N-(2,2-二甲基亚丙基)-对甲苯胺 | 189161-98-6

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 中文名称: N-(2,2-二甲基亚丙基)-对甲苯胺
• 英文名称: N-(2,2-dimethylpropylidene)-p-toluidine
• 英文别名: 1-p-Tolylimino-2,2-dimethyl-propan；2,2-dimethyl-N-(4-methylphenyl)propan-1-imine
• CAS: 189161-98-6
• 化学式: C₁₂H₁₇N
• 分子量: 175.274
• InChiKey: PHNPERHIBOVCQT-UHFFFAOYSA-N

物化性质

• 沸点：
  263.5±23.0 °C(Predicted)
• 密度：
  0.86±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.3
• 重原子数：
  13
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.42
• 拓扑面积：
  12.4
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  CpTa(NtBu)Cl2 、 N-(2,2-二甲基亚丙基)-对甲苯胺 在 p-tolylamine 作用下， 以 氘代苯 为溶剂， 生成
  参考文献：
  名称：

  Role of Trace Amine in the Metathesis of Imines by CpTa(NR)Cl₂

  摘要：

  Tantalum imido compound CpTa(=NBut)Cl-2 (1) reacts with imines to give NR exchange (metathesis) products. Addition of < 5 mol % of compound I to a 1: 1 mixture of two different imines resulted in catalytic cross metathesis of the two imines to give an equilibrium mixture of imines. Kinetic studies of the reaction of I with excess imine (Bu-t)HC=N(p-tolyl) (2a) gave an average k(obs) of 1.29 x 10(-1) min(-1) (sigma 0.28). Pseudo-first-order behavior was observed for 1. The dependence of k(obs) on the concentration of 2a was found to be nonlinear and dependent on catalytic amounts of contaminant amine p-tolylamine (9). Reaction of 1 with tert-butylamine 6) results in the formation of the imide/amide CpTa(=NBut)(NHBut)Cl 7) and HCl. Compound 7 did not react with imines to give exchange products, so it is proposed that the reaction of 1 with imines is significantly accelerated by the presence of HCl.

  DOI：

  10.1021/om011085v
• 作为产物：
  描述：

  N-(9-Borabicyclo[3.3.1]non-9-yl)toluidine 、 特戊醛 在 2,2,2-三氟苯乙酮 作用下， 以 氘代苯 为溶剂， 反应 0.17h， 以99%的产率得到N-(2,2-二甲基亚丙基)-对甲苯胺
  参考文献：
  名称：

  现成的伯氨基硼烷现成可用，可作为强大的醛二胺合成试剂

  摘要：

  伯氨基硼烷（RNHBR 2）很容易通过胺和硼烷的自发脱氢偶联在室温下与醛干净地反应生成醛亚胺。从胺到醛亚胺的整体转化可以通过顺序的一锅法反应方便地进行。这种合成策略特别适用于在脱水条件下不愿与醛反应的贫电子胺和笨重胺。使用Glorius稳健性屏幕，我们证明了这种方法是化学选择性的，并且对官能团具有耐受性。计算和实验数据支持与传统方法形成鲜明对比的醛亚胺产物的不可逆形成。

  DOI：

  10.1002/anie.201814081

文献信息

• An electron paramagnetic resonance study of intermediates generated from aromatic aldiminesElectronic supplementary information (ESI) available: Gaussian98 or Jaguar optimised structures for precursor imines and imidoyl radicals together with their energies at all levels of theory. See http://www.rsc.org/suppdata/p2/b2/b201682f/
  作者：Daniele Nanni、Patrizia Pareschi、John C. Walton

