N-(3-tert-butyl-2-hydroxy)benzylidenecyclohexylamine | 215033-70-8

• 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: N-(3-tert-butyl-2-hydroxy)benzylidenecyclohexylamine
• 英文别名: 2-tert-butyl-6-[(cyclohexylimino)methyl]phenol；N-(3-tert-butylsalicylidene)cyclohexylaminato；2-cyclohexyliminomethyl-6-tert-butylphenol；2-tBu-6-[(cyclohexyl)N=CH]C6H3OH；2-(t-Bu)-6-(C6H11NCH)C6H3OH；2-tert-Butyl-6-[(cyclohexylamino)methylidene]cyclohexa-2,4-dien-1-one；2-tert-butyl-6-(cyclohexyliminomethyl)phenol
• CAS: 215033-70-8
• 化学式: C₁₇H₂₅NO
• 分子量: 259.392
• InChiKey: VNSPDNGMZRVPBG-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.6
• 重原子数：
  19
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.59
• 拓扑面积：
  32.6
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  N-(3-tert-butyl-2-hydroxy)benzylidenecyclohexylamine 在 N,N,N-trimethylbenzenemethanaminium dichloroiodate 、 calcium carbonate 作用下， 以 甲醇 、 二氯甲烷 为溶剂， 反应 24.0h， 以96%的产率得到4-iodo-2-cyclohexyliminomethyl-6-tert-butylphenol
  参考文献：
  名称：

  二核和三核铁/钛和铁/锆配合物与杂环配体作为乙烯聚合的催化剂

  摘要：

  摘要聚烯烃树脂的性能很大程度上取决于其分子量，侧链支链的数量和分子量分布。仅在一个反应​​步骤中获得这种定制产物的一种方法是应用具有不同活性位点的不对称多核催化剂。由于每个活性位点都在产生自己的聚合物，因此产生了“分子共混”。为了达到这个目的，已经合成并表征了铁，钛和锆的各种单，双和三核络合物，其中包含2，6-双（芳基乙基）吡啶和苯氧基亚胺。碘化功能化的反应2 通过Sonogashira交叉偶联反应与炔烃官能化的苯氧基亚胺化合物形成的6-双（芳基-乙基）吡啶衍生物可生成可为两种不同金属提供配位点的配体前体。具有Ti / Fe和Zr / Fe组合的三核络合物（每个分子在两个2，6-双（芳基乙基）吡啶单元中包含两个铁原子）提供了最佳的乙烯聚合结果。由于快速的配体交换反应，不能从单（苯氧基亚胺）钛配合物和偶联的双（螯合物）配体前体的反应中分离出双核铁/钛配合物。由于金属中心在不同的聚合温度下表现出最佳性能，因此成分（因此，

  DOI：

  10.1016/j.poly.2016.07.033
• 作为产物：
  描述：

  2-叔丁基苯酚 在 乙基溴化镁 、 对甲苯磺酸 作用下， 以 四氢呋喃 、 甲苯 为溶剂， 反应 6.0h， 生成 N-(3-tert-butyl-2-hydroxy)benzylidenecyclohexylamine
  参考文献：
  名称：

  二核和三核铁/钛和铁/锆配合物与杂环配体作为乙烯聚合的催化剂

  摘要：

  摘要聚烯烃树脂的性能很大程度上取决于其分子量，侧链支链的数量和分子量分布。仅在一个反应​​步骤中获得这种定制产物的一种方法是应用具有不同活性位点的不对称多核催化剂。由于每个活性位点都在产生自己的聚合物，因此产生了“分子共混”。为了达到这个目的，已经合成并表征了铁，钛和锆的各种单，双和三核络合物，其中包含2，6-双（芳基乙基）吡啶和苯氧基亚胺。碘化功能化的反应2 通过Sonogashira交叉偶联反应与炔烃官能化的苯氧基亚胺化合物形成的6-双（芳基-乙基）吡啶衍生物可生成可为两种不同金属提供配位点的配体前体。具有Ti / Fe和Zr / Fe组合的三核络合物（每个分子在两个2，6-双（芳基乙基）吡啶单元中包含两个铁原子）提供了最佳的乙烯聚合结果。由于快速的配体交换反应，不能从单（苯氧基亚胺）钛配合物和偶联的双（螯合物）配体前体的反应中分离出双核铁/钛配合物。由于金属中心在不同的聚合温度下表现出最佳性能，因此成分（因此，

  DOI：

  10.1016/j.poly.2016.07.033

文献信息

• Synthesis of Al complexes containing phenoxy-imine ligands and their use as the catalyst precursors for efficient living ring-opening polymerisation of ε-caprolactone
  作者：Jingyu Liu、Naruhito Iwasa、Kotohiro Nomura

