2-methylene-7-octynoic acid methyl ester | 136823-40-0

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: 2-methylene-7-octynoic acid methyl ester
• 英文别名: methyl 2-methylideneoct-7-ynoate
• CAS: 136823-40-0
• 化学式: C₁₀H₁₄O₂
• 分子量: 166.22
• InChiKey: SPLSPCBUTUCDAS-UHFFFAOYSA-N

物化性质

• 沸点：
  234.1±33.0 °C(Predicted)
• 密度：
  0.945±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.91
• 重原子数：
  12.0
• 可旋转键数：
  5.0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  26.3
• 氢给体数：
  0.0
• 氢受体数：
  2.0

反应信息

• 作为产物：
  描述：

  2-methylene-7-octynoic acid 、 碘甲烷 在 potassium carbonate 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 5.0h， 生成 2-methylene-7-octynoic acid methyl ester
  参考文献：
  名称：

  Activation of carbon dioxide: nickel-catalyzed electrochemical carboxylation of diynes

  摘要：

  The simultaneous activation of carbon dioxide and diynes by electrogenerated LNi(0) complexes (L = bpy, pentamethyldiethylenetriamine: PMDTA) enables the selective incorporation of one molecule of CO2 into the unsaturated systems and the preparative-scale electrosyntheses of carboxylic acids. A series of nonconjugated diynes afforded selectively linear or cyclic adducts depending on the ligand. Diynes bearing both a terminal and an internal triple bond gave exclusive CO2 incorporation into the terminal alkynyl group, regioselectively at the 2-position. The electrocarboxylation of 1,3-diynes with the Ni-PMDTA catalytic system yielded, regio- and stereoselectively, (E)-2-vinylidene-3-yne carboxylic acids in one step. The electrosyntheses were carried out in single-compartment cells fitted with a consumable magnesium anode, and utilized a catalytic amount of an air-stable Ni(II) complex as the catalyst precursor. Cyclic voltammetry studies revealed that both carbon dioxide and the diynes are able to coordinate to LNi(0)-generated species in DMF.

  DOI：

  10.1021/jo00061a038

文献信息

• Bifunctional ligands for Pd-catalyzed selective alkoxycarbonylation of alkynes
  作者：Huimin Qi、Zijun Huang、Menglan Wang、Peiju Yang、Chen-Xia Du、Shu-Wei Chen、Yuehui Li

  DOI：10.1016/j.jcat.2018.04.007

  日期：2018.7

  represent straightforward and atom-economic synthesis of α,β-unsaturated carbonyl compounds. One of the issues associated with the currently known catalytic systems is insufficient efficiency. In this context, Pd/ligand-catalyzed regioselective and efficient alkoxycarbonylation of terminal alkynes is desirable for the synthesis of α,β-unsaturated esters. Herein, we present the use of a newly designed

  炔烃的催化羰基化代表了α，β-不饱和羰基化合物的直接且原子经济的合成。与当前已知的催化系统相关的问题之一是效率不足。在这种情况下，末端α炔的Pd /配体催化的区域选择性和有效的烷氧羰基化对于合成α，β-不饱和酯是合乎需要的。在本文中，我们介绍了新设计的双功能配体在炔烃有效Pd催化烷氧基羰基化反应中的应用。脂族和芳族炔烃均能以高选择性顺利转化为支链所需产物（28个实例，产率为45-96％，选择性为95.0-99.9％）。
• From stoichiometry to catalysis: electroreductive coupling of alkynes and carbon dioxide with nickel-bipyridine complexes. Magnesium ions as the key for catalysis
  作者：Sylvie Derien、Elisabet Dunach、Jacques Perichon

  DOI：10.1021/ja00022a037

  日期：1991.10

  The incorporation of carbon dioxide into nonactivated alkynes catalyzed by electrogenerated nickel-bipyridine complexes affords alpha,beta-unsaturated acids in moderate to good yields. The electrocarboxylation reaction was undertaken on a preparative scale in the presence of a sacrificial magnesium anode: the formation of acids from alkynes is stoichiometric with respect to the nickel complex if performed in a two-compartment cell but can be made catalytic in a single-compartment cell. An intermediate nickelacycle was isolated from the reaction with 4-octyne. The cleavage of this metallacycle by magnesium ions is the key step to explain catalysis.