(di-t-butylsilyl)amine | 138152-51-9

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机类金属化合物
• 英文名称: (di-t-butylsilyl)amine
• 英文别名: 1,1-Di-tert-butylsilanamine；2-[amino(tert-butyl)silyl]-2-methylpropane
• CAS: 138152-51-9
• 化学式: C₈H₂₁NSi
• 分子量: 159.347
• InChiKey: LZESIEOFIUDUIN-UHFFFAOYSA-N

物化性质

• 沸点：
  160.9±9.0 °C(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.27
• 重原子数：
  10
• 可旋转键数：
  2
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  26
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  (di-t-butylsilyl)amine 、 三异丁基铝 以 正己烷 为溶剂， 以70%的产率得到
  参考文献：
  名称：

  Syntheses, structures, and isomerization processes of dialkylaluminum silylamido complexes

  摘要：

  Reactions of R3SiNH2 with R'3Al in refluxing hexane afford a family of dimeric aluminum silylamides, [R'2AlN(H)SiR3]2 (R' = Me, R3 = Ph3, Et3; R' = i-Bu, R3 = Ph3, R3 = t-Bu2H). [Me2AlN(H)SiMe3]2 is prepared from [Cl2AlN(H)SiMe3]2 and dimethylmagnesium. X-ray crystallography of [Me2AlN(H)SiEt3]2 and [Me2AlN(H)SiPh3]2 indicates planar Al2N2 ring frameworks with the silyl groups oriented trans about the ring. A distorted-tetrahedral geometry at nitrogen places the silyl groups nearly in the plane of the Al2N2 ring, while the N-H bond vector is nearly orthogonal to the Al2N2 plane. The degree of distortion depends on the steric bulk of SiR3. All dimers undergo a cis-trans isomerization process in benzene. This process is fast for methylaluminum compounds but slow for isobutylaluminum ones: the methylaluminum amides attain equilibrium solution isomer distributions of ca. 50/50, while the isobutyl compounds are strongly biased toward the cis or trans isomer and do not attain equilibrium. Isomerization of the methylaluminum compounds is catalyzed by less than one equiv of 4-methylpyridine, while hindered pyridines have no effect. Greater amounts of 4-methylpyridine lead to adduct formation; the adduct (i-Bu)2(4-Me-py)AlN(H)SiPh3 is isolated. A mechanism with rate-determining attack of base at aluminum is discussed. Crystal data for [Me2AlN(H)SiPh3]2: M(r) = 662.96, triclinic, P1BAR, a = 8.821 (2) angstrom, b = 9.435 (3) angstrom, c = 13.342 (4) angstrom, alpha = 70.97 (3)-degrees, beta = 74.23 (2)-degrees, gamma = 66.02 (2)-degrees, Z = 1, R = 0.041, R(w) = 0.042. Crystal data for [Me2AlN(H)SiEt3]2: M(r) = 374.6, monoclinic, P2(1)/n, a = 7.095 (3) angstrom, b = 11.452 (5) angstrom, c = 15.467 (5) angstrom, beta = 96.83 (3)-degrees, Z = 2, R = 0.055, R(w) = 0.052.

  DOI：

  10.1021/om00038a005
• 作为产物：
  描述：

  di-tert-butylchlorosilane 在 氨 作用下， 反应 6.0h， 以68%的产率得到(di-t-butylsilyl)amine
  参考文献：
  名称：

  硅烷的 NMe2Et 加合物的化学和结构特征 Me2Si=NSitBu3 和 tBu2Si=NSiCltBu2

  摘要：

  与 tBu 2 SiN(Li)SiXtBu 2 (X = Cl, tBu) 相比，甲硅烷基酰胺 Me 2 SiClN(Li)SitBu 3 对 LiCl 消除不稳定，这意味着硅胺给体加合物 Me 2 Si=NSitBu 3 · NMe 2 Et 可以通过 Me 2 SiClN(H)SitBu 3 与 nBuLi 在 NMe 2 Et 存在下的反应以高产率合成。硅胺加合物tBu 2 Si=NSiCltBu 2 ·NMe 2 Et，在不饱和Si 中心具有庞大的tBu 取代基，可通过用NMe 2 Et 处理无供体的硅烷胺tBu 2 Si=NSiCltBu 2 来获得。硅烷胺加合物 Me 2 Si=NSitBu 3 ·NMe 2 Et（单斜晶系，P2 1 /n）的 X 射线质量晶体从戊烷在 -25 °C 下生长。在作为溶剂的 NMe 2 Et 中，加合物 Me 2 Si=NSitBu 3 ·NMe

  DOI：

  10.1002/ejic.200600614

文献信息

• New Silyl-Substituted Tin-Nitrogen Heterocubanes: Fourfold Metal-Coordinated Nitrogen and Exceptional Chemical and NMR Properties
  作者：Michael Veith、Michael Opsölder、Michael Zimmer、Volker Huch

