N,N-二甲基-3-苯基-2-丙炔-1-胺 | 2568-65-2

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 中文名称: N,N-二甲基-3-苯基-2-丙炔-1-胺
• 英文名称: N,N-Dimethyl-3-phenyl-2-propyn-1-amine
• 英文别名: N,N-dimethyl-3-phenylprop-2-yn-1-amine
• CAS: 2568-65-2
• 化学式: C₁₁H₁₃N
• 分子量: 159.231
• InChiKey: ARDFJWBFPXYFMH-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.2
• 重原子数：
  12
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.27
• 拓扑面积：
  3.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  N,N-二甲基-3-苯基-2-丙炔-1-胺 以 甲醇 、 二氯甲烷 为溶剂， 生成 Pd[κ1-C,κ1-N-C=(C6H5)C(Cl)CH2N(CH3)2](Cl)(pyridine)
  参考文献：
  名称：

  Atropisomerism in palladacycles derived from the chloropalladation of heterosubstituted alkynes

  摘要：

  The chloropalladation of 2-substituted phenyl N,N-propargylamines, Y-2-C6H4C=CCH2NMe2 (1a, Y = H; 2a, Y = CF3; 3a, Y = OMe: 4a. Y = SMe and 5a, Y = NH2) affords palladacycles in different ratios of isomers (geometric and atropisomers). In solution, the parent alkyne (Y = H) and the CF3 substituted derivative generate a mixture of cisoid and transoid chloro-bridged dimer palladacycles of the type {Pd[kappa(1)-C, kappa(1)-N-C=(Y-2-C6H4)C(cl)CH2NMe2](mu-Cl)}(2). Moreover, in the case in the case of Y = CF3 palladacyclic derivative each of the geometric isomers comprises a mixture of two diastereoisomers due to the restricted rotation of the C(vinyl)-C(aryl) sigma bond (atropisomers). Palladacycles 1a (Y = H) and 2a (Y = CF3) crystallize as the single transoid and cisoid-anti isomer. respectively. The OMe substituted alkyne yields a similar dimeric compound that crystallizes as a single cisoid-anti isomer. In solution this dimeric compound is in fast equilibrium with a monomeric pincer compound of the type Pd[kappa(1)-C, kappa(1)-N, kappa(1)-O-C=(MeO-2-C6H4)C(Cl)CH2NMe2](Cl) assisted through the weak coordination of the OMe group. Pincer palladacycles Pd[kappa(1)-C, kappa(1)-N, kappa(1)-Y-C=(Y-2-C6H4)C(Cl)CH2NMe2](Cl) (Y = SMe and NH2) were the sole products obtained in the chloropalladation of alkynes 4a and 5a. The bridge splitting reaction of the dimeric palladacycles 1b-3b with pyridine is highly selective, affording exclusively the corresponding monomeric compounds 1c-3c. The monomeric palladacycle 2d, which comprises a mixture of two atropisomers (2:1 ratio of antilsyn) was obtained from the reaction of 2b with 2-methylpyridine. Theoretical calculations indicated that the anti isomer of 2d is 5.42 kJ mol(-1) more stable than its syn isomer. (C) 2003 Elsevier Science B.V. All rights reserved.

  DOI：

  10.1016/s0020-1693(03)00011-2
• 作为产物：
  描述：

  N,N-dimethyl-3-oxo-N-(3-phenylprop-2-yn-1-yl)but-1-en-1-aminium chloride 在 氢氧化钾 作用下， 以 水 为溶剂， 反应 4.0h， 以91.2%的产率得到N,N-二甲基-3-苯基-2-丙炔-1-胺
  参考文献：
  名称：

  Behavior of ammonium salts containing propargyl-type groups in rearrangement-cleavage reactions

  摘要：

  DOI：

  10.1134/s1070363208020291

文献信息

• Tandem Palladium and Isothiourea Relay Catalysis: Enantioselective Synthesis of α-Amino Acid Derivatives via Allylic Amination and [2,3]-Sigmatropic Rearrangement
  作者：Stéphanie S. M. Spoehrle、Thomas H. West、James E. Taylor、Alexandra M. Z. Slawin、Andrew D. Smith

  DOI：10.1021/jacs.7b05619

  日期：2017.8.30

  has been developed for the enantioselective synthesis of α-amino acid derivatives containing two stereogenic centers from readily accessible N,N-disubstituted glycine aryl esters and allylic phosphates. The optimized process uses a bench-stable succinimide-based Pd precatalyst (FurCat) to promote Pd-catalyzed allylic ammonium salt generation from the allylic phosphate and the glycine aryl ester. Subsequent

