N,N'-bis(1,1-dimethylethyl)-1,2-diphenylethane-1,2-diimine | 38015-77-9

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 二苯乙烯类
• 英文名称: N,N'-bis(1,1-dimethylethyl)-1,2-diphenylethane-1,2-diimine
• 英文别名: (t)Bu-N=C(Ph)-C(Ph)=N-(t)Bu；N,N'-ditert-butyl-1,2-diphenylethane-1,2-diimine
• CAS: 38015-77-9
• 化学式: C₂₂H₂₈N₂
• 分子量: 320.478
• InChiKey: UEXWRRSBISZIPW-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.1
• 重原子数：
  24
• 可旋转键数：
  5
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.36
• 拓扑面积：
  24.7
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  N,N'-bis(1,1-dimethylethyl)-1,2-diphenylethane-1,2-diimine 、 三氯化铁 以 二氯甲烷 为溶剂， 生成 [(t)Bu-N=C(Ph)-C(Ph)=N-(t)Bu]FeCl3
  参考文献：
  名称：

  Correlation of Metal Spin-State in α-Diimine Iron Catalysts with Polymerization Mechanism

  摘要：

  The alpha-diimine iron complexes, (R',R '')[N,N]FeCl2 ((R',R '')[N,N] = R'-N=CR"-CR ''=N-R', where R' = tert-butyl (tBu), cyclohexyl (Cy) and R '' = phenyl (Ph), para-fluorophenyl (F-Ph), para-bromophenyl (Br-Ph), para-methylphenyl (Me-Ph), or para-methoxyphenyl (MeO-Ph)), are found to polymerize styrene through a catalytic chain transfer (CCT) mechanism. Magnetic moment measurements indicate that Fe(III) complexes containing these ligands possess intermediate (S = 3/2) spin-state iron centers. In contrast, Fe(III) complexes bearing proton (R '' = H) and paradimethylaminophenyl (R '' = NMe2-Ph) substituents are high-spin and are efficient atom transfer radical polymerization (ATRP) catalysts. Hammett plots show a linear correlation of the substituent constant, sigma, with polymerization rate and polymer molecular weight, respectively.

  DOI：

  10.1021/ic701500y
• 作为产物：
  描述：

  异氰酸叔丁酯 、 三苯基锑 在 palladium diacetate 作用下， 以 苯 为溶剂， 反应 18.0h， 以18%的产率得到N,N'-bis(1,1-dimethylethyl)-1,2-diphenylethane-1,2-diimine
  参考文献：
  名称：

  Palladium-Catalyzed Synthesis of α-Diimines from Triarylbismuthines and Isocyanides

  摘要：

  In this study, we report a highly selective coupling reaction between triarylbismuthines and isocyanides using palladium diacetate as the catalyst, affording alpha-diimines, with the formation of three C-C bonds. Among several aryl sources,(Ar-YLn : Y = B, Sn, Pb, Sb, Bi, I), only triarylbismuthines successfully undergo coupling with isocyanides to selectively afford alpha-diimines. The coupling reaction exhibits the advantages of high atom economy and convenient operation, with no need for any additive.

  DOI：

  10.1021/acs.orglett.5b01566

文献信息

• Palladium-Catalyzed Diarylation of Isocyanides with Tetraarylleads for the Selective Synthesis of Imines and α-Diimines
  作者：Cong Chi Tran、Shin-ichi Kawaguchi、Yohsuke Kobiki、Hitomi Matsubara、Dat Phuc Tran、Shintaro Kodama、Akihiro Nomoto、Akiya Ogawa

  DOI：10.1021/acs.joc.9b01639

  日期：2019.9.20

  Using tetraaryllead compounds (PbAr4) as arylating reagents, isocyanides undergo selective diarylation in the presence of palladium catalysts such as Pd(OAc)(2) or Pd(PPh3)(4) to afford imines and/or alpha-diimines based on the isocyanide employed. With aliphatic isocyanides, imines are obtained preferentially, whereas alpha-diimines are formed in the case of electron-rich aromatic isocyanides. The differences in imine/alpha-diimine selectivity can be attributed to the stability of imidoylpalladium intermediates formed in this catalytic reaction. Compared with other arylating reagents, tetraaryllead compounds are excellent candidates for use in the selective transformations to imines and/or alpha-diimines, especially in terms of inhibiting the oligomerization of isocyanides, which results in a lower product selectivity in many transition-metal-catalyzed reactions of isocyanides.
• Palladium-Catalyzed Synthesis of α-Diimines from Triarylbismuthines and Isocyanides
  作者：Yohsuke Kobiki、Shin-ichi Kawaguchi、Akiya Ogawa

  DOI：10.1021/acs.orglett.5b01566

  日期：2015.7.17

  In this study, we report a highly selective coupling reaction between triarylbismuthines and isocyanides using palladium diacetate as the catalyst, affording alpha-diimines, with the formation of three C-C bonds. Among several aryl sources,(Ar-YLn : Y = B, Sn, Pb, Sb, Bi, I), only triarylbismuthines successfully undergo coupling with isocyanides to selectively afford alpha-diimines. The coupling reaction exhibits the advantages of high atom economy and convenient operation, with no need for any additive.
• Correlation of Metal Spin-State in α-Diimine Iron Catalysts with Polymerization Mechanism
  作者：Laura E. N. Allan、Michael P. Shaver、Andrew J. P. White、Vernon C. Gibson

  DOI：10.1021/ic701500y

  日期：2007.10.1

  The alpha-diimine iron complexes, (R',R '')[N,N]FeCl2 ((R',R '')[N,N] = R'-N=CR"-CR ''=N-R', where R' = tert-butyl (tBu), cyclohexyl (Cy) and R '' = phenyl (Ph), para-fluorophenyl (F-Ph), para-bromophenyl (Br-Ph), para-methylphenyl (Me-Ph), or para-methoxyphenyl (MeO-Ph)), are found to polymerize styrene through a catalytic chain transfer (CCT) mechanism. Magnetic moment measurements indicate that Fe(III) complexes containing these ligands possess intermediate (S = 3/2) spin-state iron centers. In contrast, Fe(III) complexes bearing proton (R '' = H) and paradimethylaminophenyl (R '' = NMe2-Ph) substituents are high-spin and are efficient atom transfer radical polymerization (ATRP) catalysts. Hammett plots show a linear correlation of the substituent constant, sigma, with polymerization rate and polymer molecular weight, respectively.