1-(1-ethoxyprop-2-ynyl)benzene | 157022-42-9

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 1-(1-ethoxyprop-2-ynyl)benzene
• 英文别名: 3-phenyl-3-ethoxypropyne；ethyl 1-phenyl-2-propynyl ether；(+/-)-ethyl-(1-phenyl-prop-2-ynyl)-ether；(+/-)-Aethyl-(1-phenyl-prop-2-inyl)-aether；(+/-)-1-Aethoxy-1-phenyl-propin-(2)；1-Ethoxyprop-2-ynylbenzene
• CAS: 157022-42-9
• 化学式: C₁₁H₁₂O
• 分子量: 160.216
• InChiKey: OSCMJWYSYBEZKY-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.3
• 重原子数：
  12
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.27
• 拓扑面积：
  9.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为产物：
  描述：

  3-苯基-2-丙炔-1-胺 盐酸盐 在 吡啶 、 sodium hydroxide 、 nitrosonium tetrafluoroborate 、 三乙胺 作用下， 以 乙醚 、 乙醇 、 二氯甲烷 为溶剂， 反应 2.0h， 生成 1-(1-ethoxyprop-2-ynyl)benzene
  参考文献：
  名称：

  Carbene-Carbene Interconversion between 1- and 3-Phenyl-2-propynylidenes

  摘要：

  1-Phenyl-3-diazopropyne (Id) and 3-phenyl-3-diazopropyne (2d) were prepared and photolyzed under various conditions. In ethanol at ambient temperatures, both 1d and 2d gave a 1:10 +/- 1 mixture of 1-phenyl-3-ethoxypropyne (3) and 3-phenyl-3-ethoxypropyne (4). The photolyses of matrix-isolated 1d and 2d at cryogenic temperatures were followed by EPR, IR, and UV-visible spectroscopy. EPR experiments in 2-methyltetrahydrofuran (MTHF), isopentane, and ethanol-d(6) matrices at 9 K showed spectra due to a mixture of the corresponding triplet carbenes 1c (\D/hc\ = 0.543 and \E/hc\ = 0.003 cm(-1)) and 2c (\D/hc\ = 0.526 and \E/hc\ = 0.010 cm(-1)). The ratio of the generated carbenes carried the memory of the starting diazo compounds; 1c and 2c were produced mainly from 1d and 2d, respectively. Carbene 2c isomerized to 1c at 70-90 K in MTHF and ethanol-d(6) and at 44-68 K in isopentane, indicating that 1c was thermodynamically more stable than 2c on the triplet ground-state potential energy surface. IR and UV-visible absorption experiments employing various media (argon, isopentane, N-2, CO/Ar, O-2/N-2, and O-2/Ar) revealed that the photolysis of 2d afforded mostly absorptions due to 2c. Photolysis of 1d produced similar spectra, due mainly to 2c, together with weak absorptions due to 1c. The different results observed in EPR and IR experiments were explained by the difference in the matrices in which the diazo groups were photolyzed. Calculations at the ab initio MP2/DZV(d) level of theory showed that the triplet ground state of 1c was more thermodynamically stable than 2c by 1.41 kcal/mol, in agreement with the experimental results. The situation is reversed in the singlet manifold, where 2c was computed to be much lower in energy than 1c. The energy differences (Delta E(ST)) between the singlet and triplet states were computed to be 15.7 and 11.0 kcal/mol for 1c and 2c, respectively, with the DZV(d) basis set.

  DOI：

  10.1021/ja00093a017

文献信息

• The reactions of benzyne with allenes
  作者：Harry H. Wasserman、Leonard S. Keller

  DOI：10.1039/c2970001483b

  日期：——

  The reactions of benzyne with allenes may proceed by 2 + 2 cycloaddition, or by ene-like reactions with formation of a 1,3-diene or an acetylene.

