13-methylene-11-tricosyne | 88472-55-3

• 分子结构分类: 有机化合物 - 碳氢化合物 - 不饱和烃
• 英文名称: 13-methylene-11-tricosyne
• 英文别名: 13-methylenetricos-11-yne；13-Methylidenetricos-11-yne
• CAS: 88472-55-3
• 化学式: C₂₄H₄₄
• 分子量: 332.613
• InChiKey: PQOZNDDJVKZOLU-UHFFFAOYSA-N

物化性质

• 沸点：
  180 °C(Press: 3 Torr)
• 密度：
  0.825±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  12
• 重原子数：
  24
• 可旋转键数：
  18
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.83
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为产物：
  描述：

  1-十二炔 在 C₃₃H₄₇ClN₂Pd 、 三(2,6-二甲氧基苯基)磷 、 cesium pivalate 作用下， 以 甲苯 为溶剂， 反应 7.0h， 以93%的产率得到13-methylene-11-tricosyne
  参考文献：
  名称：

  炔烃区域发散二聚反应中水合和碳合途径之间的羧酸盐转换

  摘要：

  提出了末端炔烃的区域发散性钯催化的二聚化的实验和理论研究。在膦配体存在的情况下使用N杂环卡宾基钯催化剂可实现高度区域和立体选择性的头对头二聚反应。或者，将羧酸根阴离子添加到反应混合物中会触发选择性的头对尾偶联。计算研究表明，在中性反应条件下，反应通过氢化钯途径进行，有利于头对头二聚。区域选择性开关的起源可以由羧酸根阴离子的双重作用来解释。因此，通过羧酸盐去除氢原子将反应从水滑石转化为碳链石途径。此外，

  DOI：

  10.1002/chem.201402809

文献信息

• Gold-Catalyzed Regioselective Dimerization of Aliphatic Terminal Alkynes
  作者：Liming Zhang、Sheng Sun、Julien Kroll、Yingdong Luo

  DOI：10.1055/s-0031-1289567

  日期：2012.1

  A gold-catalyzed regioselective homodimerization of ­aliphatic terminal alkynes is described. Bulky and less Lewis acidic t-BuXPhosAuNTf2 is the preferred catalyst, and the additive, anhydrous NaOAc, substantially facilitates the reaction.

  描述了一种金催化的区域选择性脂肪族末端炔烃的同二聚化反应。体积较大且较少路易斯酸性的 t-BuXPhosAuNTf2 是首选催化剂，助剂无水醋酸钠显著促进了反应。
• 10.1021/acs.orglett.4c01872
  作者：Wu, Xuan、Zhang, Liming

  DOI：10.1021/acs.orglett.4c01872

  日期：——

  dimerization of terminal alkynes is achieved under mild reaction conditions and in excellent yields. In addition to homodimerizations, heterodimerizations between TBS acetylene and a range of terminal alkynes were realized using the syringe pump technique. The reaction tolerates various functional groups. The rate acceleration experienced in the reactions is enabled by metal–ligand cooperation. A binaphthyl-2-ylphosphine

  金催化的末端炔烃二聚化是在温和的反应条件下实现的，并且产率极高。除了同源二聚化外，TBS 乙炔和一系列末端炔烃之间的异二聚化是使用注射泵技术实现的。该反应耐受各种官能团。反应中经历的速率加速是通过金属-配体合作实现的。具有 3'-二异丙基磷基的二萘基-2-基膦配体通过容纳和/或去质子化其末端质子，在促进炔烃攻击中起关键作用。
• Selimov, F. A.; Rutman, O. G.; Dzhemilev, U. M., Journal of Organic Chemistry USSR (English Translation), 1983, vol. 19, p. 1621 - 1624
  作者：Selimov, F. A.、Rutman, O. G.、Dzhemilev, U. M.

  DOI：——

  日期：——
• Regio- and Stereoselective Dimerization of Terminal Alkynes to Enynes Catalyzed by a Palladium/Imidazolium System
  作者：Chuluo Yang、Steven P. Nolan

  DOI：10.1021/jo010837s

  日期：2002.1.1

  A Palladium/imidazolium chloride system has been used to mediate the dimerization of terminal alkynes to enynes. The combination of 1 mol % Pd(OAc)(2) and 2 mol % IMes.HCl in the presence Of CS2CO3 as base shows high activity and high regio- and steroselectivity for the dimerization of aryl and aliphatic terminal alkynes to enynes.
• Activity of homobimetallic ruthenium alkylidene complexes on intermolecular [2+2+2] cyclotrimerisation reactions of terminal alkynes
  作者：Bengi Özgün Öztürk、Solmaz Karabulut、Yavuz İmamoğlu

  DOI：10.1016/j.ica.2011.09.023

  日期：2011.11

  The activity of homobimetallic ruthenium alkylidene complexes, [(p-cymene)Ru(Cl)(mu-Cl)(2)Ru(Cl) (=CHPh)(PCy(3))] [Ru-I] and [(p-cymene)Ru(Cl)(mu-Cl)(2)Ru(Cl)(=CHPh)(IPr)] [Ru-II], on intermolecular [2+2+2] cyclotrimerisation reactions of monoynes has been investigated for the first time. It was found that these complexes can catalyse the chemo and regioselective cyclotrimerisation reactions of alkynes at both 25 and 50 degrees C in polar, aprotic solvents. The catalytic activity of [Ru-I] and [Ru-II] was compared to other well-known ruthenium catalysts such as Grubbs first generation catalyst [RuCl(2)(=CHPh)(PCy(3))(2)] [Ru-III], [RuCl(mu-Cl)(p-cymene)](2) [Ru-IV] and [RuCl(2)(p-cymene)PCy(3)] [Ru-V] complexes. To examine the effect of the steric hinderance of substrates on the regioselectivity of the reaction, a series of sterically hindered silicon containing alkynes (1a, 1b, 1c) were used. It was shown that the isomeric product distribution of the reaction shifts from 1,2,4-trisubstituted arenes to 1,3,5-trisubstituted arenes as the steric hinderance on the substrates increases. These homobimetallic ruthenium alkylidene complexes also catalysed regio- and chemo-selective cross-cyclotrimerisation reactions between silicon-containing alkynes (1a, 1b, 1c) and aliphatic alkynes (1d-g). (C) 2011 Elsevier B.V. All rights reserved.