N,N'-dicyclohexyl-3-(4-methylphenyl)propiolamidine | 37057-55-9

• 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'-dicyclohexyl-3-(4-methylphenyl)propiolamidine
• 英文别名: N,N'-dicyclohexyl-3-p-tolylpropiolamidine；N,N'-dicyclohexyl-3-(4-methylphenyl)prop-2-ynimidamide
• CAS: 37057-55-9
• 化学式: C₂₂H₃₀N₂
• 分子量: 322.494
• InChiKey: BLYKKYXHVVUZRA-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.9
• 重原子数：
  24
• 可旋转键数：
  5
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.59
• 拓扑面积：
  24.4
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为产物：
  描述：

  N,N'-二环己基碳二亚胺 、 4-甲苯基乙炔 在 [2-(^tBuN=CH)C₈H₅N]Sm[N(SiMe₃)₂]₂ 作用下， 以 四氢呋喃 为溶剂， 反应 12.5h， 以78%的产率得到N,N'-dicyclohexyl-3-(4-methylphenyl)propiolamidine
  参考文献：
  名称：

  合成和2-表征吨-butylimino官能的催化加成末端炔烃的碳二亚胺来吲哚基稀土类金属络合物酰胺：二聚配合物在μ-η的alkynide种类1：η 2接合模式†

  摘要：

  通过仲胺的脱氢反应，合成了一系列带有2-叔丁基亚氨基官能化的吲哚基配体的稀土金属酰胺配合物，并对其反应性和催化性能进行了研究。2-（t BuNHCH 2）C 8 H 5 NH（1）与稀土金属酰胺[（Me 3 Si）2 N] 3 RE（μ-Cl）Li（THF）3的反应提供了络合物[2 -（t BuN CH）C 8 H 5 N] RE [N（SiMe 3）2 ] 2（RE = Er（2），Y（3），Dy（4），Sm（5），Nd（6））含有通过胺脱氢成亚胺基的二齿配体。配合物2–6在向碳二亚胺中添加末端炔烃时表现出优异的催化活性，从而提供了一系列相应的N，N'-二烷基-丙酰胺基。所述催化剂还可以有效地用于制备体积庞大的N，N′-二芳基-丙酰胺基。此外，二聚复合物{（μ-η 1：η 2 -RC C）RE [2-（吨BUN CH）C 8 H ^ 5 N] 2 } 2（11：RE = Y，R = Ph值;

  DOI：

  10.1039/c9dt01582e

文献信息

• Divalent Lanthanide Complexes: Highly Active Precatalysts for the Addition of N−H and C−H Bonds to Carbodiimides
  作者：Zhu Du、Wenbo Li、Xuehua Zhu、Fan Xu、Qi Shen

  DOI：10.1021/jo801693z

  日期：2008.11.21

  lanthanide complexes with the formula LnL2(sol)x (L = N(TMS)2, sol = THF, x = 3, Ln = Sm (I), Eu (II), Yb (III); L = MeC5H4, sol = THF, x = 2, Ln = Sm (IV); L = ArO(Ar = [2,6-((t)Bu)2-4-MeC6H2]), sol = THF, x = 2, Ln = Sm (V)), especially complexes I- III, serve as excellent catalyst precursors for catalytic addition of various primary and secondary amines to carbodiimides, efficiently providing the

  各种具有式LnL2（sol）x（L = N（TMS）2，sol = THF，x = 3，Ln = Sm（I），Eu（II），Yb（III）; L = MeC5H4，溶胶＝ THF，x ＝ 2，Ln ＝ Sm（IV）； L ＝ ArO（Ar ＝ [2，6-（（t）Bu）2-4-MeC6H2]），溶胶＝ THF，x ＝ 2，Ln ＝ Sm（V）），尤其是配合物I-III，是将各种伯胺和仲胺催化加成到碳二亚胺上的极佳催化剂前体，可在无溶剂条件下有效地为相应的胍衍生物提供多种底物。该反应显示出良好的官能团耐受性。配合物I-III也是出色的预催化剂，可将末端炔烃加到碳二亚胺上，产生一系列丙lam基。在两个反应中均观察到Yb
• Cyclopentadienyl-Free Rare-Earth Metal Amides [{(CH₂SiMe₂){(2,6-<i>i</i>Pr₂C₆H₃)N}₂}Ln{N(SiMe₃)₂}(THF)] as Highly Efficient Versatile Catalysts for C–C and C–N Bond Formation
  作者：Yunjun Wu、Shaowu Wang、Lijun Zhang、Gaosheng Yang、Xiancui Zhu、Zhihong Zhou、Hong Zhu、Shihong Wu

