2,5,5-trimethylpiperidine | 73604-53-2

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 哌啶类
• 英文名称: 2,5,5-trimethylpiperidine
• 英文别名: 2,5,5-trmethylpiperidine
• CAS: 73604-53-2
• 化学式: C₈H₁₇N
• mdl: MFCD19216907
• 分子量: 127.23
• InChiKey: KYWACIHIISYYSC-UHFFFAOYSA-N

物化性质

• 沸点：
  151.0±8.0 °C(Predicted)
• 密度：
  0.790±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.9
• 重原子数：
  9
• 可旋转键数：
  0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  12
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  甲氧基-三氟甲基苯 、 2,5,5-trimethylpiperidine 在 三乙胺 作用下， 以 氘代氯仿 为溶剂， 生成
  参考文献：
  名称：

  稀土元素对映体纯的氨基idi酸酯配合物

  摘要：

  The synthesis of the new chiral amidine (S,S)-N,N'-bis(1-phenylethyl)pivalamidine ((S)-HPETA) and its corresponding lithium salt (S)-LiPETA are reported, and their solid-state structures were investigated by single-crystal X-ray diffraction. Depending on the stoichiometric ratio and the ion radius of the rare-earth metal, the reaction of (S)-LiPETA with anhydrous lanthanide trihalides (Ln = Sc, Y, La, Nd, Sm, Lu) afforded mono-, bis-, and tris(amidinate) complexes. The mono(amidinate) compound [{(S)-PETA}LaI4Li2(thf)(4)], the bis(amidinate) complexes [({(S)-PETA}(2)Ln-mu-Cl)(n)] (Ln = Sc, Y, Nd, Sm, Lu), and the tris(amidinate) compound [{(S)-PETA}(3)Y] were isolated and structurally characterized by single-crystal X-ray diffraction. For the bis(amidinate) compounds, either monomeric or chloro-bridged dimeric structures were observed in the solid state. Furthermore, chiral bis(amidinate)-amido and-alkyl complexes [{(S)-PETA}(2)Ln{E(SiMe3)(2)}] (E = N, Ln = Y; E = CH, Ln = Sc, Y, Lu) were synthesized by salt metathesis and their catalytic activity and enantioselectivities were investigated in hydroamination/cyclization reactions. All of these compounds showed very good catalytic activity, and all of the investigated substrates were converted regiospecifically into their corresponding cyclic products under mild reaction conditions within good reaction times. The lutetium alkyl compound combined a high activity with good enantioselectivity.

  DOI：

  10.1021/acs.organomet.6b00523
• 作为产物：
  描述：

  2,2-二甲基己-5-烯-1-胺 在 [9-(N-methylamino)-1-(N-methylimino)-1H-phenalene]ZnMe 、 N,N-二甲基苯铵四(五氟苯基)硼酸盐 作用下， 以 氘代苯 为溶剂， 反应 24.0h， 生成 2,5,5-trimethylpiperidine
  参考文献：
  名称：

  用于分子内加氢反应的基于酚基的有机锌催化剂：催化循环的综合催化，动力学和机理研究

  摘要：

  在本文中，我们报告了两种有机锌配合物的合成和表征，其中两种有机锌配合物均包含对称的基于菲基（PLY）的N，N-配体。苯甲烯基配体与ZnMe 2的反应导致形成有机锌络合物[ N（Me），N（Me）-PLY] ZnMe（1）和[ N（i Pr），N（i Pr）-PLY]甲烷分解下的ZnMe（2）。两种配合物（1和2）都通过NMR光谱和元素分析进行​​了表征。配合物1和2的固态结构由单晶X射线晶体学确定。配合物1和2用作未活化的伯和仲氨基烯烃的分子内加氢胺化的催化剂。结合使用NMR光谱和DFT计算的方法，可以更好地了解锌催化加氢胺化反应的机理。催化剂2催化一级和二级氨基烯烃底物的研究进展。通过详细的动力学研究（包括动力学同位素效应测量）对碳纳米管进行了研究。这些结果表明伯氨基和烯烃活化过程的拟一级动力学。对模型仲氨基烯烃底物的环化进行Eyring和Arrhenius分析，得到ΔH ≠ = 11.3

  DOI：

  10.1002/chem.201200868

文献信息

• Bis(imidazolin-2-iminato) Rare Earth Metal Complexes: Synthesis, Structural Characterization, and Catalytic Application
  作者：Alexandra G. Trambitas、Daniel Melcher、Larissa Hartenstein、Peter W. Roesky、Constantin Daniliuc、Peter G. Jones、Matthias Tamm

  DOI：10.1021/ic300407u

  日期：2012.6.18

  Sc, Y, Lu). The molecular structures of all three compounds were established by single-crystal X-ray diffraction analyses. The coordination spheres around the pentacoordinate metal atoms are best described as trigonal bipyramids. Reaction of YbI2 with 2 equiv of LiCH2SiMe3 and 2 equiv of the imino ligand ImDippNH in tetrahydrofuran did not result in a divalent complex, but instead the Yb(III) complex

