N-(2-chloroethyl)-N-(trimethylsilyl)aniline | 1365973-65-4

• 英文名称: N-(2-chloroethyl)-N-(trimethylsilyl)aniline
• 英文别名: N-(2-chloroethyl)-N-trimethylsilylaniline
• CAS: 1365973-65-4
• 化学式: C₁₁H₁₈ClNSi
• 分子量: 227.809
• InChiKey: CHLQOXMJFDSFEO-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.57
• 重原子数：
  14
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.45
• 拓扑面积：
  3.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  N-(2-chloroethyl)-N-(trimethylsilyl)aniline 在 正丁基锂 、 sodium phosphide 、 二乙胺 作用下， 以 乙二醇二甲醚 、 乙醚 、 正己烷 为溶剂， 反应 21.83h， 生成 N,N’,N’’-triphenyl-tris-(3-aminopropyl)-phosphine
  参考文献：
  名称：

  Phospha Derivatives of Tris(2-aminoethyl)amine (tren) and Tris(3-aminopropyl)amine (trpn): Synthesis and Complexation Studies with Group 4 Metals

  摘要：

  The N,N',N ''-triphenyl-substituted derivative of tris(2-aminoethyl)phosphine (Ph-3-phospha-tren, P(CH2CH2NHR)(3), R = Ph) and four derivatives of the related tris(3-aminopropyl)phosphine (phospha-trpn, P(CH2CH2CH2NHR)(3), R = Pr-i, Bu-t, (SiBuMe2)-Bu-t, Ph) have been synthesized in addition to the parent phospha-trpn. Out of these ligand systems, only the N,N',N ''-triphenyl-substituted phospha-trpn derivative P(CH2CH2CH2NHPh)(3) was found to be suitable for coordination to group 4 metals. For titanium, zirconium, and hafnium, the C-3-symmetric endo-P-configured dimethylamido complexes Ph[PN3]M(NMe2) of the former ligand have been prepared and converted into the corresponding triflates Ph[PN3]M(OTf). Starting from these triflates, the benzyl complexes Ph[PN3]M(Bn) (M = Ti, Zr, Hf) have been obtained via reaction with Bn2Mg(THF)(2). In case of titanium, the benzyl species Ph[PN3]Ti(Bn) is prone to thermal elimination of toluene, which results in the formation of a cyclometalated species. These findings are discussed in context with the very few group 4 trisamidophosphine complexes that have been reported earlier.

  DOI：

  10.1021/acs.organomet.5b00065
• 作为产物：
  描述：

  N-苯基乙醇胺 在 六氯乙烷 、 三乙胺 、 三苯基膦 作用下， 以 二氯甲烷 为溶剂， 生成 N-(2-chloroethyl)-N-(trimethylsilyl)aniline
  参考文献：
  名称：

  Iron Complex-Catalyzed Ammonia–Borane Dehydrogenation. A Potential Route toward B–N-Containing Polymer Motifs Using Earth-Abundant Metal Catalysts

  摘要：

  Ammonia-borane (NH3BH3, AB) has garnered interest as a hydrogen storage material due to its high weight percent hydrogen content and ease of H-2 release relative to metal hydrides. As a consequence of dehydrogenation, B-N-containing oligomeric/polymeric materials are formed. The ability to control this process and dictate the identity of the generated polymer opens up the possibility of the targeted synthesis of new materials. While precious metals have been used in this regard, the ability to construct such materials using earth-abundant metals such as Fe presents a more economical approach. Four Fe complexes containing amido and phosphine supporting ligands were synthesized, and their reactivity with AB was examined. Three-coordinate Fe(PCy3)[N(SiMe3)(2)](2) (1) and four-coordinate Fe(DEPE)[N(SiMe3)(2)](2) (2) yield a mixture of (NH2BH2) and (NHBH)(n) products with up to 1.7 equiv of H-2 released per AB but cannot be recycled (DEPE = 1,2-bis(diethylphosphino)ethane). In contrast, Fe supported by a bidentate P-N ligand (4) can be used in a second cycle to afford a similar product mixture. Intriguingly, the symmetric analogue of 4 (Fe(N-N)(P-P), 3), only generates (NH2BH2) and does so in minutes at room temperature. This marked difference in reactivity may be the result of the chemistry of Fe(II) vs Fe(0).

  DOI：

  10.1021/ja210542r