1-(p-chlorophenyl)-5-methyl-1,3-hexadiyn-5-ol tetrahydropyranyl ether | 136881-88-4

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 1-(p-chlorophenyl)-5-methyl-1,3-hexadiyn-5-ol tetrahydropyranyl ether
• CAS: 136881-88-4
• 化学式: C₁₈H₁₉ClO₂
• 分子量: 302.801
• InChiKey: FSTSOUOCBKHEPY-UHFFFAOYSA-N

物化性质

• 沸点：
  422.7±45.0 °C(Predicted)
• 密度：
  1.16±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.02
• 重原子数：
  21.0
• 可旋转键数：
  2.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.44
• 拓扑面积：
  18.46
• 氢给体数：
  0.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  1-(p-chlorophenyl)-5-methyl-1,3-hexadiyn-5-ol tetrahydropyranyl ether 在 正丁基锂 、 4-甲基苯磺酸吡啶 作用下， 以 乙醇 为溶剂， 反应 11.5h， 生成 6-[3-(tert-Butyl-hydroxy-amino)-4-chloro-phenyl]-2-methyl-hexa-3,5-diyn-2-ol
  参考文献：
  名称：

  An approach to organic ferromagnets. Synthesis and characterization of 1-phenyl-1,3-butadiyne polymers having a persistent nitroxide group on the phenyl ring

  摘要：

  1-[3-(N-tert-Butylhydroxyamino)-4-chlorophenyl]-1,3-butadiyne (3) was obtained as colorless needles (mp ca. 140-degrees-C from diethyl ether) that Polymerized 100% in 24 h at 120-degrees-C to give a black, ethanol-insoluble microcrystalline product. Crystals of 3 are triclinic, space group P1BAR (No. 2), with a = 8.496 (3) angstrom, b = 10.755 (5) angstrom, c = 8.004 (3) angstrom, alpha = 92.77 (4)-degrees, beta = 106.51 (3)-degrees, gamma = 74.85 (3)-degrees, V = 676.6 (5) angstrom 3, and d = 1.22 g/cm3 for Z = 2 (C14H14ClON, MW = 247.72). The observed solid-state polymerization is estimated to have taken place along the a/c diagonal. Treatment of 3 with Fremy's salt in THF/H2O at room temperature gave the corresponding nitroxide radical 4 as red crystals (mp 81.0-82.0-degrees-C, a(N) = 13.8 G, g = 2.0066 in hexane). Whereas the planned solid-state polymerization of 4 proceeded neither by heat nor UV and gamma-irradiation, mixed crystals of 3 and 4 (70:30 to 50:50) did undergo polymerization in 20 h at 140-degrees-C to give a black, ethanol-insoluble solid. A broad X-band ESR signal that showed geometrical anisotropy was observed at ca. 3000 G in addition to resonances at g = 2 due to the isolated (S = 1/2) and exchange-narrowed nitroxide spins. The magnetic susceptibility of the polymer samples measured on a Faraday balance showed that ca. 90% of the nitroxide radical centers were lost during the polymerization. Most of the remaining spins are S = 1/2, and the rest are in a segment where S > 1/2. The latter spins were found to be quenched by an anomalous phase transition at ca. 250 K when the samples were warmed up from cryogenic temperatures.

  DOI：

  10.1021/ja00026a014
• 作为产物：
  描述：

  4-溴-2-甲基丁-3-炔-2-醇 在 copper(I) chloride 、 盐酸羟胺 、 对甲苯磺酸 、 三乙胺 作用下， 以 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 4.0h， 生成 1-(p-chlorophenyl)-5-methyl-1,3-hexadiyn-5-ol tetrahydropyranyl ether
  参考文献：
  名称：

  An approach to organic ferromagnets. Synthesis and characterization of 1-phenyl-1,3-butadiyne polymers having a persistent nitroxide group on the phenyl ring

  摘要：

  1-[3-(N-tert-Butylhydroxyamino)-4-chlorophenyl]-1,3-butadiyne (3) was obtained as colorless needles (mp ca. 140-degrees-C from diethyl ether) that Polymerized 100% in 24 h at 120-degrees-C to give a black, ethanol-insoluble microcrystalline product. Crystals of 3 are triclinic, space group P1BAR (No. 2), with a = 8.496 (3) angstrom, b = 10.755 (5) angstrom, c = 8.004 (3) angstrom, alpha = 92.77 (4)-degrees, beta = 106.51 (3)-degrees, gamma = 74.85 (3)-degrees, V = 676.6 (5) angstrom 3, and d = 1.22 g/cm3 for Z = 2 (C14H14ClON, MW = 247.72). The observed solid-state polymerization is estimated to have taken place along the a/c diagonal. Treatment of 3 with Fremy's salt in THF/H2O at room temperature gave the corresponding nitroxide radical 4 as red crystals (mp 81.0-82.0-degrees-C, a(N) = 13.8 G, g = 2.0066 in hexane). Whereas the planned solid-state polymerization of 4 proceeded neither by heat nor UV and gamma-irradiation, mixed crystals of 3 and 4 (70:30 to 50:50) did undergo polymerization in 20 h at 140-degrees-C to give a black, ethanol-insoluble solid. A broad X-band ESR signal that showed geometrical anisotropy was observed at ca. 3000 G in addition to resonances at g = 2 due to the isolated (S = 1/2) and exchange-narrowed nitroxide spins. The magnetic susceptibility of the polymer samples measured on a Faraday balance showed that ca. 90% of the nitroxide radical centers were lost during the polymerization. Most of the remaining spins are S = 1/2, and the rest are in a segment where S > 1/2. The latter spins were found to be quenched by an anomalous phase transition at ca. 250 K when the samples were warmed up from cryogenic temperatures.

  DOI：

  10.1021/ja00026a014