ⁱPrNHC(NNMe₂)NHⁱPr | 1255649-85-4

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: ⁱPrNHC(NNMe₂)NHⁱPr
• 英文别名: (iPr)NHC(NNMe2)NH(iPr)；1-(Dimethylamino)-2,3-di(propan-2-yl)guanidine；1-(dimethylamino)-2,3-di(propan-2-yl)guanidine
• CAS: 1255649-85-4
• 化学式: C₉H₂₂N₄
• 分子量: 186.3
• InChiKey: LJXQOHNXRTWTPF-UHFFFAOYSA-N

物化性质

• 沸点：
  236.0±23.0 °C(Predicted)
• 密度：
  0.94±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.3
• 重原子数：
  13
• 可旋转键数：
  5
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.89
• 拓扑面积：
  39.7
• 氢给体数：
  2
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  偏二甲肼 、 N,N'-二异丙基碳二亚胺 在 [Ti(pentamethylcyclopentadienyl)(N(xylyl)C4H6N)(tert-butylimido)(tert-butylamine)] 作用下， 以 甲苯 为溶剂， 反应 18.0h， 以24%的产率得到ⁱPrNHC(NNMe₂)NHⁱPr
  参考文献：
  名称：

  Titanium-Catalyzed Hydrohydrazination of Carbodiimides

  摘要：

  Hydrazinediido complexes of the type [Cp*Ti-(NxylN)(NNR2)(L)] (R = Ph, Me; Ar, fluorene, L = (BuNH2)-Bu-t, Py; 3a-e) have been synthesized and used as catalysts for the hydrohydrazination of a series of carbodiimides, yielding aminoguanidines or fluoreneiminoguanidines. The highest yields were obtained for diarylhydrazines and fluorenone 5 hydrazone at temperatures between 80 and 105 degrees C. Stoichiometric reactions of hydraz inediido complexes with (PrNCNPr)-Pr-i-Pr-i led to an equilibrium with the resulting [2 + 2] cydoadducts 4a-f, which were characterized by H-1, C-13, and N-15 NMR spectroscopy as well as X-ray diffraction. The proposed mechanism, which is closely related to that previously established for the hydrohydrazination of alkynes and allenes, was found to be consistent with the results of a kinetic study. The dynamic structures of aminoguanidines and fluoreneiminoguanidines were characterized by NMR spectroscopy, and the minimum configurations were foud to be stabilized by intramolecular hydrogen bonding.

  DOI：

  10.1021/om400323p

文献信息

• Highly Efficient Aluminum-Catalyzed Hydro-amination/-hydrazination of Carbodiimides
  作者：Jürgen Koller、Robert G. Bergman

  DOI：10.1021/om100735q

  日期：2010.11.22

  The catalytic activity of commercially available [Al(NMe2)(3)](2) (1) and a dimethyl aluminum guanidinate complex toward the hydro-aminationi-hydrazination of carbodiimides was studied. The guanidinate-supported complex 2 was prepared via salt metathesis reactions of AlMe2Cl and an in situ generated lithium guanidinate reagent. X-ray crystallographic studies revealed the influence of the guanidinate ligand on the Al metal center. Hydroamination reactions were successfully carried out at room temperature with 2 as the catalyst, while 1 proved to be ineffective under these conditions. On the contrary, both 1 and 2 were active toward the hydro-hydrazination of carbodiimides, which were run at elevated temperatures (120 degrees C). Consequently, the reaction temperature had a significant influence on the choice of the catalyst since the catalytically active species can be generated from various precatalysts under different conditions. The formation of guanidines and aminoguanidines showed a high functional group tolerance and typically proceeded with excellent yields at low catalyst loadings. X-ray crystallographic studies of compound 4a revealed interesting structural features of the previously unknown aminoguanidine products. The independently isolated Al aminoguanidinate complex 5 showed catalytic activity toward hydro-hydrazination chemistry and provided valuable evidence in support of the proposed reaction mechanism.
• Titanium-Catalyzed Hydrohydrazination of Carbodiimides
  作者：Peter D. Schweizer、Hubert Wadepohl、Lutz H. Gade

  DOI：10.1021/om400323p

  日期：2013.7.8

  Hydrazinediido complexes of the type [Cp*Ti-(NxylN)(NNR2)(L)] (R = Ph, Me; Ar, fluorene, L = (BuNH2)-Bu-t, Py; 3a-e) have been synthesized and used as catalysts for the hydrohydrazination of a series of carbodiimides, yielding aminoguanidines or fluoreneiminoguanidines. The highest yields were obtained for diarylhydrazines and fluorenone 5 hydrazone at temperatures between 80 and 105 degrees C. Stoichiometric reactions of hydraz inediido complexes with (PrNCNPr)-Pr-i-Pr-i led to an equilibrium with the resulting [2 + 2] cydoadducts 4a-f, which were characterized by H-1, C-13, and N-15 NMR spectroscopy as well as X-ray diffraction. The proposed mechanism, which is closely related to that previously established for the hydrohydrazination of alkynes and allenes, was found to be consistent with the results of a kinetic study. The dynamic structures of aminoguanidines and fluoreneiminoguanidines were characterized by NMR spectroscopy, and the minimum configurations were foud to be stabilized by intramolecular hydrogen bonding.