1,1,3,3-tetramethyl-1,3-bis(N-methyl-N'-phenylsulfonyl-(S)-prolinamidomethyl)-1,3-disiloxane | 1375314-03-6

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: 1,1,3,3-tetramethyl-1,3-bis(N-methyl-N'-phenylsulfonyl-(S)-prolinamidomethyl)-1,3-disiloxane
• CAS: 1375314-03-6
• 化学式: C₃₀H₄₆N₄O₇S₂Si₂
• 分子量: 695.021
• InChiKey: LRPYCJPILPKPLC-NSOVKSMOSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.12
• 重原子数：
  45.0
• 可旋转键数：
  12.0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.53
• 拓扑面积：
  124.61
• 氢给体数：
  0.0
• 氢受体数：
  7.0

反应信息

• 作为反应物：
  描述：

  1,1,3,3-tetramethyl-1,3-bis(N-methyl-N'-phenylsulfonyl-(S)-prolinamidomethyl)-1,3-disiloxane 在 三氟化硼乙醚 作用下， 以 乙腈 为溶剂， 反应 2.0h， 以85%的产率得到(O->Si)chelate N'-(dimethylfluorosilylmethyl)-N'-methyl-N-phenylsulfonyl-(S)-prolinamide
  参考文献：
  名称：

  Synthesis, Structures, and Stereodynamic Behavior of Novel Pentacoordinate Fluorosilanes: Fluorosilyl Derivatives of Proline

  摘要：

  The (O -> Si)-chelate N'-(dimethylfluorosilylmethyl))-N'-methyl-N-(organosulfonyl)prolinamides RSO2-Pro-N(Me)CH2SiMe2F (2a-f, R = Me (a), Ph (b), 4-MeC6H4 (c), 4-ClC6H4 (d), 4-BrC6H4 (e), 4-NO2C6H4 (f)) were synthesized from the corresponding disiloxanes 1a-f using Et2O center dot BF3. According to the NMR and IR data, the extent of dimerization of fluorosilanes 2a-f in solution is negligible, while the O -> Si coordination in solution is weaker than that in the solid state. Comparative CP/MAS NMR and X-ray diffraction studies revealed that in solution the coordination Si-O bond length varies in a narrow range (2.22-2.24 angstrom) that is 0.02-0.11 angstrom longer than in the crystalline state. Dynamic NMR (DNMR) studies of the fluorides revealed a fine structure of the F-19 signals in the 0-20 degrees C temperature range, which was related to the structural features of the coordination set in these complexes. The temperature dependence of the SiMe2 signals in the H-1 DNMR spectra was attributed to a permutational isomerization process involving a positional exchange of equatorial ligands. The narrow range of activational barriers of the process (23-24 kcal mol(-1) and more) and high negative values of the entropy of activation are similar to those observed earlier for Si-substituted N-(dimethylsilylmethyl) and N-(methylphenylsilylmethyl) amides and lactams, which suggests similar permutational processes in all cases. Gas-phase quantum chemical studies demonstrate that the solvation of F- reduces the activation barrier.

  DOI：

  10.1021/om3002697
• 作为产物：
  描述：

  N-(dimethylchlorosilylmethyl)-N-methyl-N'-phenylsulfonyl-(S)-prolinamide 在 水 、 碳酸氢钠 作用下， 以 氯仿 为溶剂， 反应 24.0h， 以95%的产率得到1,1,3,3-tetramethyl-1,3-bis(N-methyl-N'-phenylsulfonyl-(S)-prolinamidomethyl)-1,3-disiloxane
  参考文献：
  名称：

  具有由N-甲基-N'-有机磺酰基-脯氨酰胺衍生的C，O-螯合物的五配位氯硅烷*

  摘要：

  酰胺RSO 2 -Pro-NHMe与ClCH 2 SiMe 2 Cl在（Me 3 Si）2 NH存在下的反应生成了带有有机磺酰基基团的五配位氯硅烷RSO 2 -Pro-N（Me）CH 2 SiMe 2 Cl（R = Me中的pH值，4-CLC 6 ħ 4，4- BRC 6 ħ 4，4-MEC 6 ħ 4，和4-O 2 NC 6 H ^ 4）附着在脯氨酸的氮原子上 制备这些化合物的另一种方法包括在第一步骤中通过二甲基氯甲基氯硅烷使脯氨酸甲酰胺的环甲硅烷基甲基化，得到先前未报道的杂环2-sila-5-哌嗪酮系统。合成的双环硅环烷是与脯氨酸残基缩合的2-sila5-哌嗪酮。磺酰氯RSO 2 Cl的作用导致硅烷基环Si-N键断裂，从而得到所需的氯硅烷。这些产物的水解，取决于反应条件，给出氯化硅氧鎓氯化物[RSO 2 -ProN（Me）CH 2 SiMe 2 OH 2 ] Cl或二硅氧烷[RSO 2

  DOI：

  10.1007/s10593-012-0949-7