1-(2-(N,N-dimethylamino)ethyl)-2,3,4,5-tetramethylcyclopentadiene | 149836-50-0

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: 1-(2-(N,N-dimethylamino)ethyl)-2,3,4,5-tetramethylcyclopentadiene
• 英文别名: 1-[2-(N,N-dimethylamino)ethyl]-2,3,4,5-tetramethylcyclopentadiene；(2-(dimethylamino)ethyl)tetramethylcyclopentadiene；N,N-dimethyl-2-(2,3,4,5-tetramethylcyclopenta-1,3-dien-1-yl)ethanamine
• CAS: 149836-50-0
• 化学式: C₁₃H₂₃N
• 分子量: 193.332
• InChiKey: YROGMWMCBFOLRX-UHFFFAOYSA-N

物化性质

• 沸点：
  243.6±19.0 °C(Predicted)
• 密度：
  0.858±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.8
• 重原子数：
  14
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.69
• 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：

  十羰基二铼 、 1-(2-(N,N-dimethylamino)ethyl)-2,3,4,5-tetramethylcyclopentadiene 以 癸烷 为溶剂， 反应 4.0h， 以55%的产率得到(η5-C5Me4(CH2)2NMe2)Re(CO)3
  参考文献：
  名称：

  Synthesis, structure, and reactivity of (η5:η1-C5Me4(CH2)2NMe2)Re(CO)2. Electron transfer behavior of a nitrosyl derivative

  摘要：

  The UV irradiation of a hexane solution of the complex (eta(5)-C5Me4(CH2)(2)NMe2)Re(CO)(3) (1) afforded the chelated species (eta(5):eta(1)-C5Me4(CH2)(2)NMe2)Re(CO)(2) (2). The molecular structure of 2 has been determined by X-ray crystallography. The reaction of 2 with two-electron donor ligands yields (eta(5)-C5Me4(CH2)(2)NMe2)Re(CO)(2)(L) (1, L = CO; 3, L = PMe3). The chelated species 2 also reacts with MeOTf, HBF4, and I-2 to form the cationic compounds trans-[(eta(5)-C5Me4(CH2)(2)NMe2)Re(CO)(2)X](+) ([4](+), X = Me; [5](+), X = H; [6](+), X = 1). The trans stereochemistry of 4-6 have been assigned on the basis of nu(CO) IR intensities and C-13 NMR spectroscopy. Also, complex 2 reacts with nitrosyl tetrafluoroborate to yield [(eta(5)-C5Me4(CH2)(2)NMe2NO)Re(CO)(2)(NO)]BF4 ([7](2+)). The redox behavior of the {ReNO}(6) complex [7](2+) was studied and the products obtained after two-electron reduction were characterized by IR. DFT calculations were done to optimize the structure of [7](2+) and to study the effect of the sidearm coordination on the electronic structure of a cyclopentadienyl {ReNO}(8) complex. (C) 2014 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.jorganchem.2014.04.019
• 作为产物：
  描述：

  4-Hydroxy-4-(dimethylamino-ethyl)-3,5-dimethyl-2,5-heptadiene 在 对甲苯磺酸 作用下， 以 乙醚 为溶剂， 反应 3.0h， 生成 5-[2-(dimethylamino)ethyl]-1,2,3,4-tetramethylcyclopentadiene 、 1-(2-(N,N-dimethylamino)ethyl)-2,3,4,5-tetramethylcyclopentadiene 、 1-(dimethylaminoethyl)-2,3,4,5-tetramethylcyclopentadiene
  参考文献：
  名称：

  Dimethylaminoalkyl and Methoxyalkyl Substituted Tetramethylcyclopentadienes: Synthesis of Novel Polydentate Ligands

  摘要：

  报道了具有进一步功能化的碳侧链的新型四甲基环戊二烯的合成，X(CH2)nC5Me4H (X = Cl, NMe2, OMe; n = 1, 2)。用2-氯-1-二甲基氨基乙烷处理钾的四甲基环戊二烯化物，导致[2-(N,N-二甲基氨基)乙基]四甲基环戊二烯3的混合物形成。类似地，2-氯-1-(对甲苯磺酰)乙烷与锂的四甲基环戊二烯化物反应，产生(2-氯乙基)四甲基环戊二烯5的混合物。由于邻位双取代，不存在具有烯丙基氢原子的异构体。杂原子取代的酯，Me2N(CH2)nCO2R和MeO(CH2)nCO2R (n = 1, 2)，与2-丁烯基锂的双缩合反应产生相应二烯醇8a-d。随后的酸催化脱水和环闭合反应，在良好产率下得到各种新的功能化四甲基环戊二烯9a-d。与3和5不同，仅得到具有烯丙基氢原子的异构体。因此，这些化合物是合成具有N-或O-取代侧链的全烷基化环戊二烯基系统的合适候选物。