  苯并炔与丙二烯的反应可以通过2 + 2环加成反应进行，也可以通过类似烯的反应进行，形成1,3-二烯或乙炔。
• Metal-Free Catalytic Nucleophilic Substitution of Propargylic Alcohols
  作者：Roberto Sanz、Alberto Martínez、Julia M. Álvarez-Gutiérrez、Félix Rodríguez

  DOI：10.1002/ejoc.200500960

  日期：2006.3

  Organic acids such as PTS efficiently catalyze direct nucleophilic substitutions of the hydroxy groups of propargylic alcohols with a large variety of carbon- and heteroatom-centered nucleophiles. Reactions can be conducted under mild conditions and in air without the need for dried solvents. Reactions on multigram scales are also possible. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany

  有机酸如 PTS 有效地催化炔丙醇的羟基与多种以碳和杂原子为中心的亲核试剂的直接亲核取代。反应可在温和条件下和空气中进行，无需干燥溶剂。多克级的反应也是可能的。(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)
• FeCl₃-Catalyzed Coupling of Propargylic Acetates with Alcohols
  作者：Zhuang-Ping Zhan、Hui-Juan Liu

  DOI：10.1055/s-2006-949645

  日期：2006.9

  A new method for the synthesis of propargylic ethers by FeCl3-catalyzed alcoholysis of propargylic acetates was developed. The reaction was carried out at room temperature in acetonitrile without exclusion of moisture or air. High product yields were obtained with excellent reaction regioselectivity.

  开发了一种通过FeCl3催化的炔丙基乙酸酯的醇解合成炔丙基醚的新方法。该反应在室温下、无水无氧排除的条件下，在乙腈中进行。获得了高产率的产物，并且反应具有极佳的区域选择性。
• Ruthenium-Catalyzed Propargylic Substitution Reactions of Propargylic Alcohols with Oxygen-, Nitrogen-, and Phosphorus-Centered Nucleophiles
  作者：Yoshiaki Nishibayashi、Marilyn Daisy Milton、Youichi Inada、Masato Yoshikawa、Issei Wakiji、Masanobu Hidai、Sakae Uemura

  DOI：10.1002/chem.200400833

  日期：2005.2.18

  The scope and limitations of the ruthenium-catalyzed propargylic substitution reaction of propargylic alcohols with heteroatom-centered nucleophiles are presented. Oxygen-, nitrogen-, and phosphorus-centered nucleophiles such as alcohols, amines, amides, and phosphine oxide are available for this catalytic reaction. Only the thiolate-bridged diruthenium complexes can work as catalysts for this reaction

  提出了钌催化的炔丙醇与以杂原子为中心的亲核试剂进行炔丙基取代反应的范围和局限性。以氧，氮和磷为中心的亲核试剂（例如醇，胺，酰胺和氧化膦）可用于该催化反应。仅硫醇盐桥接的二钌络合物可以用作该反应的催化剂。一些化学计量和催化反应的结果表明，催化炔丙基取代反应是通过原位形成的亚烯基络合物进行的，由此亲核试剂对亚烯基C（γ）原子的攻击是关键步骤。对炔丙醇与几种对位取代苯胺反应的相对速率常数的研究表明，苯胺对亚烯基C（γ）原子的攻击不参与速率的确定步骤，而是苯胺的共轭苯胺的酸度。苯胺攻击C（γ）原子后形成的炔基络合物被认为是决定该催化反应速率的最重要因素。通过使用硫醇盐桥连的二钌配合物来促进该催化反应的关键点被认为是在催化循环中二钌配合物上的亚乙烯基配体与另一种炔丙醇之间的配体交换步骤容易。在该催化反应中，仅硫醇盐桥接的二钌配合物相对于其他单钌配合物更容易促进配体交换步骤的原因应是一个不参与亚烯基形
• A General and Efficient FeCl₃-Catalyzed Nucleophilic Substitution of Propargylic Alcohols
  作者：Zhuang-ping Zhan、Jing-liang Yu、Hui-juan Liu、Yuan-yuan Cui、Rui-feng Yang、Wen-zhen Yang、Jun-ping Li

  DOI：10.1021/jo061234p

  日期：2006.10.1

  A general and efficient FeCl3-catalyzed substitution reaction of propargylic alcohols with carbon- and heteroatom-centered nucleophiles such as allyl trimethylsilane, alcohols, aromatic compounds, thiols, and amides, leading to the construction of C−C, C−O, C−S and C−N bonds, has been developed.

  炔丙醇与碳和杂原子中心的亲核试剂（如烯丙基三甲基硅烷，醇，芳香族化合物，硫醇和酰胺）的一般有效的FeCl 3催化取代反应，导致C，C，O，C的构建已经开发了-S和C-N键。