4-[(2-methylquinolin-8-yl)imino]pent-2-en-2-ol | 1222487-23-1

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 喹啉及其衍生物
• 英文名称: 4-[(2-methylquinolin-8-yl)imino]pent-2-en-2-ol
• CAS: 1222487-23-1
• 化学式: C₁₅H₁₆N₂O
• 分子量: 240.305
• InChiKey: RXDLZILCCBIJEL-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.1
• 重原子数：
  18.0
• 可旋转键数：
  2.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.2
• 拓扑面积：
  45.48
• 氢给体数：
  1.0
• 氢受体数：
  3.0

反应信息

• 作为反应物：
  描述：

  4-[(2-methylquinolin-8-yl)imino]pent-2-en-2-ol 、 二丁基镁 以 乙醚 、 正庚烷 为溶剂， 生成 bis[2-(N-2-methylquinolyl)-4-pentanonato]magnesium
  参考文献：
  名称：

  双连接镁配合物对L-丙交酯和ε-己内酯进行开环聚合和共聚

  摘要：

  通过新的（L 3 -H – L 5 -H）和先前报道的酮胺原配体与二丁基镁的反应合成了七个镁配合物（1–7），分离出的产率为59–70％。配合物1–7的特征已得到充分表征，由在镁中心周围以扭曲的八面体几何形状协调的双连接的均化酮亚胺盐组成。研究了该配合物引发l的开环聚合（ROP）的能力。 在4-氟苯酚助催化剂存在下，将丙交酯（L-LA）转化为聚乳酸（PLA），将ε-己内酯（ɛCL）转化为聚己内酯。对于L‐LA聚合，包含配体给电子基团（1-5）的配合物在100°C下2 h内可实现> 90％的转化，而6和7中CF 3基团的存在减慢或未检测到PLA。使用ɛCL，ROP以1–7启动导致具有类似电子效果的转化百分比降低。获得了具有低多分散指数值（1.23-1.56）的中等分子量的PLA聚合材料（14.3–21.3 kDa），ROP似乎是天然存在的。L‐LA和ɛCL的共聚仅是由ɛCL依次进行聚合，然后

  DOI：

  10.1002/pola.29280
• 作为产物：
  描述：

  8-氨基喹哪啶 、 乙酰丙酮 在 对甲苯磺酸 作用下， 以 甲苯 为溶剂， 生成 4-[(2-methylquinolin-8-yl)imino]pent-2-en-2-ol
  参考文献：
  名称：

  双连接镁配合物对L-丙交酯和ε-己内酯进行开环聚合和共聚

  摘要：

  通过新的（L 3 -H – L 5 -H）和先前报道的酮胺原配体与二丁基镁的反应合成了七个镁配合物（1–7），分离出的产率为59–70％。配合物1–7的特征已得到充分表征，由在镁中心周围以扭曲的八面体几何形状协调的双连接的均化酮亚胺盐组成。研究了该配合物引发l的开环聚合（ROP）的能力。 在4-氟苯酚助催化剂存在下，将丙交酯（L-LA）转化为聚乳酸（PLA），将ε-己内酯（ɛCL）转化为聚己内酯。对于L‐LA聚合，包含配体给电子基团（1-5）的配合物在100°C下2 h内可实现> 90％的转化，而6和7中CF 3基团的存在减慢或未检测到PLA。使用ɛCL，ROP以1–7启动导致具有类似电子效果的转化百分比降低。获得了具有低多分散指数值（1.23-1.56）的中等分子量的PLA聚合材料（14.3–21.3 kDa），ROP似乎是天然存在的。L‐LA和ɛCL的共聚仅是由ɛCL依次进行聚合，然后

  DOI：

  10.1002/pola.29280

文献信息

• Synthesis and Structures of Tridentate Ketoiminate Zinc Complexes That Act As <scp>l</scp>-Lactide Ring-Opening Polymerization Catalysts
  作者：Courtney C. Roberts、Brandon R. Barnett、David B. Green、Joseph M. Fritsch

  DOI：10.1021/om200865w

  日期：2012.6.11

  and zinc phenoxide structures showed mononuclear complexes with tridentate coordination by the ketoiminate ligands. ROP of l-lactide with the zinc amides and phenoxide complexes gave isotactic poly-l-lactide with generally low molecular weight distributions. As compared to their amide counterparts, the zinc phenoxide complexes showed superior lactide ROP behavior in terms of percent conversion as a