  DOI：

  10.1055/s-1993-25921

文献信息

• Synthesis of New Iridium N-Heterocyclic Carbene Complexes Bearing a Functionalized Cp* Ligand and Their High Catalytic Activities in the Oppenauer-Type Oxidation of Alcohol
  作者：Fumihiro Hanasaka、Ken-ichi Fujita、Ryohei Yamaguchi

  DOI：10.1021/om060475k

  日期：2006.9.1

  The new iridium N-heterocyclic carbene complexes Cp*NIr(IMeMe)Cl2 and Cp*NIr(IMe)Cl2 (Cp*N = η5-1-[2-(dimethylamino)ethyl]-2,3,4,5-tetramethylcyclopentadienyl; IMeMe = 1,3,4,5-tetramethylimidazol-2-ylidene; IMe = 1,3-dimethylimidazol-2-ylidene) have been synthesized by reaction of η5:η1-Cp*NIrCl2 with silver(I) carbene complexes or a free carbene. The catalytic systems using new iridium carbene complexes

  新的铱N-杂环卡宾络合物的Cp * Ñ的Ir（IMeMe）氯2 1和Cp * Ñ的Ir（IME）氯2（CP * Ñ =η 5 -1- [2-（二甲基氨基）乙基] -2,3,4,5- 4,5-四甲基环戊二烯; IMeMe = 1,3,4,5- tetramethylimidazol -2-亚基; IME = 1,3-二甲基咪唑烷-2-亚基）已经由η的反应合成5：η 1 -Cp * ñ的IrCl 2个与银（I）卡宾配合物或游离卡宾一起使用。使用新型铱卡宾络合物作为催化剂前体和AgOTf的催化体系在酒精的Oppenauer型氧化中显示出高催化活性，适用于通过使用[Cp * Ir（IMeMe）难以氧化的酸敏感性醇的氧化（MeCN）2 ] [OTf] 2。
• Rare-Earth-Metal Allyl Complexes Supported by the [2-(<i>N</i>,<i>N</i>-Dimethylamino)ethyl]tetramethylcyclopentadienyl Ligand: Structural Characterization, Reactivity, and Isoprene Polymerization
  作者：Lars N. Jende、Christoph O. Hollfelder、Cäcilia Maichle-Mössmer、Reiner Anwander

  DOI：10.1021/om500725g

  日期：2015.1.12

  species for isoprene polymerization but led to [allyl] → [Cl] exchange and isolation of the hexameric rare-earth-metal clusters [(CpNMe2AlEt3)2(CpNMe2)Ln3(μ2-Cl)3(μ3-Cl)2}(μ2-Cl)]2 (Ln = Y, Ho). The complexes CpNMe2Ln(η3-C3H5)2 (Ln = Y, Ho, Lu), [CpNMe2Nd(η3-C3H5)(μ-Cl)]2, and [(CpNMe2AlEt3)2(CpNMe2)Ln3(μ2-Cl)3(μ3-Cl)2}(μ2-Cl)]2 (Ln = Y, Ho) were analyzed by X-ray crystallography.

  含氨基官能化环戊二烯基配体（Cp NMe2 = 1- [2-（N，N-二甲基氨基）乙基] -2,3,4,5-四甲基环戊二烯基）的稀土金属半三明治烯丙基络合物两步盐复分解反应。LnCl的治疗3（THF）X与LICP NME2，接着是在与格氏原位反应试剂C 3 ħ 5的MgCl，生成的双（烯丙基）半夹心络合物的Cp NME2 LN（η 3 -C 3 H ^ 5）2个仅适用于较小的稀土金属（Ln = Y，Ho，Lu），且产率高（82–88％）。在较大的钕的情况下，二聚单（烯丙基）chlorido半夹心络合物的[Cp NME2钕（η 3 -C 3 H ^ 5）（μ-Cl）的] 2在68％，得到的产率。在有机硼酸酯[Ph 3 C] [B（C 6 F 5）4 ]和[PhNMe 2 H] [B（C 6 F 5）4 ]，钇，hol阳离子化后，所有络合物在异戊二烯聚合反应中均显示中等至高活性。和钕金属中心主要产生3
• (Dimethylaminoethyl)cyclopentadienyl-liganden in der chemie von gruppe-13-elementen (Al, Ga, In
  作者：Peter Jutzi、Jürgen Dahlhaus、Michael Bangel

  DOI：10.1016/0022-328x(93)83153-m

  日期：1993.11

  The synthesis of cyclopentadienyl complexes containing polydentate C5R4(CH2CH2NMe2) ligands (R  H, Me) and Group 13 elements (Al, Ga, In) is described. The compounds (C5Me4CH2CH2NMe2) AlX2 (X  Me, Cl, Br, I), (C5Me4CH2CH2NMe2)MCl 2 (M  Ga, In), (C5H4CH2CH2NMe2)AlX2 (X  H, Me, Et, Cl), (C5H4CH2- CH2NMe2)GaCl2,and (C5H4CH2CH2NMe2)InMe2 are obtained by three different procedures. All compounds that

