(2,6-Diisopropyl-phenyl)-isopropylidene-amine | 350038-41-4

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: (2,6-Diisopropyl-phenyl)-isopropylidene-amine
• 英文别名: N-[2,6-di(propan-2-yl)phenyl]propan-2-imine
• CAS: 350038-41-4
• 化学式: C₁₅H₂₃N
• 分子量: 217.354
• InChiKey: BHLQZDYAUUIXIZ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4
• 重原子数：
  16
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.53
• 拓扑面积：
  12.4
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  (2,6-Diisopropyl-phenyl)-isopropylidene-amine 在 氘代三氟乙酸 、 重水 作用下， 以 重水 为溶剂， 反应 6.0h， 以92%的产率得到
  参考文献：
  名称：

  末端亚氨基钪存在的证据：涉及亚氨基-钪键形成和 C-H 活化反应的机理研究

  摘要：

  苯胺-甲基复合物 (PNP)Sc(NH[DIPP])(CH(3)) (1) [PNP(-) = 双(2-二异丙基膦基-4-甲苯基)酰胺，DIPP = 2,6-二异丙基苯基]在吡啶存在下消除甲烷（k(avg) = 5.13 × 10(-4) M(-1) s(-1) at 50 °C）以生成瞬态亚氨基钪 (PNP)Sc=N[DIPP] (NC(5)H(5)) (A-py)，以 1,2-加成方式快速激活吡啶的 CH 键，形成稳定的吡啶基络合物 (PNP)Sc(NH[DIPP])(η( 2)-NC(5)H(4)) (2)。机理研究表明 CH 活化过程总体上是二阶的：一阶在钪中，一阶在底物（吡啶）中。吡啶结合先于甲烷的消除，并且 α-氢提取是总体速率决定性的 [1-d(1) 转化为 2 的动力学同位素效应 (KIE) 在 35 °C 和 4.9(14) 时为 5.37(6)在 50 °C] 激活参数

  DOI：

  10.1021/ja307279r
• 作为产物：
  描述：

  2-[1-(2,6-diisopropylphenylamino)methylethyl]pyridine-N-oxide 在 甲基锂 作用下， 生成 (2,6-Diisopropyl-phenyl)-isopropylidene-amine
  参考文献：
  名称：

  (N-Arylaminomethyl)pyridine-N-oxides: Synthesis and characterization of potential ligand systems and the formation of their N,O-chelate aluminum complexes

  摘要：

  Pyridine-N-oxide-2-carbaldehyde (4a) was converted to the corresponding imine (5a) by treatment with 2,6-diisopropylaniline. Subsequent reduction with a sodium borohydride gave the corresponding ( N-arylaminomethyl) pyridine-N-oxide derivative (6a). A series of analogous compounds was prepared starting from the respective ( aldimino) quinoline-N-oxide ( 4b) or ( ketimino) pyridine-N-oxide ( 10) systems. Deprotonation of the ( aminomethyl) pyridine-N-oxides resulted in a series of unexpected reactions, such as coupling, internal redox reactions or fragmentation. Eventually, the N,O-chelate aluminum complexes ( 22, 23) derived from the ( aminoethyl) pyridine-N-oxide ligand systems could be obtained by treatment of the respective iminopyridine-N-oxides with trimethylaluminum. Many products were characterized by X-ray diffraction. (C) 2008 Elsevier B. V. All rights reserved.

  DOI：

  10.1016/j.jorganchem.2008.05.032

文献信息

• The ‘one-pot’ syntheses of α,α′-diphosphino-substituted imines: a unique reaction of bulky bis(dialkylamino)chlorophosphines
  作者：Antoine Baceiredo、Guy Bertrand、Philip W. Dyer、John Fawcett、Nina Griep-Raming、Olivier Guerret、Martin J. Hanton、David R. Russell、Anna-Maria Williamson

  DOI：10.1039/b009867l

  日期：——

  The reaction between various bis(dialkylamino)chlorophosphines and N-isopropyl-substituted lithium amides afforded bis(α,α′-phosphino)imines in a ‘one-pot’ procedure. These compounds react with sulfur to generate intramolecularly hydrogen-bonded ylide derivatives. The molecular structure of (Pr2iN)2PCH2C(NBut)CH2P(NPri)2 has been determined by X-ray crystallography.

