4-dimethylaminomethyl-1,8-bis(dimethylamino)naphthalene | 180538-07-2

• 分子结构分类: 有机化合物 - 苯类化合物 - 萘
• 英文名称: 4-dimethylaminomethyl-1,8-bis(dimethylamino)naphthalene
• 英文别名: 4-[(dimethylamino)methyl]-1-N,1-N,8-N,8-N-tetramethylnaphthalene-1,8-diamine
• CAS: 180538-07-2
• 化学式: C₁₇H₂₅N₃
• 分子量: 271.406
• InChiKey: NNMXALSZPKSWDV-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.03
• 重原子数：
  20.0
• 可旋转键数：
  4.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.41
• 拓扑面积：
  9.72
• 氢给体数：
  0.0
• 氢受体数：
  3.0

反应信息

• 作为反应物：
  描述：

  4-dimethylaminomethyl-1,8-bis(dimethylamino)naphthalene 在 sodium tetrahydroborate 作用下， 以 乙腈 为溶剂， 反应 1.25h， 生成 1,8-bis(dimethylamino)-4-methylnaphthalene
  参考文献：
  名称：

  结合“支撑”和“晒衣夹”效应以达到质子海绵阳离子中最短的NHN氢键

  摘要：

  一系列先前未知的2,4,5-三和2,4,5,7-四取代的1,8-双（二​​甲基氨基）萘及其与HBF 4的盐，它们都包含大球形的取代基（Me，Br和SiMe 3）在萘环中已经合成。使用X射线衍射分析11个样品，研究了所谓的“支撑”和“衣夹”效应对其分子结构和固体阳离子中NHN氢键几何形状的影响。已显示两种作用的联合作用显着增加了氢键的压缩。结果，先前的氢键短度记录（N···N = 2.524Å）已被超过2.502Å，这是针对2,4,5,7-tetramethyl-1,8-bis的四氟硼酸盐发现的（二甲基氨基）萘。后者的分子结构因[NHN] +中的完美对称性和几乎无障碍的质子转移而有所不同键。根据量子化学计算的结果，建议值2.502Å可能代表或非常接近胺型氮原子之间短氢键的理论极限。

  DOI：

  10.1021/acs.joc.0c03008
• 作为产物：
  描述：

  四甲基甲烷二胺 、 1,8-双二甲氨基萘 在 溶剂黄146 作用下， 反应 24.0h， 以79%的产率得到4-dimethylaminomethyl-1,8-bis(dimethylamino)naphthalene
  参考文献：
  名称：

  摘要：

  Aminomethylation of 1,8-bis(dimethylamino) naphthalene ("proton sponge") afforded a series of its 4-dialkylaminomethyl-substituted derivatives. An attempt to introduce the second peri-dialkylaminomethyl group unexpectedly led to the formation of salts with the 2,2-dialkyl-6,7-bis(dimethylamino)-2-azonia-2,3-dihydrophenalene cation. The structure of one of these salts was established by X-ray diffraction analysis. Treatment of 1,8-bis(dimethylamino)-4-piperidinomethylnaphthale ne with iodomethane gave a spiro compound rather than the expected N-[4,5-bis(dimethylamino)-1-naphthylmethyl]-N-methylpiperidinium iodide. This spiro, compound was generated through cyclodimerization of the 1-naphthylmethyl carbocations. These transformations provide evidence that "proton sponge"-derived Mannich bases quaternized at the dialkylaminomethyl group are unstable and undergo the spontaneous transformation into the resonance-stabilized 4,5-bis(dimethylamino)-1-naphthylmethyl carbocation. By contrast, 4-dialkylamino-1 -dimethylaminomethylnaphthalenes gave methoiodides, which are stable under standard conditions. The latter compounds undergo the nucleophilic substitution of the NR3 group typical of such salts.

  DOI：

  10.1023/a:1022477205623

文献信息

• Alumina-catalyzed cyclodimerization of 4-hydroxymethyl derivatives of 1,8-bis(dimethylamino)- and 1,8-dimethoxynaphthalenes to symmetrical spiro compounds
  作者：A. F. Pozharskii、N. V. Vistorobskii

  DOI：10.1007/bf01431337

  日期：1996.4

  4-Hydroxymethyl derivatives of 1,8-bis(dimethylamino)- and 1,8-dimethoxynaphthalenes undergo cyclodimerization on alumina to form symmetrical spiro compounds of the ''head-to-tail'' type. The reaction is considered to be a two-step electrophilic substitution with the participation of naphthylmethyl carbocations.