  描述了含有多齿C 5 R 4（CH 2 CH 2 NMe 2）配体（R H，Me）和13族元素（Al，Ga，In）的环戊二烯基配合物的合成。化合物（C 5 Me 4 CH 2 CH 2 NMe 2）AlX 2（XMe，Cl，Br，I），（C 5 Me 4 CH 2 CH 2 NMe 2）MCl 2（MGa，In）， （C 5 H 4 CH 2 CH 2 NMe 2）AlX2（XH，Me，Et，Cl），（C 5 H 4 CH 2- CH 2 NMe 2）GaCl 2和（C 5 H 4 CH 2 CH 2 NMe 2）InMe 2是通过三种不同的方法获得的。到目前为止，所有已通过X射线衍射研究表征的化合物均显示了侧链中氮原子的额外分子内配位作用。单体结构和足够的挥发性使其成为MOCVD工艺的潜在候选者。
• Rare-Earth-Metal Alkylaluminates Supported by N-Donor-Functionalized Cyclopentadienyl Ligands: CH Bond Activation and Performance in Isoprene Polymerization
  作者：Lars N. Jende、Cäcilia Maichle-Mössmer、Reiner Anwander

  DOI：10.1002/chem.201302388

  日期：2013.11.25

  with the larger rare‐earth‐metal ions lanthanum and neodymium. X‐ray diffraction analysis revealed the formation of isostructural complexes and the CH bond activation of one aminomethyl group. The formation of Ln(μ‐CH2)Al moieties was further corroborated by 13C and 1H‐13C HSQC NMR spectroscopy. In the case of the largest metal center, lanthanum, this CH bond activation could be suppressed at −35 °C

  同质四甲基铝酸盐配合物[Ln（AlMe 4）3 ]（Ln = La，Nd，Y）与HCp NMe2（Cp NMe2 = 1- [2-（N，N-二甲基氨基）-乙基] -2,3,4， 5-戊基环戊二烯基）在-35°C的戊烷中生成半三明治稀土金属配合物[C 5 Me 4 CH 2 CH 2 NMe 2（AlMe 3）} Ln（AlMe 4）2 ]。通过使用等摩尔量的Et 2通过取代供体来去除N-供体配位的三甲基铝基团Ø在环境温度下仅产生的亚甲基桥接的配合物[C 5我4 CH 2 CH 2 NME（μ-CH 2）阿尔梅3 } LN（阿尔梅4）]有较大的稀土类金属离子的镧和钕。X射线衍射分析显示同构结构的形成和一个氨基甲基的CH键活化。Ln的形成（μ-CH 2）的A1基团通过进一步证明13 C和1个H- 13 C ^ HSQC NMR谱。在最大的金属中心，镧，本C的情况下H键激活可以在-35°C抑制，从而导致[[Cp
• Synthesis, structure, and reactivity of (η5:η1-C5Me4(CH2)2NMe2)Re(CO)2. Electron transfer behavior of a nitrosyl derivative
  作者：Fernando Godoy、Alejandra Gómez、Rodrigo Segura、Fabio Doctorovich、Juan Pellegrino、Carina Gaviglio、Paulina Guerrero、A. Hugo Klahn、Mauricio Fuentealba、María Teresa Garland

  DOI：10.1016/j.jorganchem.2014.04.019

  日期：2014.8

  The UV irradiation of a hexane solution of the complex (eta(5)-C5Me4(CH2)(2)NMe2)Re(CO)(3) (1) afforded the chelated species (eta(5):eta(1)-C5Me4(CH2)(2)NMe2)Re(CO)(2) (2). The molecular structure of 2 has been determined by X-ray crystallography. The reaction of 2 with two-electron donor ligands yields (eta(5)-C5Me4(CH2)(2)NMe2)Re(CO)(2)(L) (1, L = CO; 3, L = PMe3). The chelated species 2 also reacts with MeOTf, HBF4, and I-2 to form the cationic compounds trans-[(eta(5)-C5Me4(CH2)(2)NMe2)Re(CO)(2)X](+) ([4](+), X = Me; [5](+), X = H; [6](+), X = 1). The trans stereochemistry of 4-6 have been assigned on the basis of nu(CO) IR intensities and C-13 NMR spectroscopy. Also, complex 2 reacts with nitrosyl tetrafluoroborate to yield [(eta(5)-C5Me4(CH2)(2)NMe2NO)Re(CO)(2)(NO)]BF4 ([7](2+)). The redox behavior of the ReNO}(6) complex [7](2+) was studied and the products obtained after two-electron reduction were characterized by IR. DFT calculations were done to optimize the structure of [7](2+) and to study the effect of the sidearm coordination on the electronic structure of a cyclopentadienyl ReNO}(8) complex. (C) 2014 Elsevier B.V. All rights reserved.