2-(4-N-cetylpyridinium)-5-(dicyanomethanido)thiophene

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡啶及其衍生物
• 英文名称: 2-(4-N-cetylpyridinium)-5-(dicyanomethanido)thiophene
• 英文别名: 2-[5-(1-Hexadecylpyridin-4-ylidene)thiophen-2-ylidene]propanedinitrile；2-[5-(1-hexadecylpyridin-4-ylidene)thiophen-2-ylidene]propanedinitrile
• 化学式: C₂₈H₃₉N₃S
• 分子量: 449.704
• InChiKey: DBVMKMPAJIPKRJ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  9.7
• 重原子数：
  32
• 可旋转键数：
  15
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.57
• 拓扑面积：
  76.1
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为产物：
  描述：

  4-溴吡啶 在 (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride 、 四(三苯基膦)钯 溴 、 sodium hydride 作用下， 以 乙醚 、 二氯甲烷 、 丙酮 为溶剂， 反应 31.33h， 生成 2-(4-N-cetylpyridinium)-5-(dicyanomethanido)thiophene
  参考文献：
  名称：

  Facile, Regioselective Synthesis of Highly Solvatochromic Thiophene-Spaced N-Alkylpyridinium Dicyanomethanides for Second-Harmonic Generation

  摘要：

  The facile and clean synthesis of a navel class of highly solvatochromic chromophores 1 is reported. Compounds 1 are push-pull systems containing a negatively charged dicyanomethanide as a donor group and a positively charged N-alkylpyridinium as an acceptor group. The terminal polar functions are spaced by a thiophene-based moiety containing one or two heterocyclic rings and none, one, or two ethylene bridges. Chromophores 1 have been obtained through a general synthetic scheme involving, as the last step, the 100% regioselective alkylation of the precursor bidentate anions 2, where two competing nucleophilic sites, one neutral at the pyridic nitrogen and one anionic at the carbanionic carbon of the dicyanomethanide group, are present. The unprecedented highly regioselective attack of the alkylating agent onto the neutral pyridic nitrogen rather than the highly charged carbanionic carbon has been also confirmed in the case of the intermolecular competition. Multinuclear (C-13 and N-15) NMR spectroscopy has been used to investigate the structure and the extent of intramolecular charge transfer in 1, which are shown to exist in the ground state as highly charge-separated zwitterionic systems. Experimental results are discussed and compared with semiempirical (PM3) computations. The solvatochromic response of compounds 1, among the highest ever reported in the literature for similar systems, candidates this class of compounds as very attractive active components of nonlinear optical materials.

  DOI：

  10.1021/jo970059x

文献信息

• Facile, Regioselective Synthesis of Highly Solvatochromic Thiophene-Spaced <i>N</i>-Alkylpyridinium Dicyanomethanides for Second-Harmonic Generation
  作者：Alessandro Abbotto、Silvia Bradamante、Antonio Facchetti、Giorgio A. Pagani

  DOI：10.1021/jo970059x

  日期：1997.8.1

  The facile and clean synthesis of a navel class of highly solvatochromic chromophores 1 is reported. Compounds 1 are push-pull systems containing a negatively charged dicyanomethanide as a donor group and a positively charged N-alkylpyridinium as an acceptor group. The terminal polar functions are spaced by a thiophene-based moiety containing one or two heterocyclic rings and none, one, or two ethylene bridges. Chromophores 1 have been obtained through a general synthetic scheme involving, as the last step, the 100% regioselective alkylation of the precursor bidentate anions 2, where two competing nucleophilic sites, one neutral at the pyridic nitrogen and one anionic at the carbanionic carbon of the dicyanomethanide group, are present. The unprecedented highly regioselective attack of the alkylating agent onto the neutral pyridic nitrogen rather than the highly charged carbanionic carbon has been also confirmed in the case of the intermolecular competition. Multinuclear (C-13 and N-15) NMR spectroscopy has been used to investigate the structure and the extent of intramolecular charge transfer in 1, which are shown to exist in the ground state as highly charge-separated zwitterionic systems. Experimental results are discussed and compared with semiempirical (PM3) computations. The solvatochromic response of compounds 1, among the highest ever reported in the literature for similar systems, candidates this class of compounds as very attractive active components of nonlinear optical materials.