  各种双（二烷基氨基）氯膦与N-异丙基取代的氨基酰胺之间的反应以“一锅法”得到双（α，α'-膦基）亚胺。这些化合物与硫反应生成分子内氢键的叶立德衍生物。 通过X射线晶体学测定了（Pr 2 i N）2 PCH 2 C（NBu t）CH 2 P（NPr i）2的分子结构。
• Nickel and palladium phosphinimine-imine ligand complexes
  作者：Jason D. Masuda、Pingrong Wei、Douglas W. Stephan

  DOI：10.1039/b306110h

  日期：——

  The imine (C6H3i-Pr2)NCMe21 was prepared and used to make the phosphine (C6H3i-Pr2)NC(Me)CH2PPh22. Oxidation with the substituted arylazide resulted in the isolation of the phosphinimine-imine species (C6H3i-Pr2)NC(Me)CH2PPh2(NC6H3i-Pr2) 3. The ligand 3 forms the neutral Ni-complex NiBr2((C6H3i-Pr2)NC(Me)CH2PPh2(NC6H3i-Pr2)) 4 while attempts to prepare the analogous Pd species were unsuccessful. Reaction of 3 with n-BuLi produced the Li-salt Li(thf)((C6H3i-Pr2)NC(Me)CHPPh2(NC6H3i-Pr2)) 5. Subsequent reaction with NiBr2(dme) afforded [Ni((C6H3i-Pr2)NC(Me)CHPPh2(NC6H3i-Pr2))(μ-Br)2Li(thf)2] 6. In related syntheses 5 reacted with NiBr2(dme) or (PhCN)2PdCl2 and PPh3 to give the complexes of formulation MX((C6H3i-Pr2)NC(Me)CHPPh2(NC6H3i-Pr2))(PPh3) (X = Br, M = Ni 7; X = Cl, M = Pd 8). The latter complexes 7 and 8 are phosphinimine-N–C bound. Structural studies of 2 and 4–8 are reported. The implications of these studies for the utility of this phosphinimine-imine ligand in olefin polymerization catalysts are considered.

  制备亚胺(C6H3i-Pr2)NCMe21并用于制备膦(C6H3i-Pr2)NC(Me)CH2PPh22。用取代的芳基叠氮进行氧化，分离出膦亚胺-亚胺 (C6H3i-Pr2)NC(Me)CH2PPh2(NC6H3i-Pr2) 3.配体3形成中性Ni配合物NiBr2((C6H3i-Pr2)NC(Me)CH2PPh2(NC6H3i-Pr2)) 4 而尝试制备类似的 Pd 物质却没有成功。 3与正丁基锂反应生成锂盐Li(thf)((C6H3i-Pr2)NC(Me)CHPPh2(NC6H3i-Pr2)) 5. 随后与 NiBr2(dme) 反应得到 [Ni((C6H3i-Pr2)NC(Me)CHPPh2(NC6H3i-Pr2))(μ-Br)2Li(thf)2] 6. 在相关合成 5 中，与 NiBr2(dme) 或 (PhCN)2PdCl2 和 PPh3 反应，得到配方 MX((C6H3i-Pr2)NC(Me)CHPPh2(NC6H3i-Pr2))(PPh3) 的复合物 （X = Br，M = Ni 7；X = Cl，M = Pd 8）。后者配合物 7 和 8 是膦亚胺-N-C 结合的。 2 和 4-8 的结构研究已有报道。考虑了这些研究对这种膦亚胺-亚胺配体在烯烃聚合催化剂中的应用的影响。
• Alkali Metal Amide Salts of a Bulky Nitrogen Tethered Phosphonium Fluorenide Ligand
  作者：Tanner George、Jason D. Masuda

  DOI：10.1021/acs.organomet.3c00204

  日期：2023.9.11

  0.5(THF, n-hexane) solvate of 3 occur as the (Z)-enamine, while co-crystallization of either diethyl ether or 3 molecules of THF resulted in the (E)-enamine of 3. The ability for compound 3 to participate in two types of hydrogen bonds between either the methyne or amine protons with THF was observed from the 0.5(THF, n-hexane) and 3(THF) solvates, respectively. Subsequent deprotonation of the secondary

