2,6-diethynyl-4-N,N-dimethylaminopyridine | 672936-36-6

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: 2,6-diethynyl-4-N,N-dimethylaminopyridine
• 英文别名: 2,6-diethynyl-4-dimethylaminopyridine；2,6-Diethynyl-N,N-dimethylpyridin-4-amine；2,6-diethynyl-N,N-dimethylpyridin-4-amine
• CAS: 672936-36-6
• 化学式: C₁₁H₁₀N₂
• 分子量: 170.214
• InChiKey: JXTJSMAFIRNHPU-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.5
• 重原子数：
  13
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.18
• 拓扑面积：
  16.1
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  2,6-diethynyl-4-N,N-dimethylaminopyridine 、 2-[2-(2-methoxyethoxy)ethoxy]ethyl 3-iodobenzoate 在 copper(l) iodide tris(dibenzylideneacetone)dipalladium (0) 、 三乙胺 、 三苯基膦 作用下， 以 乙腈 为溶剂， 反应 20.0h， 以0.0886 g的产率得到2-[2-(2-Methoxyethoxy)ethoxy]ethyl 3-[2-[4-(dimethylamino)-6-[2-[3-[2-[2-(2-methoxyethoxy)ethoxy]ethoxycarbonyl]phenyl]ethynyl]pyridin-2-yl]ethynyl]benzoate
  参考文献：
  名称：

  Pyridine-Containing m-Phenylene Ethynylene Oligomers Having Tunable Basicities

  摘要：

  Incorporation of a pyridine monomer into the backbone of a m-phenylene ethynylene oligomer allows functionalization of the interior binding cavity of the folded oligomer. The basicity of the inwardly directed pyridine moiety was modulated by changing the substituents on the pyridine ring and through oligomer folding, granting access to a pK(a) range of 5-14 in acetonitrile.

  DOI：

  10.1021/ol0363016
• 作为产物：
  描述：

  N,N-dimethyl-2,6-bis[2-tri(propan-2-yl)silylethynyl]pyridin-4-amine 在 四丁基氟化铵 、 溶剂黄146 作用下， 以 四氢呋喃 为溶剂， 反应 0.03h， 以94%的产率得到2,6-diethynyl-4-N,N-dimethylaminopyridine
  参考文献：
  名称：

  螺旋 DMAP 类似物的折叠促进甲基化

  摘要：

  一系列含吡啶的亚苯基亚乙炔低聚物的甲基化速率表现出对链长的非线性依赖性，对于采用折叠螺旋构象的低聚物观察到显着的速率增强。折叠结构提供了一个微环境，降低了甲基化反应的能量障碍。在这些非共价相互作用中，最大的稳定性可能是由于甲基碘在折叠寡聚体的疏水腔中的结合，靠近吡啶亲核试剂。

  DOI：

  10.1021/ja031842b

文献信息

• Preparation of Shape-Persistent Macrocycles with a Single Pyridine Unit by Double Cross-Coupling Reactions of Aryl Bromides and Alkynes
  作者：Ryu Yamasaki、Atsushi Shigeto、Shinichi Saito

  DOI：10.1021/jo2018944

  日期：2011.12.16

  A double Sonogashira-type coupling reaction between aryl bromides and alkynes using a catalytic Pd/XPhos (2-dicyclohexylphosphino-2′,4′,6′-triisopropylbiphenyl) system was introduced as an efficient method for the synthesis of shape-persistent macrocycles (SPMs). This approach is advantageous in the synthesis of SPMs with a single pyridine unit.

  介绍了使用催化Pd / XPhos（2-dicyclohexylphosphino-2'，4'，6'-triisopropylbiphenyl）系统在芳基溴化物和炔烃之间进行的双重Sonogashira型偶联反应，作为合成形状持久大环化合物的有效方法（ SPM）。该方法在具有单个吡啶单元的SPM的合成中是有利的。
• Pyridine-Containing <i>m</i>-Phenylene Ethynylene Oligomers Having Tunable Basicities
  作者：Jennifer M. Heemstra、Jeffrey S. Moore

  DOI：10.1021/ol0363016

  日期：2004.3.1

  Incorporation of a pyridine monomer into the backbone of a m-phenylene ethynylene oligomer allows functionalization of the interior binding cavity of the folded oligomer. The basicity of the inwardly directed pyridine moiety was modulated by changing the substituents on the pyridine ring and through oligomer folding, granting access to a pK(a) range of 5-14 in acetonitrile.
• Single-Site Modifications and Their Effect on the Folding Stability of <i>m</i>-Phenylene Ethynylene Oligomers
  作者：Hirofumi Goto、Jennifer M. Heemstra、David J. Hill、Jeffrey S. Moore

  DOI：10.1021/ol036376+

  日期：2004.3.1

  The folded structure of a m-phenylene ethynylene oligomer is tolerant to single-site modifications to both the backbone sequence and end groups. The helical structure is reinforced by multiple noncovalent interactions, allowing the oligomer sequence to be customized without a significant change in stability in most cases. The small changes that are observed are consistent with the expected behavior of pi-stacked systems and demonstrate subtle control over folding through single-site modifications.
• Foldamers as Reactive Sieves:  Reactivity as a Probe of Conformational Flexibility
  作者：Ronald A. Smaldone、Jeffrey S. Moore

  DOI：10.1021/ja067670a

  日期：2007.5.1

  A series of m-phenyleneethynylene (mPE) oligomers modified with a dimethylaminopyridine (DMAP) unit were treated with methyl sulfonates of varying sizes and shapes, and the relative reactivities were measured by UV spectrophotometry. Using a small-molecule DMAP analogue as a reference, each of the methyl sulfonates was shown to react at nearly identical rate. In great contrast, oligomers that are long enough to fold, and hence capable of binding the methyl sulfonate, experience rate enhancements of 18-1600-fold relative to that of the small-molecule analogue, depending on the type of alkyl chain attached to the guest. Three different oligomer lengths were studied, with the longest oligomers exhibiting the fastest rate and greatest substrate specificity. Even large, bulky guests show slightly enhanced methylation rates compared to that with the reference DMAP, which suggests a dynamic nature to the oligomer's binding cavity. Several mechanistic models to describe this behavior are discussed.
• Folding-Promoted Methylation of a Helical DMAP Analogue
  作者：Jennifer M. Heemstra、Jeffrey S. Moore

  DOI：10.1021/ja031842b

  日期：2004.2.1

  The methylation rate for a series of pyridine-containing phenylene ethynylene oligomers shows a nonlinear dependence on chain length, with a significant rate enhancement observed for oligomers that adopt a folded, helical conformation. The folded structure provides a microenvironment that lowers the energy barrier for the methylation reaction. Of these noncovalent interactions, the largest stabilization

  一系列含吡啶的亚苯基亚乙炔低聚物的甲基化速率表现出对链长的非线性依赖性，对于采用折叠螺旋构象的低聚物观察到显着的速率增强。折叠结构提供了一个微环境，降低了甲基化反应的能量障碍。在这些非共价相互作用中，最大的稳定性可能是由于甲基碘在折叠寡聚体的疏水腔中的结合，靠近吡啶亲核试剂。