  DOI：10.1002/ejoc.200901015

  日期：2010.1

  Efficient methods have been developed for the direct synthesis of amides from aldehydes and a straightforward route to propiolamidines using cyclopentadienyl-free rare-earth metal amides [(CH 2 SiMe 2 )(2,6-iPr 2 C 6 H 3 )N} 2 }LnN(SiMe 3 ) 2 }-(THF)] [Ln = Yb (1), Y (2), Dy (3), Sm (4), Nd (5)] as versatile catalysts. The results indicate that in the direct synthesis of amides from aldehydes the

  已经开发出从醛直接合成酰胺的有效方法和使用不含环戊二烯基的稀土金属酰胺 [(CH 2 SiMe 2 )(2,6-iPr 2 C 6 H 3 )N } 2 }LnN(SiMe 3 ) 2 }-(THF)] [Ln = Yb (1), Y (2), Dy (3), Sm (4), Nd (5)] 作为通用催化剂。结果表明，在醛直接合成酰胺中，催化剂的活性顺序为2>1∼3∼4∼5。这些方法具有催化剂制备容易、催化剂载量低、底物转化产物转化率高、反应条件温和以及与多种底物相容等优点。
• CNC-Pincer Rare-Earth Metal Amido Complexes with a Diarylamido Linked Biscarbene Ligand: Synthesis, Characterization, and Catalytic Activity
  作者：Xiaoxia Gu、Xiancui Zhu、Yun Wei、Shaowu Wang、Shuangliu Zhou、Guangchao Zhang、Xiaolong Mu

  DOI：10.1021/om500354s

  日期：2014.5.12

  In preparation of CNC-pincer rare-earth metal amido complexes with a diarylamido linked biscarbene ligand, it is found that conditions have a key influence on final products. Reaction of a THF suspension of bis[2-(3-benzylimidazolium)-4-methylphenyl]amine dichlorides (H3LCl2) with [(Me3Si)(2)N](3)RE(mu-Cl)Li(THF)(3) (RE = Yb, Eu, Sm) in THF at room temperature afforded the only unexpected fused-heterocyclic compound 8,9-dibenzyl-3,14-dimethyl-8a,9-dihydro-8H-benzo[4,5]imidazo-[2',1':2,3]imidazo[1,2-a]imidazo[2,1-c]quinoxaline (1) containing an imidazolyl ring and a piperidyl ring, which formed through carbene C-C and C-N coupling. However, the reaction of H3LCl2 with [(Me3Si)(2)N](3)Er(mu-Cl)Li(THF)(3) in toluene afforded the CNC-pincer erbium amido complex incorporating a diarylamido linked biscarbene ligand LEr[N(SiMe3)(2)](2) (2) in low yield and the above fused-heterocyclic compound 1. The stepwise reaction of H3LCl2 with strong bases (n-BuLi or LiCH2SiMe3) in THF for 4 h, followed by treatment with [(Me3Si)(2)N](3)RE(mu-Cl)Li(THF)(3), generated zwitterion complexes [L2RE][REClN(SiMe3)(2)}(3)] (L = [4-CH3-2-(C6H4CH2-[N(CH)(2)CN]}C6H3](2)N; RE = Y (3), Er (4), Yb (5)) in less than 20% yields together with fused-heterocyclic compound 1. Additionally, the reaction of H3LCl2 with 6 equiv of NaN(SiMe3)(2) in THF for 4 h, followed by treatment with YbCl3, generated a novel discrete complex [L2Yb][Na(mu-N(SiMe3)(2))}(5)(mu(5)-Cl)] (6). The one-pot reaction of H3LCl2 with n-BuLi, followed by reaction with [(Me3Si)(2)N](3)RE(mu-Cl)Li(THF)(3) in THF at -78 degrees C, generated the CNC-pincer lanthanide bisamido complexes LRE[N(SiMe3)(2)](2) (RE = Er (2), Y (7), Sm (8), Eu (9)) in moderate yields. These kinds of biscarbene supported pincer bisamido complexes could also be prepared by a one-pot reaction of bis(imidazolium) salt (H3LCl2) with 5 equiv of NaN(SiMe3)(2), followed by treatment with RECl3, in good yields at -78 degrees C. Investigation of the catalytic activity of complexes 2 and 7-9 indicated that all complexes showed a high activity toward the addition of terminal alkynes to carbodiimides producing propiolimidines, which represents the first example of rare-earth metal CNC-pincer-type catalysts applied for catalytic C-H bond addition of terminal alkynes to carbodiimides at room temperature.