[(N,N'-dibenzyl-2-amino-4-iminopent-2-ene(-1H))ZnEt] | 1226915-08-7

• 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,N'-dibenzyl-2-amino-4-iminopent-2-ene(-1H))ZnEt]
• 英文别名: (nacnac(Bn))ZnEt
• CAS: 1226915-08-7
• 化学式: C₂₁H₂₆N₂Zn
• 分子量: 371.841
• InChiKey: OTTRBOJBEALXQR-QPVFFDEVSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
  None
• 可旋转键数：
  None
• 环数：
  None
• sp3杂化的碳原子比例：
  None
• 拓扑面积：
  None
• 氢给体数：
  None
• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  [(N,N'-dibenzyl-2-amino-4-iminopent-2-ene(-1H))ZnEt] 在 rac-lactide 作用下， 以 二氯甲烷-D2 、 异丙醇 为溶剂， 生成 [(N,N'-dibenzyl-2-amino-4-iminopent-2-ene(-1H))2Zn]
  参考文献：
  名称：

  Lactide Polymerization with Chiral β-Diketiminate Zinc Complexes

  摘要：

  N,N'-Di(S-phenylethyl)-2-amino-4-iminopent-2-ene, S,S-nacnac(CH(Me)Ph)H, 1a, and N,N'-dibenzyl-2-amino-4-iminopent-2-ene, nacnac(Bn)H, 1b, react with ZnEt(2) to form the corresponding nacnacZnEt complexes 2a and 2b. Neither complex is reactive with 2-propanol or methyl lactate to produce the corresponding alkoxide complexes. In reactions with 2b, ligand redistribution occurs and nacnaca(2)(Bn)Zn was obtained. Reaction of 1a and 1b with Zn(N(SiMe(3))(2))(2) yielded nacnacZnN(SiMe(3))(2), 6a and 6b. From further reactions with 2-propanol nacnacZnOiPr, 7a and 7b, were obtained. Both complexes were catalytically active for polymerization of rac-lactide with apparent first-order rate constants of k(app) = 0.013-0.019 min(-1) and 0.019-0.038 min(-1) for 7a and 7b, respectively. Obtained polymers were highly heterotactic, with P(r) = 0.84-0.87 (7a) and 0.65-0.71 (7b). Analysis of remaining monomer after 75% conversion showed negligible ee and indicates that chiral 7a does not show enantioselectivity in rac-lactide polymerization. Complex 7a, but not 7b, catalyzes unselective transesterification of the polymer during and after polymerization. PLA microstructures in polymerizations with 7b were independent of temperature (23 or 0 degrees C) or monomer/catalyst ratio (100:1 to 400:1). However, slightly higher Pr values were obtained in the presence of 10-100 equiv of MeCN or pyridine. Complexes nacnac(2)(Bn)ZN, 2b, 6b, and 7a were characterized by an X-ray diffraction study.

  DOI：

  10.1021/om100154w
• 作为产物：
  描述：

  2-Benzylamino-4-benzylimino-penten-2 以 正己烷 、 氘代苯 为溶剂， 生成 [(N,N'-dibenzyl-2-amino-4-iminopent-2-ene(-1H))ZnEt]
  参考文献：
  名称：

  Lactide Polymerization with Chiral β-Diketiminate Zinc Complexes

  摘要：

  N,N'-Di(S-phenylethyl)-2-amino-4-iminopent-2-ene, S,S-nacnac(CH(Me)Ph)H, 1a, and N,N'-dibenzyl-2-amino-4-iminopent-2-ene, nacnac(Bn)H, 1b, react with ZnEt(2) to form the corresponding nacnacZnEt complexes 2a and 2b. Neither complex is reactive with 2-propanol or methyl lactate to produce the corresponding alkoxide complexes. In reactions with 2b, ligand redistribution occurs and nacnaca(2)(Bn)Zn was obtained. Reaction of 1a and 1b with Zn(N(SiMe(3))(2))(2) yielded nacnacZnN(SiMe(3))(2), 6a and 6b. From further reactions with 2-propanol nacnacZnOiPr, 7a and 7b, were obtained. Both complexes were catalytically active for polymerization of rac-lactide with apparent first-order rate constants of k(app) = 0.013-0.019 min(-1) and 0.019-0.038 min(-1) for 7a and 7b, respectively. Obtained polymers were highly heterotactic, with P(r) = 0.84-0.87 (7a) and 0.65-0.71 (7b). Analysis of remaining monomer after 75% conversion showed negligible ee and indicates that chiral 7a does not show enantioselectivity in rac-lactide polymerization. Complex 7a, but not 7b, catalyzes unselective transesterification of the polymer during and after polymerization. PLA microstructures in polymerizations with 7b were independent of temperature (23 or 0 degrees C) or monomer/catalyst ratio (100:1 to 400:1). However, slightly higher Pr values were obtained in the presence of 10-100 equiv of MeCN or pyridine. Complexes nacnac(2)(Bn)ZN, 2b, 6b, and 7a were characterized by an X-ray diffraction study.

  DOI：

  10.1021/om100154w

文献信息

• A Bifunctional Diketimine Ligand for Secondary Building Blocks: Formation of a 2D Copper–Zinc Coordination Polymer
  作者：Élodie Rousset、Todd J. J. Whitehorne、Valérie Baslon、Christian Reber、Frank Schaper

  DOI：10.1002/ejic.201000903

  日期：2011.1

  no-4-imino-pent-2-ene, nacnacCH2PyH, a diketimine with pendant pyridine donors.Under the same conditions, 2- and 4-(aminomethyl)pyridine afforded the respective 1-(2-pyridyl)- and 1-(4-pyridyl)-2,4-dimethylpyrrol. The heteroleptic complex (nacnacCH2Py)(nacnacBn)Zn was obtained upon reaction of nacnacCH2PyH with nacnacBnZnEt. Combining 2 equiv. of this ligand with ZnEt2 afforded the homoleptic complex

  3-（氨基甲基）吡啶与乙酰丙酮在 2 当量存在下的缩合反应。HCl 得到 N,N'-双（3-吡啶基甲基）-2-氨基-4-亚氨基-戊-2-烯，nacnacCH2PyH，一种带有侧链吡啶供体的双酮亚胺。在相同条件下，2-和4-（氨基甲基）吡啶得到相应的 1-(2-吡啶基)-和 1-(4-吡啶基)-2,4-二甲基吡咯。通过 nacnacCH2PyH 与 nacnacBnZnEt 反应获得杂配复合物 (nacnacCH2Py)(nacnacBn)Zn。结合2当量。该配体与 ZnEt2 的反应得到均配复合物 nacnacCH2Py2Zn。后者在与 [Cu(NCMe)4][PF6] 反应后形成二维配位聚合物，在环境温度下显示出短暂的发光。配位聚合物和配合物 (nacnacCH2Py)(nacnacBn)Zn 通过单晶 X 射线衍射表征。