  先前报道的膦-亚胺配体与9-溴芴的反应提供了溴化鏻(E)-烯胺，其在去质子化后提供了与氟化鏻部分相连的烯胺。分离该烯胺的各种晶体并随后通过单晶X射线衍射分析表明存在(E)-和(Z)-异构体，这由C 6 D 6 中的三种动态异构体支持。1 H NMR 光谱表明，烯胺鏻氟化物是主要异构体，并且在3的所有四种固态晶体结构中也观察到。无溶剂的3和3的0.5(THF，正己烷)溶剂化物以 (Z)-烯胺的形式出现，而乙醚或 3 分子 THF 的共结晶产生3的 (E)-烯胺。化合物3参与次甲基或胺质子与 THF 之间两种类型氢键的能力分别从 0.5（THF，正己烷）和 3（THF）溶剂合物中观察到。随后用含锂、钠和钾的碱对仲胺进行去质子化，产生金属酰胺，主要形成单体结构。每种碱金属均由一个配体与配位溶剂分子 (Et 2O或THF），唯一的例外是缺乏配位溶剂的钾络合物。该钾络合物的供体空位通过与相邻 6 元
• Hexacoordinated tin complexes catalyse imine hydrogenation with H₂
  作者：Andrea Žáková、Pritha Saha、Alexandros Paparakis、Martin Zábranský、Gabriela Gastelu、Jaroslav Kukla、Jorge G. Uranga、Martin Hulla

  DOI：10.1039/d3cc05878f

  日期：2024.3.19

  that hexacoordinated tin complexes with Schiff base ligands catalyse imine hydrogenation via activation of H2(g). As shown by hydrogen–deuterium scrambling, [Sn(tBu2Salen)(OTf)2] activated H2(g) at 25 °C and 10 bar of H2. After tuning the ligands, we found that [Sn(Salen)Cl2] was the most efficient imine hydrogenation catalyst despite having the lowest activity in H2(g) activation. Moreover, various imines

  受阻路易斯对（FLP）加氢催化剂主要使用烷基和芳基取代的路易斯酸（LA），它们提供有限数量的取代基组合，限制了我们调节其性质并最终调节其反应性的能力。尽管如此，主族配合物有许多可用于此类目的的配体，这可以使我们扩大 FLP 催化的范围。为了支持这一假设，我们在此证明了具有希夫碱配体的六配位锡络合物通过活化 H 2(g) 来催化亚胺氢化。如氢-氘加扰所示，[Sn( t Bu 2 Salen)(OTf) 2 ] 在 25 °C 和 10 bar 的 H 2下活化了 H 2(g) 。调整配体后，我们发现[Sn(Salen)Cl 2 ]是最有效的亚胺氢化催化剂，尽管其在H 2(g)活化中的活性最低。此外，各种亚胺的氢化收率高达98%，从而为开发基于主族元素六配位LA的新型FLP氢化催化剂提供了机会。
• Rich C–H bond activations of yttrium alkyl complexes bearing phosphinimino-amine ligands
  作者：Danfeng Li、Shihui Li、Dongmei Cui、Xuequan Zhang

  DOI：10.1016/j.jorganchem.2010.09.005

  日期：2010.12

  Aseries of phosphinimino-amine compounds (2,6-iPr(2)-C6H3NH)C(Me)CHPPh2(NAr)(Ar = 2,6-iPr(2)-C6H3 (HL1),2,6-Et-2-C6H3 (HL2),2,6-Me-2-C6H3 (HL3), C6H5 (HL4), 3-CF3-C6H4 (HL5)) that existed in imine and amine forms were synthesized and fully characterized. Treatment of HL1-5 with Y(CH2SiMe3)(3)(THF)(2) afforded the corresponding yttrium mono- or bis(alkyl) complexes that depended significantly on the ancillary ligands. The reactions between HL1-3 and Y(CH2SiMe3)(3)(THF)(2) at room temperature generated mononuclear monoalkyl complexes 1-3 via deprotonation and C-H bond activation. However, when compounds HL4,5 were used, the dialkyl complexes 4 and 5 were isolated by deprotonation only. The molecular structures of complexes 1-4 were characterized with X-ray crystallography and discussed. (c) 2010 Elsevier B.V. All rights reserved.