinylallenes), which gave the corresponding [4+2] cycloadducts. On the other hand, substituted ethylene- or five-membered heterocycle-bridged bis(phosphinylallenes) provided [4+2] cycloadducts. Reaction of benzene-bridged diallene bearing both a sulfinyl group and a phosphinyl group on the two allenyl groups was also described. (c) 2006 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2006.08.083

文献信息

• Generation of Endocyclic Vinyl Carbene Complexes via Gold-Catalyzed Oxidative Cyclization of Terminal Diynes: Toward Naphthoquinones and Carbazolequinones
  作者：Chao Shu、Chong-Yang Shi、Qing Sun、Bo Zhou、Tian-You Li、Qiao He、Xin Lu、Rai-Shung Liu、Long-Wu Ye

  DOI：10.1021/acscatal.8b04455

  日期：2019.2.1

  generation of endocyclic vinyl carbene complexes was involved in this oxidative cyclization, which is distinctively different from previous protocols. This method allows the facile synthesis of various valuable naphthoquinones and carbazolequinones from readily available diynes under exceptionally mild reaction conditions and features a broad substrate scope and wide functional group tolerance. Moreover

  在过去的几十年中，涉及卡宾/炔烃复分解的卡宾级联反应引起了人们的极大关注，因为这种化学方法具有巨大的潜力来构建复杂的环状分子。然而，在这些反应中形成的乙烯基金属类胡萝卜素仅限于环外碳烯，并且内环乙烯基卡宾配合物的产生仍未探索。在这里，我们报告了前所未有的金催化末端二炔的氧化环化反应。重要的是，这种氧化环化过程涉及内环乙烯基卡宾配合物的产生，这与以前的方案截然不同。该方法可以在非常温和的反应条件下轻松地从容易获得的二炔中轻松合成各种有价值的萘醌和咔唑醌，并且具有广泛的底物范围和宽泛的官能团耐受性。而且，理论计算为该环化反应的不同选择性提供了进一步的证据。
• Borylative Radical Cyclizations of Benzo[3,4]cyclodec‐3‐ene‐1,5‐diynes and N‐Heterocyclic Carbene‐Boranes
  作者：Takashi Watanabe、Daisuke Hirose、Dennis P. Curran、Tsuyoshi Taniguchi

  DOI：10.1002/chem.201700689

  日期：2017.4.24

  Borylative radical cyclization of benzo[3,4]cyclodec‐3‐ene‐1,5‐diynes to provide 5‐borylated 6,7,8,9‐tetrahydrobenzo[a]azulenes has been developed. The experimental results suggest that the reaction proceeds by a radical chain mechanism, in which di‐tert‐butyl hyponitrite (TBHN) works as a good radical initiator to form boryl radicals from N‐heterocyclic carbene–boranes (NHC‐boranes). The present reaction

  已开发出苯并[3,4] cyclodec-3-烯-1,5-二炔的硼酸自由基环化反应，以提供5硼酸化的6,7,8,9-四氢苯并[ a ] azulenes。实验结果表明，反应是通过自由基链机理进行的，其中二叔丁基亚硝酸盐（TBHN）作为良好的自由基引发剂，可从N杂环卡宾-硼烷（NHC-硼烷）形成硼自由基。本反应是罕见的模型，其说明了向炔烃中加硼基。
• Ortho Effect in the Bergman Cyclization:  Interception of <i>p</i>-Benzyne Intermediate by Intramolecular Hydrogen Abstraction
  作者：Tarek A. Zeidan、Mariappan Manoharan、Igor V. Alabugin

  DOI：10.1021/jo051857n

  日期：2006.2.1

  Intramolecular hydrogen atom (H-atom) abstraction from the o-OCH3 group effectively intercepts the p-benzyne intermediate in the Bergman cycloaromatization of 2,3-diethynyl-1-methoxybenzene (1) before this intermediate undergoes either retro-Bergman ring opening or external H-atom abstraction. This process leads to the formation of a new diradical and renders the cyclization step essentially irreversible. Chemical and kinetic consequences of this phenomenon were investigated through the combination of computational and experimental studies.
• Reaction of ene-bis(phosphinylallenes): [2+2] versus [4+2] cycloaddition
  作者：Shinji Kitagaki、Yuki Okumura、Chisato Mukai

  DOI：10.1016/j.tet.2006.08.083

  日期：2006.10

  Reaction of ene-bis(phosphinylallenes), derived from ene-bis(propargyl alcohols) and chlorodiphenylphosphine, was investigated. Benzene-bridged bis(phosphinylallenes) exclusively gave intramolecular [2+2] cycloadducts in the presence of dimethyl fumarate in sharp contrast to the reaction of benzene-bridged bis(sulfinylallenes), which gave the corresponding [4+2] cycloadducts. On the other hand, substituted ethylene- or five-membered heterocycle-bridged bis(phosphinylallenes) provided [4+2] cycloadducts. Reaction of benzene-bridged diallene bearing both a sulfinyl group and a phosphinyl group on the two allenyl groups was also described. (c) 2006 Elsevier Ltd. All rights reserved.
• Tuning Rate of the Bergman Cyclization of Benzannelated Enediynes with Ortho Substituents
  作者：Igor V. Alabugin、Mariappan Manoharan、Serguei V. Kovalenko

  DOI：10.1021/ol0255054

  日期：2002.4.1

  [reaction: see text] The Bergman cyclization of benzannelated enediynes is highly sensitive to ortho substitution. This finding opens possibilities for the rational design of conformer-specific and pH-dependent DNA-cleaving agents.

  [反应：见正文]苯甲酰化二炔的Bergman环化对邻位取代非常敏感。这一发现为合理设计构象特异性和pH依赖性DNA切割剂提供了可能性。