1-phenylazasilantrane | 31701-37-8

• 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: 1-phenylazasilantrane
• 英文别名: 1-phenyl-2,5,8,9-tetraaza-1-sila-bicyclo[3.3.3]undecane；(TB-5-13)-phenyl-[tris-(2-amino-ethyl)-aminato(3-)-N,N',N'',N''']-silicon；1-Phenyl-2,5,8,9-tetraza-1-silabicyclo[3.3.3]undecane
• CAS: 31701-37-8
• 化学式: C₁₂H₂₀N₄Si
• 分子量: 248.403
• InChiKey: AHGRRPHLACQJSP-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -1.07
• 重原子数：
  17
• 可旋转键数：
  1
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  39.3
• 氢给体数：
  3
• 氢受体数：
  4

反应信息

• 作为产物：
  描述：

  三[2-(甲基氨基)乙基]胺 在 四氯化碳 、 N-氯代丁二酰亚胺 作用下， 以 乙醚 、 二氯甲烷 、 环己烷 、 氘代苯 、 甲苯 为溶剂， 反应 17.0h， 生成 1-phenylazasilantrane
  参考文献：
  名称：

  Hydride and Fluoride Transfer Reactions Accompanying Nucleophilic Substitution at Pentacoordinate Silicon

  摘要：

  The syntheses of aminoazasilatranes of the type R(2)NSi(R'NCH2CH2)(3)N (R' = H, R = H (2a), CH3 (3a), CH2CH3 (4a), Si(CH3)(3) (6a), R' = CH3, R = H (2b), CH3 (3b), CH2CH3 (4b), Si(CH3)(3) (6b) via nucleophilic substitution reactions of ClSi(R'NCH2CH2)(3)N (R' = H (7a), R' = CH3 (7b), respectively) with amide anions are reported. Reactivities of 7a and 7b;toward other nucleophilic reagents such as alkyllithiums and Group 1 metal alkoxides are also described. It is found that the equatorial NR' functionalities significantly influence the reaction pathways. With strong bases, lithiation of the equatorial NH hydrogens of 7a predominated along with some nucleophilic substitution products and hydride transfer product HSi(HNCH2CH2)(3)N, 1a. With 7b, however, equatorial nitrogen Lithiation is precluded and its reaction with nucleophiles can produce substantial amounts of nucleophilic substitution product as well as hydride transfer product HSi(CH3NCH2CH2)(3)N, 1b. The relative ratios of these products depend substantially on stereoelectronic factors, the nature of the nucleophilic reagents, and the reaction conditions. In the case of the reaction of 7b with BrC5F5/n-BuLi, three products, namely, C6F5Si(CH3NCH2CH2)(3)N (13b), FSi(CH3NCH2CH2)(3)N (14b), and C6F5Si(CH3NCH2CH2)(2)(o-C6F4CH3NCH2CH2)N (15) formed in;an approximate ratio of 1:2:1. The formation of 15 is attributed to perfluorobenzyne insertion into a Si-N-eq bond of (13b). Interestingly, the plane defined by the axial NSi2 moiety in 6a is found to be fixed at the apical position of the silicon, providing an interesting example of p pi-d pi interaction between a pentacoordinate silicon and a nitrogen. However, the axial moiety in analogue 6b freely rotates around the apical Si-N bond due to steric interactions with nearby methyl groups on the cage.

  DOI：

  10.1021/ja00106a018

文献信息

• Lukevits,E. et al., Journal of general chemistry of the USSR, 1977, vol. 47, p. 98 - 101
  作者：Lukevits,E. et al.

  DOI：——

  日期：——
• Hydride and Fluoride Transfer Reactions Accompanying Nucleophilic Substitution at Pentacoordinate Silicon
  作者：Yanjian Wan、John G. Verkade

  DOI：10.1021/ja00106a018

  日期：1995.1

  The syntheses of aminoazasilatranes of the type R(2)NSi(R'NCH2CH2)(3)N (R' = H, R = H (2a), CH3 (3a), CH2CH3 (4a), Si(CH3)(3) (6a), R' = CH3, R = H (2b), CH3 (3b), CH2CH3 (4b), Si(CH3)(3) (6b) via nucleophilic substitution reactions of ClSi(R'NCH2CH2)(3)N (R' = H (7a), R' = CH3 (7b), respectively) with amide anions are reported. Reactivities of 7a and 7b;toward other nucleophilic reagents such as alkyllithiums and Group 1 metal alkoxides are also described. It is found that the equatorial NR' functionalities significantly influence the reaction pathways. With strong bases, lithiation of the equatorial NH hydrogens of 7a predominated along with some nucleophilic substitution products and hydride transfer product HSi(HNCH2CH2)(3)N, 1a. With 7b, however, equatorial nitrogen Lithiation is precluded and its reaction with nucleophiles can produce substantial amounts of nucleophilic substitution product as well as hydride transfer product HSi(CH3NCH2CH2)(3)N, 1b. The relative ratios of these products depend substantially on stereoelectronic factors, the nature of the nucleophilic reagents, and the reaction conditions. In the case of the reaction of 7b with BrC5F5/n-BuLi, three products, namely, C6F5Si(CH3NCH2CH2)(3)N (13b), FSi(CH3NCH2CH2)(3)N (14b), and C6F5Si(CH3NCH2CH2)(2)(o-C6F4CH3NCH2CH2)N (15) formed in;an approximate ratio of 1:2:1. The formation of 15 is attributed to perfluorobenzyne insertion into a Si-N-eq bond of (13b). Interestingly, the plane defined by the axial NSi2 moiety in 6a is found to be fixed at the apical position of the silicon, providing an interesting example of p pi-d pi interaction between a pentacoordinate silicon and a nitrogen. However, the axial moiety in analogue 6b freely rotates around the apical Si-N bond due to steric interactions with nearby methyl groups on the cage.