HZ2 | 42165-92-4

• 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: HZ2
• 英文别名: Dimethyl 2,4-bis(2-pyridinyl)-3,7-diazabicyclo-[3.3.1]-nonane-9-on-1,5-dicarboxylate；dimethyl [3,7-dimethyl-9,9'-dihydroxy-2,4-di-(2-pyridyl)-3,7-diazabicyclononan-1,5-dicaboxylate]；(1R,2S,4R,5S)-dimethyl 3,7-dimethyl-9-oxo-2,4-di(pyridin-2-yl)-3,7-diazabicyclo[3.3.1]nonane-1,5-dicarboxylate；dimethyl (1R,2S,4R,5S)-3,7-dimethyl-9-oxo-2,4-dipyridin-2-yl-3,7-diazabicyclo[3.3.1]nonane-1,5-dicarboxylate
• CAS: 42165-92-4
• 化学式: C₂₃H₂₆N₄O₅
• 分子量: 438.483
• InChiKey: NXOACBKUEYYEQP-SGNKAXLRSA-N

物化性质

• 沸点：
  577.6±50.0 °C(Predicted)
• 密度：
  1.294±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.4
• 重原子数：
  32
• 可旋转键数：
  6
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.43
• 拓扑面积：
  102
• 氢给体数：
  0
• 氢受体数：
  9

反应信息

• 作为反应物：
  描述：

  HZ2 在 sodium tetrahydroborate 作用下， 以 1,4-二氧六环 、 水 为溶剂， 生成
  参考文献：
  名称：

  通过改变芳香族供体基团的碱度来调节过渡金属联吡啶的配合物的性质

  摘要：

  联吡啶（3,7-二氮杂双环[3.3.1]壬烷）是非常刚性和高度组织化的配体，在配位化学领域得到广泛应用，它们的过渡金属配合物的氧化还原电势在高氧氧化反应中很重要。价铁络合物，铜络合物催化的叠氮化和64 Cu铜正电子发射断层显像剂成像。在这里，我们显示了15个四齿联吡啶的铜（II）配合物的氧化还原电势和稳定性常数可以通过取代吡啶环来改变（氧化还原电势在约450 mV以上的变化和复合物稳定性在约10 mV以上的变化）日志单位）。还表明，这些变化可以通过p K a预测。吡啶基团的值以及取代基的哈米特参数，以及基于密度泛函理论的能量分解分析，还可以使人们准确地预测氧化还原电势和随之而来的配合物稳定性。结果表明，主要贡献来自于静电相互作用能，因此吡啶供体基团的部分电荷也与氧化还原电势相关。

  DOI：

  10.1021/ic4004214
• 作为产物：
  描述：

  聚合甲醛 、 1-methyl-4-oxo-2,6-bis(2-pyridyl)piperidine-3,5-dicarboxylic acid dimethyl ester 、 甲胺 以 甲醇 、 水 为溶剂， 生成 HZ2
  参考文献：
  名称：

  Synthesis and Opioid Receptor Affinity of a Series of 2,4-Diaryl-Substituted 3,7-Diazabicylononanones

  摘要：

  3,7-Diazabicyclo[3.3.1]nonan-9-ones having aryl rings in positions 2 and 4 with systematically varied substituents were synthesized using a double Mannich procedure. Radioligand binding assays were performed to measure the affinity of the compounds to the mu-, delta-, and kappa-opioid receptors. The affinity of all 2,4-diphenyl-substituted 3,7-diazabicyclo[3.3.1]nonan-9-ones to the mu- and delta-receptors was found to be low. In contrast, with exception of the nitro- and cyanophenyl-substituted compounds, most of the diazabicycles showed considerable affinity for the kappa-receptor. In particular, the m-fluoro-, p-methoxy-, and m-hydroxy-substituted compounds have an affinity in the submicromolar range. Due to solubility problems in aqueous media, salts of HZ2 were synthesized. The methiodide shows high kappa-affinity and may, thus, be a promising candidate for development of a peripheral kappa-agonist, e.g. for use in the case of rheumatoid arthritis.

  DOI：

  10.1021/jm0009484

文献信息

• Spin-Crossover in an Iron(III)−Bispidine−Alkylperoxide System
  作者：Jochen Bautz、Peter Comba、Lawrence Que

  DOI：10.1021/ic0602401

  日期：2006.9.1

  The iron(II) complex of a tetradentate bispidine ligand with two tertiary amines and two pyridine groups (L = dimethyl [3,7-dimethyl-9,9'-dihydroxy-2,4-di-(2-pyridyl)-3,7-diazabicyclo nonan-1,5-dicaboxylate]) is oxidized with tert-butyl hydroperoxide to the corresponding end-on tert-butylperoxo complex [Fe(III)(L)(OOtBu)(X)]n+ (X = solvent, anion). UV-vis, resonance Raman, and EPR spectroscopy, as