  DOI：10.1039/b201682f

  日期：2002.5.22

  It was shown by EPR spectroscopy that N-aryl-imines undergo hydrogen atom abstraction by tert-butoxyl radicals to generate imidoyl radicals in competition with addition to the CN double bond to generate aminyl radicals. The latter were subsequently oxidised to nitroxides (aminoxyls) and also fragmented to release tert-butyl radicals and iminyl ethers. The main products identified were imines formed by combination of the imidoyl radicals with other radicals in the system. Thus, hydrogen abstraction is probably the most important homolytic pathway for the precursor imines. A similar reactivity pattern was found for N-tert-butyl-imines. DFT computations (B3LYP with a 6-31G* basis set) indicated that α-scissions of imidoyl radicals, ArNC˙R (R = t-Bu or Me), to produce isonitriles, ArNC, were too endothermic to occur under the present experimental conditions. tert-Butoxyl radicals were shown to add to 1-isocyano-4-chlorobenzene to generate N-arylimidoyl radicals that fragmented to afford 4-chloro-1-isocyanatobenzene.

  EPR 光谱显示，N-芳基-亚胺通过叔丁氧自由基抽取氢原子生成亚胺酰自由基，与此同时，CN 双键加成生成氨基自由基。后者随后被氧化成亚硝基（aminoxyls），并破碎释放出叔丁基自由基和亚氨基醚。鉴定出的主要产物是咪酰基与系统中其他自由基结合形成的亚胺。因此，氢抽取可能是前体亚胺最重要的均聚途径。在 N-叔丁基亚胺中也发现了类似的反应模式。DFT 计算（采用 6-31G* 基集的 B3LYP）表明，在目前的实验条件下，亚胺酰基 ArNC˙R（R = t-Bu 或 Me）生成异腈 ArNC 的 α 裂解反应过于耗热。
• Role of Trace Amine in the Metathesis of Imines by CpTa(NR)Cl₂
  作者：Matthew C. Burland、Timothy W. Pontz、Tara Y. Meyer

  DOI：10.1021/om011085v

  日期：2002.4.29

  Tantalum imido compound CpTa(=NBut)Cl-2 (1) reacts with imines to give NR exchange (metathesis) products. Addition of < 5 mol % of compound I to a 1: 1 mixture of two different imines resulted in catalytic cross metathesis of the two imines to give an equilibrium mixture of imines. Kinetic studies of the reaction of I with excess imine (Bu-t)HC=N(p-tolyl) (2a) gave an average k(obs) of 1.29 x 10(-1) min(-1) (sigma 0.28). Pseudo-first-order behavior was observed for 1. The dependence of k(obs) on the concentration of 2a was found to be nonlinear and dependent on catalytic amounts of contaminant amine p-tolylamine (9). Reaction of 1 with tert-butylamine 6) results in the formation of the imide/amide CpTa(=NBut)(NHBut)Cl 7) and HCl. Compound 7 did not react with imines to give exchange products, so it is proposed that the reaction of 1 with imines is significantly accelerated by the presence of HCl.
• Readily Available Primary Aminoboranes as Powerful Reagents for Aldimine Synthesis
  作者：Glen P. Junor、Erik A. Romero、Xi Chen、Rodolphe Jazzar、Guy Bertrand

  DOI：10.1002/anie.201814081

  日期：2019.2.25

  Primary aminoboranes (RNHBR2), which are readily available by spontaneous dehydrocoupling of amines and boranes cleanly react at room temperature with aldehydes to give aldimines. The overall transformation from amines to aldimines can be conveniently performed by a sequential one‐pot reaction. This synthetic strategy is especially useful for electron poor and bulky amines which are reluctant to react

  伯氨基硼烷（RNHBR 2）很容易通过胺和硼烷的自发脱氢偶联在室温下与醛干净地反应生成醛亚胺。从胺到醛亚胺的整体转化可以通过顺序的一锅法反应方便地进行。这种合成策略特别适用于在脱水条件下不愿与醛反应的贫电子胺和笨重胺。使用Glorius稳健性屏幕，我们证明了这种方法是化学选择性的，并且对官能团具有耐受性。计算和实验数据支持与传统方法形成鲜明对比的醛亚胺产物的不可逆形成。