  一系列的NNO三齿Schiff碱配体用于制备酰胺锌和酚盐锌配合物，这些配合物被证明是有效的1-丙交酯开环聚合（ROP）催化剂。该复合物是由带有侧基喹啉供体的酮亚胺，双（三甲基甲硅烷基）酰胺锌和2,6-二叔丁基苯酚制备的。它们的特征在于1 H和13 C NMR，吸收光谱，显微分析和X射线晶体学。酰胺锌和苯酚锌结构显示单核络合物，由酮亚胺基配体具有三齿配位。l-丙交酯与酰胺化锌和酚盐配合物的ROP生成等规聚l-低分子量分布的丙交酯。与它们的酰胺对应物相比，苯氧锌络合物在转化百分率随时间变化，测得的分子量更接近预测值以及较低的多分散指数值方面表现出优异的丙交酯ROP行为。喹啉（H，Me，Ph）的2位取代基尺寸的增加改善了配合物的合成，但对ROP产生了不利影响。
• Synthesis, spectroscopy, and crystallography of mononuclear, five-coordinate aluminum complexes that act as cyclic ester polymerization initiators
  作者：Alexandria M. McCollum、Angela M. Longo、Amanda E. Stahl、Abigail S. Butler、Arnold L. Rheingold、Thomas R. Cundari、David B. Green、Kelsey R. Brereton、Joseph M. Fritsch

  DOI：10.1016/j.poly.2021.115233

  日期：2021.8

  single-crystal X-ray crystallography. These mononuclear complexes differ from previously reported aluminum ion-pair complexes due to the symmetric cleavage of tris-dimethylphenoxide aluminum dimer by THF and were shown to have distorted trigonal bipyramidal coordination geometries (τ5 = 0.73–0.89). In a preliminary study, the aluminum complexes were demonstrated to be effective initiators for ring-opening

  制备了三个带有喹啉基侧基的酮亚胺和一系列五配位的酮亚胺铝配合物，并在光谱和晶体学上进行了表征。酮亚胺的合成完成了一系列十种区域异构体，对于这些异构体而言，产物比例在邻近烷基/芳基或邻近三氟甲基取代基的喹啉加成产物之间变化。定量的酮亚胺区域异构体比率为19F NMR证明了空间阻滞在席夫碱缩合反应的亲核进攻机理步骤中的作用，并进一步得到了具有Charton空间参数和DFT计算的线性自由能关系的支持。从酮亚胺和三（2,6-二甲基苯氧基）铝二聚体制备了八种五配位铝络合物，收率为57-92％，并具有1 H，13 C，19 F和27 Al核磁共振波谱，具有紫外可见性吸收光谱，元素分析和单晶X射线晶体学。这些单核配合物由于tris的对称裂解而不同于先前报道的铝离子对配合物由THF -dimethylphenoxide铝二聚体和显示具有扭曲的三角双锥协调的几何形状（τ 5  = 0.73-0.89）。在初
• Synthesis and structures of bis-ligated zinc complexes supported by tridentate ketoimines that initiate<scp>l</scp>-lactide polymerization
  作者：Kimberly A. Gerling、Nomaan M. Rezayee、Arnold L. Rheingold、David B. Green、Joseph M. Fritsch

  DOI：10.1039/c4dt01607f

  日期：——

  Eight bis-ligated, homoleptic, zinc complexes were synthesized through the reaction of NNO Schiff base ketoimines bearing varying substituents with diethyl zinc in an inert atmosphere glovebox at room temperature and isolated in 62–95% yield. The complexes were characterized with 1H, 13C, and 19F nuclear magnetic resonance spectroscopy, absorbance spectroscopy, high resolution mass spectrometry, elemental analysis, and single crystal X-ray crystallography. The complexes were shown to adopt distorted octahedral coordination geometry around zinc. The 1H and 19F NMR spectra of complexes 1–7 showed stable zinc coordination at 300 K while the effect of steric encumbrance and two trifluoromethyl groups in complex 8 was investigated with variable temperature NMR. The bis-ligated zinc complexes were effective initiators for the ring opening polymerization of L-lactide into poly-L-lactic acid (PLLA). With [L-lac]/[Zn complex] = 50, the bis-ligated zinc complexes yielded percentage conversion of 14–98% with polymerization times varying from 15–1440 min, where the longest reaction times were required when two trifluoromethyl groups were present. The addition of 4-fluorophenol co-catalyst resulted in up to a 5-fold increase in the percentage conversion in toluene solution and up to a 14-fold increase in bulk melt polymerization with reductions in the poly-dispersity index values for the isolated PLLA. Addition of 4-fluorophenol to complex 1 was studied with 1H and 19F NMR and appeared to yield an in situ generated zinc alkoxide complex.