  四齿联吡啶的配体与两个叔胺和两个吡啶基的铁（II）配合物（L =二甲基[3,7-二甲基-9,9'-二羟基-2,4-二-（2-吡啶基）-3 ，7-二氮杂双环壬基-1,5-二甲氧基化物]）被氢过氧化叔丁基氧化成相应的叔丁基过氧配合物[Fe（III）（L）（OOtBu）（X）] n +（X =溶剂，阴离子）。UV-vis，共振拉曼光谱和EPR光谱，作为溶剂的函数，表明这是一种自旋交联化合物。低旋转和高旋转异构体的实验观察到的拉曼振动与DFT计算得出的一致。
• Synthesis, X-ray analysis and spectroscopic characterization of the hemiaminal cyclization product from 2,4-dipyridine substituted 3,7-diazabicyclo[3.3.1]nonanone 1,5-diesters
  作者：Ulrich Kuhl、Antonella Cambareri、Christian Sauber、Fritz Sörgel、Rudolf Hartmann、Harald Euler、Armin Kirfel、Ulrike Holzgrabe

  DOI：10.1039/a904472h

  日期：——

  The 2,4-dipyridine substituted 3,7-dimethyl-3,7-diazabicyclo[3.3.1]nonan-9-one 1,5-diester, HZ2, is characterized by a high analgesic potency. The attempt to form ammonium salts of HZ2 or to N-demethylate position 7 resulted in an unexpected hemiaminal cyclization product 1. The structure was elucidated by an X-ray analysis, the 1H- and 13C-NMR spectra could be fully assigned by means of H,H-COSY, Grad-HSQC-EA and ACCORD-HMBC experiments. The MS spectra of 1 exhibit a ring opening. Interestingly, ESI-MS/MS experiments of HZ2 in aqueous solution showed the formation of a hydrated product. The fragmentation pathways of HZ2 and the hydrated product are rather different indicating the formation of a carboxylate.
• Tuning of the Properties of Transition-Metal Bispidine Complexes by Variation of the Basicity of the Aromatic Donor Groups
  作者：Peter Comba、Michael Morgen、Hubert Wadepohl

  DOI：10.1021/ic4004214

  日期：2013.6.3

  find broad application in the field of coordination chemistry, and the redox potentials of their transition-metal complexes are of importance in oxidation reactions by high-valent iron complexes, aziridination catalyzed by copper complexes, and imaging by 64Cu positron emission tomography tracers. Here, we show that the redox potentials and stability constants of the copper(II) complexes of 15 tetradentate

  联吡啶（3,7-二氮杂双环[3.3.1]壬烷）是非常刚性和高度组织化的配体，在配位化学领域得到广泛应用，它们的过渡金属配合物的氧化还原电势在高氧氧化反应中很重要。价铁络合物，铜络合物催化的叠氮化和64 Cu铜正电子发射断层显像剂成像。在这里，我们显示了15个四齿联吡啶的铜（II）配合物的氧化还原电势和稳定性常数可以通过取代吡啶环来改变（氧化还原电势在约450 mV以上的变化和复合物稳定性在约10 mV以上的变化）日志单位）。还表明，这些变化可以通过p K a预测。吡啶基团的值以及取代基的哈米特参数，以及基于密度泛函理论的能量分解分析，还可以使人们准确地预测氧化还原电势和随之而来的配合物稳定性。结果表明，主要贡献来自于静电相互作用能，因此吡啶供体基团的部分电荷也与氧化还原电势相关。
• Synthesis and Opioid Receptor Affinity of a Series of 2,4-Diaryl-Substituted 3,7-Diazabicylononanones
  作者：Tom Siener、Antonella Cambareri、Ulrich Kuhl、Werner Englberger、Michael Haurand、Babette Kögel、Ulrike Holzgrabe

  DOI：10.1021/jm0009484

  日期：2000.10.1

  3,7-Diazabicyclo[3.3.1]nonan-9-ones having aryl rings in positions 2 and 4 with systematically varied substituents were synthesized using a double Mannich procedure. Radioligand binding assays were performed to measure the affinity of the compounds to the mu-, delta-, and kappa-opioid receptors. The affinity of all 2,4-diphenyl-substituted 3,7-diazabicyclo[3.3.1]nonan-9-ones to the mu- and delta-receptors was found to be low. In contrast, with exception of the nitro- and cyanophenyl-substituted compounds, most of the diazabicycles showed considerable affinity for the kappa-receptor. In particular, the m-fluoro-, p-methoxy-, and m-hydroxy-substituted compounds have an affinity in the submicromolar range. Due to solubility problems in aqueous media, salts of HZ2 were synthesized. The methiodide shows high kappa-affinity and may, thus, be a promising candidate for development of a peripheral kappa-agonist, e.g. for use in the case of rheumatoid arthritis.