Methyl 2-<2-<2-(1-oxoethyl)phenyl>ethynyl>benzoate | 166757-06-8

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: Methyl 2-<2-<2-(1-oxoethyl)phenyl>ethynyl>benzoate
• 英文别名: 1-(2-(1-(2-methoxycarbonylphenyl)ethynyl)phenyl)ethan-1-one；methyl 2-[(2-acetylphenyl)ethynyl]benzoate；Methyl 2-[2-(2-acetylphenyl)ethynyl]benzoate
• CAS: 166757-06-8
• 化学式: C₁₈H₁₄O₃
• 分子量: 278.307
• InChiKey: NZZGMQIOHPWYSU-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.5
• 重原子数：
  21
• 可旋转键数：
  5
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.11
• 拓扑面积：
  43.4
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  Methyl 2-<2-<2-(1-oxoethyl)phenyl>ethynyl>benzoate 在 sodium hydride 作用下， 以 四氢呋喃 为溶剂， 反应 4.0h， 以83%的产率得到Methyl 2-<2-<2-(1-oxoethyl)phenyl>-1-oxoethyl>benzoate
  参考文献：
  名称：

  An Unusual Example of a 6-Endo-Dig Addition to an Unactivated Carbon-Carbon Triple Bond

  摘要：

  Methyl 2-[2-[2-(1-hydroxy-1-ethyl)phenyl]ethynyl]benzoate was prepared as an intermediate for subsequent conversion to an a-diazo ketone. Under the basic conditions used to hydrolyze the methyl ester, the neighboring hydroxyl functionality underwent reaction with the unactivated acetylenic group, producing a benzopyranyl-substituted alpha-diazoacetophenone. Treatment of this diazocarbonyl compound with a catalytic quantity of rhodium(II) mandelate afforded a novel dibenzo[a,e]cyclononenone derivative. The reaction proceeds via an initially formed oxonium ylide which rearranges further by means of a 1,2-alkyl shift. A prime factor in determining the direction of internal cyclization to the triple bond is the presence of the carbomethoxy group in the ortho position of the beta-phenyl ring. Thus, in contrast with related systems which exhibit a clear preference for 5-exo-dig cyclization at the acetylenic center, the 6-endo-dig addition is the preferred pathway for the o-formyl- and o-carbomethoxy-substituted alkynyl alcohols. Careful monitoring of the reaction actually showed that the reaction proceeds by initial formation of the 5-exo-dig product followed by a novel rearrangement to the 6-endo product.

  DOI：

  10.1021/jo00122a047
• 作为产物：
  描述：

  2-(1-羟乙基)-1-乙炔基苯 在 copper(l) iodide 、 bis(triphenylphosphine)palladium(II)-chloride 、 三乙胺 、 pyridinium chlorochromate 作用下， 以 二氯甲烷 为溶剂， 反应 20.0h， 生成 Methyl 2-<2-<2-(1-oxoethyl)phenyl>ethynyl>benzoate
  参考文献：
  名称：

  An Unusual Example of a 6-Endo-Dig Addition to an Unactivated Carbon-Carbon Triple Bond

  摘要：

  Methyl 2-[2-[2-(1-hydroxy-1-ethyl)phenyl]ethynyl]benzoate was prepared as an intermediate for subsequent conversion to an a-diazo ketone. Under the basic conditions used to hydrolyze the methyl ester, the neighboring hydroxyl functionality underwent reaction with the unactivated acetylenic group, producing a benzopyranyl-substituted alpha-diazoacetophenone. Treatment of this diazocarbonyl compound with a catalytic quantity of rhodium(II) mandelate afforded a novel dibenzo[a,e]cyclononenone derivative. The reaction proceeds via an initially formed oxonium ylide which rearranges further by means of a 1,2-alkyl shift. A prime factor in determining the direction of internal cyclization to the triple bond is the presence of the carbomethoxy group in the ortho position of the beta-phenyl ring. Thus, in contrast with related systems which exhibit a clear preference for 5-exo-dig cyclization at the acetylenic center, the 6-endo-dig addition is the preferred pathway for the o-formyl- and o-carbomethoxy-substituted alkynyl alcohols. Careful monitoring of the reaction actually showed that the reaction proceeds by initial formation of the 5-exo-dig product followed by a novel rearrangement to the 6-endo product.

  DOI：

  10.1021/jo00122a047

文献信息

• Competition Studies in Alkyne Electrophilic Cyclization Reactions
  作者：Saurabh Mehta、Jesse P. Waldo、Richard C. Larock

  DOI：10.1021/jo802196r

  日期：2009.2.6

  toward alkyne electrophilic cyclization reactions has been studied. The required diarylalkynes have been prepared by consecutive Sonogashira reactions of appropriately substituted aryl halides and competitive cyclizations have been performed using I2, ICl, NBS and PhSeCl as electrophiles. The results indicate that the nucleophilicity of the competing functional groups, polarization of the alkyne triple

  已经研究了各种官能团对炔烃亲电环化反应的相对反应性。所需的二芳基炔已通过适当取代的芳基卤化物的连续 Sonogashira 反应制备，并使用 I 2、ICl、NBS 和 PhSeCl 作为亲电子试剂进行竞争性环化。结果表明，竞争官能团的亲核性、炔烃三键的极化和中间体的阳离子性质是决定这些反应结果的最重要因素。
• Silver-catalyzed C–C bond formation with carbon dioxide: significant synthesis of dihydroisobenzofurans
  作者：Kohei Sekine、Ayano Takayanagi、Satoshi Kikuchi、Tohru Yamada

  DOI：10.1039/c3cc47221c

  日期：——

  The silver salt catalyzed the C–C bond forming reaction of o-alkynylacetophenone derivatives and carbon dioxide. In this reaction, a carbonyl group and a furan skeleton were successively constructed to afford the corresponding dihydroisobenzofuran derivatives.

  银盐催化了o-炔基乙酰苯酮衍生物与二氧化碳之间的C–C键形成反应。在该反应中，羰基和呋喃骨架被连续构建，从而得到相应的二氢异苯并呋喃衍生物。
• Single Cu(I)-Photosensitizer Enabling Combination of Energy-Transfer and Photoredox Catalysis for the Synthesis of Benzo[<i>b</i>]fluorenols from 1,6-Enynes
  作者：Limeng Zheng、Han Xue、Bingwei Zhou、Shu-Ping Luo、Hongwei Jin、Yunkui Liu

  DOI：10.1021/acs.orglett.1c01427

  日期：2021.6.4

  An efficient, mild, and atom-economical synthesis of benzo[b]fluorenols from 1,6-enynes has been developed under photocatalytic conditions. A single P/N heteroleptic Cu(I)-photosensitizer might exhibit both energy-transfer and photoredox catalytic activities in the formation of benzo[b]fluorenols.

  已经在光催化条件下开发了一种从 1,6-烯炔有效、温和且原子经济地合成苯并 [ b ] 芴醇的方法。单个 P/N 杂配 Cu(I)-光敏剂可能在苯并 [ b ] 芴醇的形成过程中表现出能量转移和光氧化还原催化活性。
• CATALYSTS FOR THE ALKYNE METATHESIS
  申请人：Fuerstner Alois

  公开号：US20130144102A1

  公开（公告）日：2013-06-06

  Organometallic compounds of the general formula (I), in which M=Mo, W, are claimed.

  声称具有一般式(I)的有机金属化合物，其中M=Mo，W。
• US8993470B2
  申请人：——

  公开号：US8993470B2

  公开（公告）日：2015-03-31