  在室温的惰性气氛手套箱中，通过含有不同取代基的 NNO 席夫碱酮亚胺与二乙基锌的反应，合成了八种双配位同型锌络合物，并以 62-95% 的收率进行了分离。利用 1H、13C 和 19F 核磁共振谱、吸光度光谱、高分辨率质谱、元素分析和单晶 X 射线晶体学对这些复合物进行了表征。结果表明，这些配合物在锌周围呈扭曲的八面体配位几何形状。配合物 1-7 的 1H 和 19F NMR 光谱显示，锌在 300 K 时配位稳定，而配合物 8 中的立体包络和两个三氟甲基的影响则通过变温 NMR 进行了研究。双配位锌配合物是 L-内酰胺开环聚合成聚 L-乳酸（PLA）的有效引发剂。当[L-LAc]/[锌络合物] = 50 时，双配位锌络合物的转化率为 14-98%，聚合时间为 15-1440 分钟不等，当存在两个三氟甲基时，反应时间最长。添加 4-氟苯酚助催化剂后，甲苯溶液中的转化率提高了 5 倍，大量熔融聚合的转化率提高了 14 倍，但分离的聚乳酸的聚分散指数值却降低了。用 1H 和 19F NMR 研究了向复合物 1 添加 4-氟苯酚的情况，结果显示生成了一种原位生成的烷氧化锌复合物。
• Synthesis and structures of aluminum ion-pair complexes that act as L- and racemic-lactide ring opening polymerization initiators
  作者：Logan A. Schmitz、Alexandria M. McCollum、Arnold L. Rheingold、David B. Green、Joseph M. Fritsch

  DOI：10.1016/j.poly.2018.03.011

  日期：2018.6

  Seven aluminum ion-pair complexes (1-7) were synthesized by reaction of NNO Schiff base ketoimines with differing substituents with tris(2,6-dimethylphenoxy) aluminum dimer in an inert atmosphere glovebox at room temperature. The complexes were characterized with H-1, C-13, and F-19 nuclear magnetic resonance spectroscopy, absorbance spectroscopy, and elemental analysis. Furthermore, the dinuclear nature of the complexes was elucidated with single crystal X-ray crystallography and (27)AI NMR. The ion-pair complexes consisted of a bis-ligating homoleptic ketoiminate with octahedral coordination as an aluminum cation complex and a tetrahedral aluminum anion complex of 2,6-dimethylphenoxide. Each ion-pair was used to initiate the ring opening polymerization (ROP) of L- and rac-lactide to poly-lactic acid (PLA) in toluene at 100 degrees C at a 100:1 [LA]:[ion-pair] ratio. Proton NMR spectra showed percentage conversions of monomer to polymer of 96-99% in 18 h. The isolated polymeric materials were determined to have moderate molecular weights with low to moderate polydispersity index values using gel permeation chromatography. The bis-ligated aluminum cation and tetraphenoxide aluminate anions of 1 were isolated into separate compounds (8 and 9) with unreactive counter ions, and each yielded low molecular weight PLA under the polymerization conditions. Thus, lactide polymerization appeared to require both ion-pair components to yield the moderately high molecular weight PLA, and this was investigated spectroscopically. (C) 2018 Elsevier Ltd. All rights reserved.
• Synthesis and crystal structures of magnesium complexes with NNO Schiff base ligands bearing quinolyl pendant donors
  作者：Courtney C. Roberts、Joseph M. Fritsch

  DOI：10.1016/j.poly.2010.01.001

  日期：2010.3

  A series of ketoimines bearing quinolyl pendants was prepared through Schiff base condensation of 1,3-diketones (2,4-pentanedione, benzoylmethane, and 1-benzoylacetone) and 8-aminoquinoline or 8-amino-2-methylquinoline. The ketoimines were isolated in 46-90% yield and characterized spectroscopically and crystallographically. Reaction of the ketoimines with magnesium 4-methylbenzylalkoxide yielded octahedral magnesium complexes in 67-90% yield. The spectroscopic and crystallographic properties of the magnesium complexes were explored. Structures of 1, 4, 8, 10, and 11 are reported. (C) 2010 Elsevier Ltd. An rights reserved.