1,8-bis[tris(pyrrolidino)phosphazenyl bis(pyrrolidino)phosphazenyl]naphthalene

• 分子结构分类: 有机化合物 - 苯类化合物 - 萘
• 英文名称: 1,8-bis[tris(pyrrolidino)phosphazenyl bis(pyrrolidino)phosphazenyl]naphthalene
• 化学式: C₅₀H₈₆N₁₄P₄
• 分子量: 1007.22
• InChiKey: HJKUUIBEXSDQKX-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  12.85
• 重原子数：
  68.0
• 可旋转键数：
  14.0
• 环数：
  12.0
• sp3杂化的碳原子比例：
  0.8
• 拓扑面积：
  81.84
• 氢给体数：
  0.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  1,8-bis[tris(pyrrolidino)phosphazenyl bis(pyrrolidino)phosphazenyl]naphthalene 、 双三氟甲烷磺酰亚胺 以 四氢呋喃 为溶剂， 以62%的产率得到
  参考文献：
  名称：

  A New Synthetic Pathway to the Second and Third Generation of Superbasic Bisphosphazene Proton Sponges: The Run for the Best Chelating Ligand for a Proton

  摘要：

  We present the up to now strongest chelating neutral pincer ligand for the simplest electrophile of chemistry, the proton. Two novel bisphosphazene proton sponges, 1,8-bis(trispyrrolidinophosphazenyl)naphthalene (TPPN) and its higher homologue P-2-TPPN, were obtained via a Staudinger reaction and investigated concerning their structural features and basic properties by experimental and computational means. They exhibit experimental pK(BH)(+) values in acetonitrile of 32.3 and 42.1, respectively, exceeding the existing basicitiy record for proton sponges by more than 10 orders of magnitude. We show that Schwesinger's concept of homologization of phosphazene bases and Alder's concept of proton chelation in a constrained geometry regime of basic centers can be combined in the design of highly basic nonionic superbases of pincer type.

  DOI：

  10.1021/ja409760z
• 作为产物：
  描述：

  三吡咯烷膦 在 benzyl potassium 、 三氯化磷 作用下， 以 四氢呋喃 、 5,5-dimethyl-1,3-cyclohexadiene 、 甲苯 为溶剂， 反应 50.5h， 生成 1,8-bis[tris(pyrrolidino)phosphazenyl bis(pyrrolidino)phosphazenyl]naphthalene
  参考文献：
  名称：

  A New Synthetic Pathway to the Second and Third Generation of Superbasic Bisphosphazene Proton Sponges: The Run for the Best Chelating Ligand for a Proton

  摘要：

  We present the up to now strongest chelating neutral pincer ligand for the simplest electrophile of chemistry, the proton. Two novel bisphosphazene proton sponges, 1,8-bis(trispyrrolidinophosphazenyl)naphthalene (TPPN) and its higher homologue P-2-TPPN, were obtained via a Staudinger reaction and investigated concerning their structural features and basic properties by experimental and computational means. They exhibit experimental pK(BH)(+) values in acetonitrile of 32.3 and 42.1, respectively, exceeding the existing basicitiy record for proton sponges by more than 10 orders of magnitude. We show that Schwesinger's concept of homologization of phosphazene bases and Alder's concept of proton chelation in a constrained geometry regime of basic centers can be combined in the design of highly basic nonionic superbases of pincer type.

  DOI：

  10.1021/ja409760z

文献信息

• A New Synthetic Pathway to the Second and Third Generation of Superbasic Bisphosphazene Proton Sponges: The Run for the Best Chelating Ligand for a Proton
  作者：Julius F. Kögel、Benjamin Oelkers、Borislav Kovačević、Jörg Sundermeyer

  DOI：10.1021/ja409760z

  日期：2013.11.27

  We present the up to now strongest chelating neutral pincer ligand for the simplest electrophile of chemistry, the proton. Two novel bisphosphazene proton sponges, 1,8-bis(trispyrrolidinophosphazenyl)naphthalene (TPPN) and its higher homologue P-2-TPPN, were obtained via a Staudinger reaction and investigated concerning their structural features and basic properties by experimental and computational means. They exhibit experimental pK(BH)(+) values in acetonitrile of 32.3 and 42.1, respectively, exceeding the existing basicitiy record for proton sponges by more than 10 orders of magnitude. We show that Schwesinger's concept of homologization of phosphazene bases and Alder's concept of proton chelation in a constrained geometry regime of basic centers can be combined in the design of highly basic nonionic superbases of pincer type.