  无水稀土金属卤化物MCl 3与2当量的1,3-双（2,6-二异丙基苯基）咪唑啉-2-亚胺（Im Dipp NH）和2当量的三甲基甲硅烷基甲基锂（Me 3 SiCH 2 Li）在THF中的反应提供了配合物[（Im Dipp N）2 MCl（THF）n ]（M = Sc，Y，Lu）。通过单晶X射线衍射分析确定了所有三种化合物的分子结构。最好将五配位金属原子周围的配位球描述为三角双锥。YbI 2与2当量的LiCH 2 SiMe 3和2当量的亚氨基配体Im Dipp反应四氢呋喃中的NH不会生成二价络合物，而是获得了Yb（III）络合物[（Im Dipp N）2 YbI（THF）2 ]并进行了结构表征。用1当量的LiCH 2 SiMe 3处理[（Im Dipp N）2 MCl（THF）n ]导致形成[[Im Dipp N）2 M（CH 2 SiMe 3）（THF）n]。这些化合物在固态金属原子上的配
• Chiral lutetium benzamidinate complexes
  作者：Paul Benndorf、Jelena Jenter、Larissa Zielke、Peter W. Roesky

  DOI：10.1039/c0cc04962j

  日期：——

  Enantiomerically pure lutetium complexes were synthesized as the first rare earth metal complexes containing a chiral amidinate ligand. The catalytic activity and the enantioselectivity in hydroamination reactions were studied.

  手性酰胺配体的单一异构体镥络合物被合成出来，这是首例含有手性酰胺配体的稀土金属络合物。研究了其氢氨化反应的催化活性和对映选择性。
• Intramolecular Hydroamination of Aminoalkenes by Calcium and Magnesium Complexes: A Synthetic and Mechanistic Study
  作者：Mark R. Crimmin、Merle Arrowsmith、Anthony G. M. Barrett、Ian J. Casely、Michael S. Hill、Panayiotis A. Procopiou

  DOI：10.1021/ja9003377

  日期：2009.7.22

  aminoalkenes. The reactions proceeded under mild conditions, allowing the synthesis of five-, six-, and seven-membered heterocyclic compounds. Qualitative assessment of these reactions revealed that the ease of catalytic turnover increases (i) for smaller ring sizes (5 > 6 > 7), (ii) substrates that benefit from favorable Thorpe-Ingold effects, and (iii) substrates that do not possess additional substitution

  β-二酮亚胺稳定的氨基钙络合物 [ArNC(Me)CHC(Me)NAr}CaN(SiMe(3))(2)}(THF)]（Ar = 2,6-二异丙基苯基）和甲基镁据报道，络合物 [ArNC(Me)CHC(Me)NAr}Mg(Me)(THF)] 是氨基烯烃加氢胺化/环化的有效预催化剂。反应在温和的条件下进行，可以合成五元、六元和七元杂环化合物。对这些反应的定性评估表明，催化转化的容易程度增加 (i) 对于较小的环尺寸 (5 > 6 > 7)，(ii) 受益于有利的 Thorpe-Ingold 效应的底物，以及 (iii) 不具有的底物烯烃实体上的额外取代。前手性底物可以根据现有立体中心的位置进行非对映选择性加氢胺化/环化。此外，确定了这些反应的一些次要副产品，这些副产品来自竞争性烯烃异构化反应。预催化剂和伯胺之间的一系列化学计量反应为催化剂引发提供了一个重要的模型，并表明这些反应在室温下很容易，钙预催化剂与苄胺的反应以
• Highly efficient, base-catalysed, intramolecular hydroamination of non-activated olefins
  作者：Coralie Quinet、Pierre Jourdain、Christophe Hermans、Ali Ates、Isabelle Lucas、István E. Markó

  DOI：10.1016/j.tet.2007.11.066

  日期：2008.2

  The intramolecular hydroamination of a large variety of non-activated alkenes can be efficiently catalysed by small amounts of lithium bases, providing smoothly and in high yields the corresponding five- and six-membered ring heterocycles. Fused and bridged bicyclic amines, of varying ring sizes, can be readily prepared either by a sequential hydroamination process or by a tandem, double addition reaction

  少量的锂碱可以有效地催化多种非活化烯烃的分子内加氢胺化反应，从而以高收率平稳地提供相应的五元和六元环杂环。环大小不同的熔融和桥接双环胺可以很容易地通过顺序加氢胺化工艺或串联，双加成反应制备。
• A novel chiral yttrium complex with a tridentate linked amido-indenyl ligand for intramolecular hydroamination
  作者：Zhuo Chai、Dezhi Hua、Kui Li、Jiang Chu、Gaosheng Yang

  DOI：10.1039/c3cc47006g

  日期：——

  A new chiral silicon-linked tridentate amido-indenyl ligand was developed from indene and enantiopure 1,2-cyclohexanediamine. Its yttrium complex was synthesized, characterized and applied to efficiently catalyze the intramolecular hydroamination of non-activated olefins with up to 97% ee.

  一种新的手性硅联接的三齿氨基-茚基配体是由茚和对映纯的1,2-环己二胺开发的。其钇配合物被合成、表征，并用于高效催化非活化烯烃的分子内氢氨化反应，获得了高达97%的对映纯度。