6,19-dioxa-3,9,12,13,16,22,25,26-octaazatricyclo-[22.2.1.1^11,14]-octacosa-1(27),11,14(28),24-tetraene | 244217-89-8

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: 6,19-dioxa-3,9,12,13,16,22,25,26-octaazatricyclo-[22.2.1.1^11,14]-octacosa-1(27),11,14(28),24-tetraene
• 英文别名: 6,19-Dioxa-3,9,12,13,16,22,25,26-octazatricyclo[22.2.1.111,14]octacosa-1(26),11,14(28),24(27)-tetraene
• CAS: 244217-89-8
• 化学式: C₁₈H₃₂N₈O₂
• 分子量: 392.504
• InChiKey: DAMPXGOGRYOLCU-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -2.7
• 重原子数：
  28
• 可旋转键数：
  0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  124
• 氢给体数：
  6
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  6,19-dioxa-3,9,12,13,16,22,25,26-octaazatricyclo-[22.2.1.1^11,14]-octacosa-1(27),11,14(28),24-tetraene 在 sodium hydroxide 作用下， 以 氘代二甲亚砜 、 重水 为溶剂， 生成
  参考文献：
  名称：

  New macrocyclic polyamines of 3,5-disubstituted 1-pyrazole. A 13C NMR study of deprotonation and formation of Zn2+ dinuclear complexes.

  摘要：

  Dipodal (2+2) condensation of 3,5-(1H-pyrazole)dicarbaldehyde (3) with 1,5-diamino-3-oxapentane (4) and diethylerketriamine (5) followed by hydrogenation of the resulting Schiff bases (6 and 8), affords two new 26 membered polyaza macrocycles of 1H-pyrazole (7 and 9). The deprotonation of both crowns in basic medium as well as the formation of dinuclear Zn2+ complexes (7b and 9b) from the dipyrazolate salts 7a and 9a have been studied by C-13 NMR.

  DOI：

  10.1016/s0040-4039(00)93406-3
• 作为产物：
  描述：

  3,5-吡唑二甲酸 在 盐酸 、 manganese(IV) oxide 、 sodium tetrahydroborate 、 二异丁基氢化铝 作用下， 以 丙醇 、 乙二醇二甲醚 、 乙醇 、 甲苯 为溶剂， 反应 28.0h， 生成 6,19-dioxa-3,9,12,13,16,22,25,26-octaazatricyclo-[22.2.1.1^11,14]-octacosa-1(27),11,14(28),24-tetraene
  参考文献：
  名称：

  Synthesis and Protonation Behavior of 26-Membered Oxaaza and Polyaza Macrocycles Containing Two Heteroaromatic Units of 3,5-Disubstituted Pyrazole or 1-Benzylpyrazole. A Potentiometric and ¹H and ¹³C NMR Study

  摘要：

  The synthesis and acid-base behavior of two series of 26-membered dioxatetraamine and hexaamine heterocyclophanes containing two nuclei of either pyrazole (4a and 6a) or 1-benzylpyrazole (4b and 6b), respectively, are reported. Dipodal (2 + 2) condensations of 3,5-pyrazoledicarbaldehyde 2a or its 1-benzyl derivative 2b with 1,5-diamino-3-oxapentane afford in both cases the stable Schiff bases 3a,b in 90% yield, which after reduction with NaBH4 gave 4a;b in 75% and 84% yield, respectively. Condensation of 2a with diethylenetriamine leads to a complex mixture containing imidazolidine isomers, which was reduced in situ to afford 6a in 30% yield. Condensation of 2b with the same amine gave the stable diimidazolidine derivative 5b, which after crystallization was isolated as a pure compound in 80% yield and fully identified from analytical and H-1 and C-13 NMR data as a constitutional isomer with both imidazolidine rings located at the side of the pyrazole closer to the benzylic substituents. Reduction of 5b with NaBH4 afforded the polyamine 6b in 86% yield. Protonation constants of 4a,b and 6a,b have been determined by potentiometric methods in the pH 2-11 range, and their protonation sequences were established by a H-1 and C-13 NMR study in D2O at variable pH. For each compound, the number of protonation constants equals the number of nitrogens in the side chains. In the pH range studied, the pyrazole rings are not involved in protonation or deprotonation processes.

  DOI：

  10.1021/jo981699i