  DOI：10.1039/b801561a

  日期：——

  Al complexes containing phenoxy-imine ligands of type, Me2Al[O-2-R1-6-(R2NCH)C6H3] [R1 = Me, R2 = 2,6-iPr2C6H3 (1a), tBu (1b); R1 = tBu, R2 = 2,6-iPr2C6H3 (2a), tBu (2b), cyclohexyl (2c), adamantyl (2d), C6H5 (2e), 2,6-Me2C6H3 (2f), C6F5 (2g)] have been prepared in high yields from AlMe3 by treating with 1.0 equiv. of 2-R1-6-(R2NCH)C6H3OH in n-hexane. Structures for 1a, 1b, 2a–e and 2g were determined by X-ray crystallography, and these complexes have a distorted tetrahedral geometry around Al; both the Al–O and the Al–N bond distances were influenced by substituents in both the aryloxo and the imino groups. Me2Al[μ2-O-2-(R2NCH)C6H4](AlMe3) [R2 = 2,6-iPr2C6H3 (3a), tBu (3b)] were prepared exclusively by reaction of AlMe3 with 2-(R2NCH)C6H4OH, and these complexes form a distorted tetrahedral geometry around each Al centre with additional AlMe3 coordinating to the oxygen in the phenoxy-imine ligand. Complexes 1a, 1b and 2a–g were tested as catalyst precursors for ring-opening polymerisation (ROP) of ε-caprolactone (CL) in the presence of nBuOH (1.0 equiv. to Al), and their catalytic activities were strongly influenced by the imino substituent (R2). The efficient ROP has been achieved using the C6F5 analogue (2g), with the ROP taking place in a living manner.

  含有苯氧亚胺配体类型的 Al 配合物 Me2Al[O-2-R1-6-(R2NCH)C6H3] [R1 = Me, R2 = 2,6-iPr2C6H3 (1a), tBu (1b); R1 = tBu, R2 = 2,6-iPr2C6H3 (2a), tBu (2b), cyclohexyl (2c), adamantyl (2d), C6H5 (2e), 2,6-Me2C6H3 (2f), C6F5 (2g)],通过在 n-己烷中用 1.0 当量的 2-R1-6-(R2NCH)C6H3OH 处理 AlMe3 高产率地制备。通过 X 射线晶体学确定了 1a, 1b, 2a–e 和 2g 的结构, 这些配合物在 Al 周围具有扭曲的四面体几何结构; Al–O 和 Al–N 键距离都受到 aryloxo 和 imino 基团中取代基的影响。 Me2Al[μ2-O-2-(R2NCH)C6H4](AlMe3) [R2 = 2,6-iPr2C6H3 (3a), tBu (3b)], 通过 AlMe3 与 2-(R2NCH)C6H4OH 的反应独有地制备, 这些配合物在每个 Al 中心周围形成扭曲的四面体几何结构, 并额外有 AlMe3 与苯氧亚胺配体中的氧配位。 1a, 1b 和 2a–g 被测试为环开聚合 (ROP) 的催化剂前体, 在 nBuOH (相对于 Al 为 1.0 当量) 存在下进行 ε-己内酯 (CL) 的 ROP, 其催化活性强烈受到 imino 取代基 (R2) 的影响。使用 类似物 (2g) 实现了高效的 ROP, 其中 ROP 以活性方式进行。
• Zirconium Complexes Having Phenoxy/Cycloalkylimine Chelate Ligands for the Polymerization of Ethylene for Vinyl-Terminated Low Molecular Weight Polyethylenes
  作者：Sei-ichi Ishii、Makoto Mitani、Junji Saito、Sadahiko Matsuura、Shin-ichi Kojoh、Norio Kashiwa、Terunori Fujita

  DOI：10.1246/cl.2002.740

  日期：2002.7

  Zirconium complexes bearing phenoxy/cyclopropyl-, cyclobutyl- or cyclopentyl-imine chelate ligands, when activated with methylalumoxane (MAO), produced vinyl-terminated low molecular weight polyethylenes (Mw<5000) with higher activities than Cp2ZrCl2 at 25 °C. The complex having a cyclobutyl group provided the lowest molecular weight polyethylene (Mw 2100).

  含有苯氧基/环丙基、环丁基或环戊基亚胺螯合配体的锆络合物在用甲基铝氧烷（MAO）活化时，可生成乙烯基封端的低分子量聚乙烯（Mw<5000），在 25 ℃ 下的活性高于 Cp2ZrCl2。具有环丁基的复合物提供了分子量最低的聚乙烯（Mw 2100）。
• Ethylene polymerization activity under practical conditions displayed by zirconium complexes having two phenoxy-imine chelate ligands
  作者：Naoto Matsukawa、Shigekazu Matsui、Makoto Mitani、Junji Saito、Kazutaka Tsuru、Norio Kashiwa、Terunori Fujita

  DOI：10.1016/s1381-1169(01)00050-4

  日期：2001.3

  however, the activity at 75°C was still lower than that at 50°C. The combination of an n-hexyl or a cyclohexyl group on the imine nitrogen and a methoxy group at the para-position of the phenoxy oxygen enhanced activity at 75°C. Thus, N-[(3-t-butyl-5-methoxysalicylidene)-n-hexylaminato]zirconium(IV)dichloride (5) and N-[(3-t-butyl-5-methoxysalicylidene)cyclohexylaminato]zirconium(IV)dichloride (6) displayed

