1,3-dimethyl-2-(prop-1-yn-1-yl)benzene | 1073191-50-0

• 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: 1,3-dimethyl-2-(prop-1-yn-1-yl)benzene
• 英文别名: 1,3-dimethyl-2-(1-propynyl)benzene；1-(2,6-dimethylphenyl)-1-propyne；1,3-Dimethyl-2-prop-1-ynylbenzene；1,3-dimethyl-2-prop-1-ynylbenzene
• CAS: 1073191-50-0
• 化学式: C₁₁H₁₂
• 分子量: 144.216
• InChiKey: YYKXHHPUGFJFKF-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.4
• 重原子数：
  11
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.27
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  1,3-dimethyl-2-(prop-1-yn-1-yl)benzene 、 联硼酸频那醇酯 在 potassium tert-butylate 、 三(邻甲基苯基)磷 、 copper(l) chloride 、 甲醇 作用下， 以 四氢呋喃 为溶剂， 反应 0.17h， 以89%的产率得到(Z)-2-(1-(2,6-dimethylphenyl)prop-1-en-2-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane
  参考文献：
  名称：

  通过铜催化的硼向双取代炔烃的加成反应，高度区域选择性地合成烯基硼酸酯。

  摘要：

  在甲醇的存在下，铜催化的双（频哪醇）二硼在内部炔烃中的加成反应会生成具有高区域选择性和立体选择性的烯基硼化合物。通过使用单齿膦配体，尤其是P（对甲苯基）（3），可以提高催化效率，并以良好的产率将一系列内部炔烃进行硼化。

  DOI：

  10.1039/c0cc04496b
• 作为产物：
  描述：

  2,6-dimethylbenzaldehyde p-toluenesulfonylhydrazone 、 乙炔 在 copper(l) iodide 、 lithium tert-butoxide 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 90.0 ℃ 、101.33 kPa 条件下， 反应 4.0h， 以74%的产率得到1,3-dimethyl-2-(prop-1-yn-1-yl)benzene
  参考文献：
  名称：

  Synthesis of Terminal Allenes through Copper-Mediated Cross-Coupling of Ethyne withN-Tosylhydrazones or α-Diazoesters

  摘要：

  Ethyne is employed as coupling partner in copper-mediated cross-coupling reactions with N-tosylhydrazones and alpha-diazoacetate, leading to the development of a new synthetic method for terminal allenes. With this novel coupling method, the terminal allenes were obtained in good yields and with excellent functional group tolerance. Copper carbene migratory insertion is proposed as the key step in these transformations.

  DOI：

  10.1021/jo502316q

文献信息

• Synthesis of 7<i>H</i>-Benzo[<i>e</i>]naphtho[1,8-<i>bc</i>]silines by Rhodium-catalyzed [2 + 2 + 2] Cycloaddition
  作者：Takumi Maesato、Ryo Shintani

  DOI：10.1246/cl.200025

  日期：2020.4.5

  An efficient synthesis of 7H-benzo[e]naphtho[1,8-bc]silines has been developed by a rhodium-catalyzed [2 + 2 + 2] cycloaddition of alkynyl(8-alkynyl-1-naphthyl)silanes with internal alkynes. High c...

  7H-苯并[e]萘并[1,8-bc]硅烷的有效合成是通过炔基（8-炔基-1-萘基）硅烷与内部炔烃的铑催化[2 + 2 + 2]环加成反应开发的. 高...
• Synthesis, Structure, and Reactivity of Rare-Earth Metallocene η³-Propargyl/Allenyl Complexes
  作者：Victor F. Quiroga Norambuena、André Heeres、Hero J. Heeres、Auke Meetsma、Jan H. Teuben、Bart Hessen

  DOI：10.1021/om800547n

  日期：2008.11.10

  The reaction of the alkyl complexes Cp*2LnCH(SiMe3)2 (Ln = Y 1-Y, Ce 1-Ce, La 1-La; Cp* = η5-C5Me5) and Me2Si(η5-C5Me4)2LnCH(SiMe3)2 (Ln = Ce 5-Ce) with 1-methylalk-2-ynes CH3C≡CR (R = Me 3a, Et 3b, nPr 3c, tBu 3d, SiMe3 3e, Ph 3f, C6H4Me-2 3g, C6H3Me2-2,6 3h, C6H3iPr2-2,6 3i, C6F5 3j) affords the corresponding η3-propargyl/allenyl complexes Cp*2LnCH2CCR (4a−j-Ln) and Me2Si(η5-C5Me4)2CeCH2CCR (6a−j-Ce)