  DOI：10.1002/(sici)1099-0682(200006)2000:6<1143::aid-ejic1143>3.3.co;2-h

  日期：2000.6
• Chemical and Structural Features of NMe ₂ Et Adducts of the Silanimines Me ₂ Si=NSi <i>t</i> Bu ₃ and <i>t</i> Bu ₂ Si=NSiCl <i>t</i> Bu ₂
  作者：Hans‐Wolfram Lerner、Michael Bolte、Klaus Schurz、Nils Wiberg、Gerhard Baum、Dieter Fenske、Jan W. Bats、Matthias Wagner

  DOI：10.1002/ejic.200600614

  日期：2006.12

  produce EtN(Me)CH 2 SiMe 2 N(H)SitBu 3 and EtN(Me)CH-[Me 2 SiN(H)SitBu 3 ] 2 , and EtN(Me)CH 2 SitBu 2 N(H)SiCltBu 2 , respectively. In contrast, the thermolysis of Me 2 Si=NSitBu 3 . NMe 2 Et in vacuo gives the silanimine dimer (Me 2 SiNSitBu 3 ) 2 (monoclinic, P2 1 /n) in 80 % yield. The benzophenone imine Ph 2 C=NSitBu 3 (triclinic, P1) was obtained from the Wittig-like reaction of Me 2 Si=N-SitBu 3

  与 tBu 2 SiN(Li)SiXtBu 2 (X = Cl, tBu) 相比，甲硅烷基酰胺 Me 2 SiClN(Li)SitBu 3 对 LiCl 消除不稳定，这意味着硅胺给体加合物 Me 2 Si=NSitBu 3 · NMe 2 Et 可以通过 Me 2 SiClN(H)SitBu 3 与 nBuLi 在 NMe 2 Et 存在下的反应以高产率合成。硅胺加合物tBu 2 Si=NSiCltBu 2 ·NMe 2 Et，在不饱和Si 中心具有庞大的tBu 取代基，可通过用NMe 2 Et 处理无供体的硅烷胺tBu 2 Si=NSiCltBu 2 来获得。硅烷胺加合物 Me 2 Si=NSitBu 3 ·NMe 2 Et（单斜晶系，P2 1 /n）的 X 射线质量晶体从戊烷在 -25 °C 下生长。在作为溶剂的 NMe 2 Et 中，加合物 Me 2 Si=NSitBu 3 ·NMe
• Syntheses, structures, and isomerization processes of dialkylaluminum silylamido complexes
  作者：Deborah M. Choquette、Mary Jo Timm、Jason L. Hobbs、M. Marufur Rahim、Kazi J. Ahmed、Roy P. Planalp

  DOI：10.1021/om00038a005

  日期：1992.2

  Reactions of R3SiNH2 with R'3Al in refluxing hexane afford a family of dimeric aluminum silylamides, [R'2AlN(H)SiR3]2 (R' = Me, R3 = Ph3, Et3; R' = i-Bu, R3 = Ph3, R3 = t-Bu2H). [Me2AlN(H)SiMe3]2 is prepared from [Cl2AlN(H)SiMe3]2 and dimethylmagnesium. X-ray crystallography of [Me2AlN(H)SiEt3]2 and [Me2AlN(H)SiPh3]2 indicates planar Al2N2 ring frameworks with the silyl groups oriented trans about the ring. A distorted-tetrahedral geometry at nitrogen places the silyl groups nearly in the plane of the Al2N2 ring, while the N-H bond vector is nearly orthogonal to the Al2N2 plane. The degree of distortion depends on the steric bulk of SiR3. All dimers undergo a cis-trans isomerization process in benzene. This process is fast for methylaluminum compounds but slow for isobutylaluminum ones: the methylaluminum amides attain equilibrium solution isomer distributions of ca. 50/50, while the isobutyl compounds are strongly biased toward the cis or trans isomer and do not attain equilibrium. Isomerization of the methylaluminum compounds is catalyzed by less than one equiv of 4-methylpyridine, while hindered pyridines have no effect. Greater amounts of 4-methylpyridine lead to adduct formation; the adduct (i-Bu)2(4-Me-py)AlN(H)SiPh3 is isolated. A mechanism with rate-determining attack of base at aluminum is discussed. Crystal data for [Me2AlN(H)SiPh3]2: M(r) = 662.96, triclinic, P1BAR, a = 8.821 (2) angstrom, b = 9.435 (3) angstrom, c = 13.342 (4) angstrom, alpha = 70.97 (3)-degrees, beta = 74.23 (2)-degrees, gamma = 66.02 (2)-degrees, Z = 1, R = 0.041, R(w) = 0.042. Crystal data for [Me2AlN(H)SiEt3]2: M(r) = 374.6, monoclinic, P2(1)/n, a = 7.095 (3) angstrom, b = 11.452 (5) angstrom, c = 15.467 (5) angstrom, beta = 96.83 (3)-degrees, Z = 2, R = 0.055, R(w) = 0.052.