  在50和75℃，0.9 MPa乙烯压力下，研究了使用具有两个苯氧基-亚胺螯合物的锆配合物进行的乙烯聚合。在原催化剂的活性，ñ - [（3-叔丁基亚水杨基）anilinato]锆（IV）二氯化物（1），降低了提高聚合温度（50℃：1192公斤-PE /毫摩尔锆·H ，75℃：209kg-PE / mmol-Zr·h）。在亚胺氮上或苯环中苯氧基氧的对位引入供电子基团（例如正己基和甲氧基）可抑制活性降低，但在75°C时的活性为仍然低于50°C时的温度。一个n-的组合亚胺氮上的己基或环己基和苯氧基氧对位的甲氧基在75°C时增强了活性。因此，Ñ - [（3-叔丁基-5- methoxysalicylidene） - N- hexylaminato]锆（IV）二氯化物（5）和ñ - [（3-叔丁基-5- methoxysalicylidene）cyclohexylaminato]锆（IV）二氯化物（6）的活度大于1000
• Monocyclopentadienyl phenoxy-imine and phenoxy-amine complexes of titanium and zirconium and their application as catalysts for 1-alkene polymerisation
  作者：Robyn K.J Bott、David L Hughes、Mark Schormann、Manfred Bochmann、Simon J Lancaster

  DOI：10.1016/s0022-328x(02)02106-x

  日期：2003.1

  Deprotonation of the phenol-imines 2-Bu'-6-(RNCH)C6H3OH (R = 2,4,6-Me3C6H2 (1a), C6F5 (1b), C6H11 (1c) and phenolamines 2,4-Bu'(2)-6-(R'NCH2)C6H2OH (R' = C4H8 (1d), C5H10 (1e)) with n -BuLi gives the corresponding lithium phenoxides. The reaction with MCl4 in THF solution leads to the bis(ligand) complexes 2-Bu'-6-(RNCH)C6H3H3O}(2)MCl2 and 2,4-Bu'(2)-6-(R'NCH2)C6H2O}(2)MCl2 (M=Ti: 2a, 2d, 2e, Zr: 3a, 3d and 3e). The cyclopentadienyl phenoxy-imine and -amine complexes Cp2-Bu'-6-(RNCH)C6H3O}MCl2 and Cp2,4-Bu'(2)-6-(R'NCH2)C6H2O}MCl2 (M = Ti: 4a-4e, Zr: 5a-5e) were prepared similarly through reaction with CPMCl3. The crystal and molecular structures of 2a, 3a, 4a and 4c have been determined. 2a and 3a are isostructural and exhibit a distorted octahedral geometry. 4a has a distorted square-pyramidal structure whereas 4e is essentially tetrahedral and the nitrogen does not coordinate. All new complexes are active for the polymerisation of ethene when activated with methyaluminoxane. 4b, 5a, 5d and 5e are active for the copolymerisation of ethene and 1-hexene and the oligomerisation of 1-hexene. (C) 2002 Elsevier Science B.V. All rights reserved.
• Synthesis, structure and catalytic activity of new iminophenolato complexes of scandium and yttrium
  作者：Agustı́n Lara-Sanchez、Antonio Rodriguez、David L Hughes、Mark Schormann、Manfred Bochmann

  DOI：10.1016/s0022-328x(02)01657-1

  日期：2002.12

  The reaction of equimolar amounts of 2-(2,4,6-Me3C6H2N = CH)(6-Bu')C6H3OH (HL') with M(CH2SiMe3)(3)(THF)(3) (M = Sc or Y) under mild conditions gives M(CH2SiMe3)(2)(THF)(L-1). The trigonal-bipyramidal structure of these dialkyls was confirmed crystallographically for M = Sc. Whereas the scandium complex is stable in solution at room temperature, the yttrium derivative slowly disproportionates to give Y(L-1)(3) which is also accessible from Y(CH2SiMe3)(3)(THF)(3) and three HL'. The X-ray structure of Y(L)3 indicates a chiral tris-chelate complex. While the reaction of the related ligand (2-CyN = CH)(6-Bu')C6H3OH (HL2, CY = cyclohexyl) with Sc(CH2SiMe3)(3)(THF)(3) gives the expected dialkyl Sc(CH2SiMe3)(2)(THF)(L-2), the reaction with the yttrium analogue affords the six-coordinate monoalkyl product Y(CH2SiMe3)(THF)(L-2)(2). This product is stable in solution towards disproportionation. The reaction of Y[N(SiMe3)(2)](3) with (2-C6F5N = CH)(6-Bu')C6H3OH (HL3) affords YN(SiMe3)(2)}(L-3)(2) and Y(L-3)(3). Both complexes are seven-coordinate in the solid state due to Y...F co-ordination to the C6F5 substituents. The scandium alkyl complexes are efficient catalysts for the ring-opening polymerisation of F-caprolactone. (C) 2002 Elsevier Science B.V. All rights reserved.