N-(Benzyl)-N'-(benzylmethyl)-1,8-diaminonaphthalene | 210362-82-6

• 分子结构分类: 有机化合物 - 苯类化合物 - 萘
• 英文名称: N-(Benzyl)-N'-(benzylmethyl)-1,8-diaminonaphthalene
• 英文别名: 1-N,8-N-dibenzyl-1-N-methylnaphthalene-1,8-diamine
• CAS: 210362-82-6
• 化学式: C₂₅H₂₄N₂
• 分子量: 352.479
• InChiKey: ATGWEDWSVBTPMR-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.3
• 重原子数：
  27
• 可旋转键数：
  6
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.12
• 拓扑面积：
  15.3
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  N-(Benzyl)-N'-(benzylmethyl)-1,8-diaminonaphthalene 在 lithium methanolate 、 重水 作用下， 以 二氯甲烷 为溶剂， 生成
  参考文献：
  名称：

  Entropy-Driven Hydrogen Bonding: Stereodynamics of a Protonated,N,N-Chiral “Proton Sponge”

  摘要：

  The C-2-symmetric ("[DL]") and achiral ("[meso]") diastereoisomers of the hydrogen iodide salt of 1,8-bis-(N-benzyl-N-methylamino)naphthalene ([2H](+)[I](-)) interconvert in solution. Direct interconversion of the diastereoisomers of [2H](+) must involve hydrogen bond fission (to give "[nonHB-2H(+)]'') and rotation-inversion of the non-protonated nitrogen centre. The global activation parameters (DeltaH(not equal) and DeltaS(not equal)) for diastereoisomer interconversion in [D-7]DMF have been determined from rate data obtained by temperature-drop and magnetisation-transfer C-13 NMR spectroscopy over a temperature range of 170 degreesC. The process is found to have a high entropy of activation in both directions (DeltaS(not equal) = 163(+/-4) and 169(+/-4) J K-1 mol(-1)) and this is suggested to arise through hydrogen bonding of the ammonium centre in [nonHB-2H(+)] with the solvent ([D-7]DMF). Comparison of the enthalpy of activation (DeltaH(not equal)) with that earlier found for diastereoisomer interconversion of the free-base form 2 suggests that the intramolecular hydrogen bond in [2H](+) is roughly equal in enthalpic strength (DeltaH) with that made with the solvent ([D-7]DMF) in the non-hydrogen-bonded intermediate [nonHB-2H(+)]. As such, the hydrogen bonding in [2H](+) may be considered as predominantly an entropically driven process, without any unusual enthalpic strength.

  DOI：

  10.1002/1521-3765(20001215)6:24<4451::aid-chem4451>3.0.co;2-h
• 作为产物：
  描述：

  N,N'-bis(benzyl)-1,8-diaminonaphthalene 、 碘甲烷 在 sodium hydride 作用下， 以 四氢呋喃 为溶剂， 反应 1.0h， 以87.5%的产率得到N-(Benzyl)-N'-(benzylmethyl)-1,8-diaminonaphthalene
  参考文献：
  名称：

  Charmant, Jonathan P. H.; Lloyd-Jones, Guy C.; Peakman, Torren M., European Journal of Organic Chemistry, 1999, # 10, p. 2501 - 2510

  摘要：

  DOI：

文献信息

• Synthesis of a protonated C2-symmetric N,N-chiral “proton sponge”
  作者：Jonathan P.H. Charmant、Guy C. Lloyd-Jones、Torren M. Peakman、Robert L. Woodward

  DOI：10.1016/s0040-4039(98)00930-7

  日期：1998.6

  The hydrogen iodide salt of 1,8-bis-(N-benzyl-N-methylamino)naphthalene was synthesised as an 89/11 ratio of diastereomers in good yield. The structure of the major (+)-(RNRN/SNSN) diastereomer was determined by single crystal X-ray diffraction. The minor diastereomer is shown to be the meso-(RNSN) form by performing H-1 NMR n.O.e studies on isotopically desymmetrized 1-(N-benzyl-N-[C-13]-methylamino)-8-(N'-benzyl-N'-methylamino) naphthalene (HI salt). The half-life of interconversion of meso and dl forms is less than 2 minutes in CD2Cl2, at ambient temperature. (C) 1998 Elsevier Science Ltd. All rights reserved.
• Charmant, Jonathan P. H.; Lloyd-Jones, Guy C.; Peakman, Torren M., European Journal of Organic Chemistry, 1999, # 10, p. 2501 - 2510
  作者：Charmant, Jonathan P. H.、Lloyd-Jones, Guy C.、Peakman, Torren M.、Woodward, Robert L.

  DOI：——

  日期：——
• Entropy-Driven Hydrogen Bonding: Stereodynamics of a Protonated,N,N-Chiral “Proton Sponge”
  作者：Paul Hodgson、Guy C. Lloyd-Jones、Martin Murray、Torren M. Peakman、Robert L. Woodward

  DOI：10.1002/1521-3765(20001215)6:24<4451::aid-chem4451>3.0.co;2-h

  日期：2000.12.15

  The C-2-symmetric ("[DL]") and achiral ("[meso]") diastereoisomers of the hydrogen iodide salt of 1,8-bis-(N-benzyl-N-methylamino)naphthalene ([2H](+)[I](-)) interconvert in solution. Direct interconversion of the diastereoisomers of [2H](+) must involve hydrogen bond fission (to give "[nonHB-2H(+)]'') and rotation-inversion of the non-protonated nitrogen centre. The global activation parameters (DeltaH(not equal) and DeltaS(not equal)) for diastereoisomer interconversion in [D-7]DMF have been determined from rate data obtained by temperature-drop and magnetisation-transfer C-13 NMR spectroscopy over a temperature range of 170 degreesC. The process is found to have a high entropy of activation in both directions (DeltaS(not equal) = 163(+/-4) and 169(+/-4) J K-1 mol(-1)) and this is suggested to arise through hydrogen bonding of the ammonium centre in [nonHB-2H(+)] with the solvent ([D-7]DMF). Comparison of the enthalpy of activation (DeltaH(not equal)) with that earlier found for diastereoisomer interconversion of the free-base form 2 suggests that the intramolecular hydrogen bond in [2H](+) is roughly equal in enthalpic strength (DeltaH) with that made with the solvent ([D-7]DMF) in the non-hydrogen-bonded intermediate [nonHB-2H(+)]. As such, the hydrogen bonding in [2H](+) may be considered as predominantly an entropically driven process, without any unusual enthalpic strength.