  烷基络合物Cp的反应* 2 LnCH（森达3）2（LN = Y 1-Y，Ce的1铈，拉1-拉;的Cp * =η 5 -C 5我5）和Me 2的Si（η 5 -C 5我4）2 LnCH（森达3）2（Ln为铈5铈）与1- methylalk -2-炔CH 3 C≡CR（R =我3A，等3b中，ñ镨3C，吨卜3D，SiMe3 3e，Ph 3f，C 6 H 4 Me-2 3g，C 6 H 3 Me 2 -2,6 3h，C 6 H 3 i Pr 2 -2,6 3i，C 6 F 5 3j）得到相应的η 3 -propargyl /丙二烯基配合物的Cp * 2 LnCH 2 CCR（图4a-J-LN）和Me 2的Si（η 5 -C 5我4）2切克2通过炔丙基金属化的CCR（6a-j-Ce）。氢化物配合物[Cp * 2 Ln（μ-H）] 2（Ln = Y 2-Y，Ce 2-Ce，La 2-La）与3迅速反
• Iron‐Catalyzed Allylic C(<i>sp</i>^<i>3</i>)−H Silylation: Spin‐Crossover‐Efficiency‐Determined Chemoselectivity
  作者：Peng He、Mu‐Han Guan、Meng‐Yang Hu、Yuan‐Jun Zhou、Ming‐Yao Huang、Shou‐Fei Zhu

  DOI：10.1002/anie.202402044

  日期：——

  The nuanced role of spin effects remains a critical gap in designing proficient open‐shell catalysts. This study elucidates an iron‐catalyzed allylic C(sp³)−H silylation/alkyne hydrosilylation reaction, in which the spin state of the open‐shell iron catalyst dictates the reaction kinetics and pathway. Specifically, spin crossover led to alkyne hydrosilylation, whereas spin conservation resulted in a novel allylic C(sp³)−H silylation reaction. This chemoselectivity, governed by the spin‐crossover efficiency, reveals an unexpected dimension in spin effects and a first in the realm of transition‐metal‐catalyzed in situ silylation of allylic C(sp³)−H bonds, which had been previously inhibited by the heightened reactivity of alkenes in hydrosilylation reactions. Furthermore, this spin crossover can either accelerate or hinder the reaction at different stages within a single catalytic reaction, a phenomenon scarcely documented. Moreover, we identify a substrate‐assisted C−H activation mechanism, a departure from known ligand‐assisted processes, offering a fresh perspective on C−H activation strategies.
• Synthesis of Terminal Allenes through Copper-Mediated Cross-Coupling of Ethyne with<i>N</i>-Tosylhydrazones or α-Diazoesters
  作者：Fei Ye、Chengpeng Wang、Xiaoshen Ma、Mohammad Lokman Hossain、Ying Xia、Yan Zhang、Jianbo Wang

  DOI：10.1021/jo502316q

  日期：2015.1.2

  Ethyne is employed as coupling partner in copper-mediated cross-coupling reactions with N-tosylhydrazones and alpha-diazoacetate, leading to the development of a new synthetic method for terminal allenes. With this novel coupling method, the terminal allenes were obtained in good yields and with excellent functional group tolerance. Copper carbene migratory insertion is proposed as the key step in these transformations.
• Highly regio- and stereoselective synthesis of alkenylboronic esters by copper-catalyzed boron additions to disubstituted alkynes
  作者：Hye Ryung Kim、Jaesook Yun

  DOI：10.1039/c0cc04496b

  日期：——

  The copper-catalyzed addition of bis(pinacolato)diboron to internal alkynes in the presence of methanol generates alkenylboron compounds with high levels of regio- and stereoselectivities. The catalytic efficiency is increased by using monodentate phosphine ligands, especially P(p-tolyl)(3) and a range of internal alkynes was borylated in good yields.

  在甲醇的存在下，铜催化的双（频哪醇）二硼在内部炔烃中的加成反应会生成具有高区域选择性和立体选择性的烯基硼化合物。通过使用单齿膦配体，尤其是P（对甲苯基）（3），可以提高催化效率，并以良好的产率将一系列内部炔烃进行硼化。