  已经开发了使用Pd和异硫脲催化的串联中继催化方案，用于从容易获得的N，N-二取代的甘氨酸芳基酯和烯丙基磷酸酯对映体选择性地合成包含两个立构中心的α-氨基酸衍生物。优化的过程使用了稳定的基于琥珀酰亚胺的Pd预催化剂（FurCat）来促进Pd催化的烯丙基磷酸酯和甘氨酸芳基酯生成的烯丙基铵盐。异硫脲苯并四咪唑催化的随后原位对映选择性[2,3]-σ重排形成syn具有高非对映选择性和对映选择性的-α-氨基酸衍生物。使用4-硝基苯基甘氨酸酯时，该方法最有效，并且可以耐受各种取代的肉桂酸和苯乙烯基烯丙基烯丙基乙基磷酸酯。在不影响立体选择性的情况下，在催化中继条件下也可以耐受使用具有挑战性的不对称N-烯丙基-N-甲基甘氨酸酯。
• Catalyst-free activation of methylene chloride and alkynes by amines in a three-component coupling reaction to synthesize propargylamines
  作者：Vikas S. Rawat、Thulasiram Bathini、S. Govardan、Bojja Sreedhar

  DOI：10.1039/c4ob00986j

  日期：——

  Propargylamines are synthesized via metal-free activation of the C–halogen bond of dihalomethanes and the C–H bond of terminal alkynes in a three-component coupling without catalyst or additional base and under mild reaction conditions. The dihalomethanes are used both as solvents as well as precursors for the methylene fragment (C1) in the final product. The scope of the reaction and the influence

  炔丙基胺是通过无卤活化二卤甲烷的C-卤键和末端炔烃的C-H键以三组分偶联的方式合成的，无需催化剂或额外的碱，并且在温和的反应条件下进行。二卤甲烷既用作溶剂，也用作最终产品中亚甲基片段（C 1）的前体。已经研究了反应范围和各种反应变量的影响。提出了一个合理的反应机理，并讨论了可能在该过程中原位产生的各种中间体的参与。不含金属的条件也使该协议在环境上无害，并且原子经济。
• Mechanistic Insights into the One-Pot Synthesis of Propargylamines from Terminal Alkynes and Amines in Chlorinated Solvents Catalyzed by Gold Compounds and Nanoparticles
  作者：David Aguilar、Maria Contel、Esteban P. Urriolabeitia

  DOI：10.1002/chem.201000587

  日期：——

  Propargylamines can be obtained from secondary amines and terminal alkynes in chlorinated solvents by a three‐ and two‐component synthesis catalyzed by gold compounds and nanoparticles (Au‐NP) under mild conditions. The use of dichloromethane allows for the activation of two CCl bonds and a clean transfer of the methylene fragment to the final product. The scope of the reaction as well as the influence

  炔丙基胺可以在温和的条件下，由金化合物和纳米颗粒（Au-NP）催化的三组分和二组分合成，从氯化胺中的仲胺和末端炔烃获得。使用二氯甲烷可激活两个CCl键，并将亚甲基片段完全转移至最终产物。已经研究了反应的范围以及不同的金（III）环金络合物和盐的影响。讨论了原位生成的金纳米粒子的参与过程，并根据获得的数据提出了合理的反应机理。
• Copper-Catalyzed Tandem Sulfuration/Annulation of Propargylamines with Sulfur via C–N Bond Cleavage
  作者：Hong-Hui Xu、Xiao-Hong Zhang、Xing-Guo Zhang

  DOI：10.1021/acs.joc.9b00685

  日期：2019.6.21

  oxidative sulfuration and annulation of propargylamines with elemental sulfur is described. The tandem reaction involves C–N bond cleavage and the formation of multiple C–S bonds, affording 1,2-dithiole-3-thiones in good to excellent yields with good functional group tolerance.

  描述了铜催化的好氧氧化硫化和炔丙胺与元素硫的环化。串联反应涉及C–N键断裂和多个C–S键的形成，从而以良好的收率和优异的收率提供了1,2-二硫代3-硫酮，并且具有良好的官能团耐受性。
• Base catalysed rearrangements involving ylide intermediates. Part 7. The rearrangements of allyl(pentadienyl)- and propynyl(pentadienyl)ammonium cations. The [5,4] sigmatropic rearrangement
  作者：Trevor Laird、W. David Ollis、Ian O. Sutherland

  DOI：10.1039/p19800002033

  日期：——

  The base catalysed rearrangements of the cations (7), (17), (22), and (27) gave the enamines (9), (18), (23), and (28), which on hydrolysis yielded the aldehydes (10), (19), (24), and (29) respectively. The reactions are shown to be concerted [5,4] sigmatropic rearrangements proceeding via a nine-membered transition state involving 10π electrons. The base catalysed rearrangements of the 3-phenylprop-2-ynyl

  阳离子（7），（17），（22）和（27）的碱催化重排产生烯胺（9），（18），（23）和（28），水解后产生醛（ 10），（19），（24）和（29）。该反应显示为通过包含10π电子的九元过渡态进行的[5,4]σ重排。3-苯基丙-2-炔基（戊二烯基）铵阳离子的碱催化重排（51），（52），（60）和（61），但仅产生[1,2]，[3， 2]和[5,2]σ重排。