3-pyrazolyl imino nitroxide | 696604-99-6

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 亚胺内酰胺
• 英文名称: 3-pyrazolyl imino nitroxide
• 英文别名: pzINH
• CAS: 696604-99-6
• 化学式: C₁₀H₁₅N₄O
• 分子量: 207.255
• InChiKey: OOOCLKQAKBXGIX-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.4
• 重原子数：
  15
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.6
• 拓扑面积：
  45.3
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  silver perchlorate 、 3-pyrazolyl imino nitroxide 在 1,8-diazabicyclo[5.4.0]-7-undecene 作用下， 以 乙腈 为溶剂， 以37%的产率得到
  参考文献：
  名称：

  使用吡唑并银（I）图案的金属自由基固体的超分子三角形和线性阵列。

  摘要：

  制备了新的螯合自由基配体pzNNH，pzINH和pzbisINH（分别为3-吡唑基硝酰基硝基氧，3-吡唑基亚氨基硝基氧和吡唑-3,5-二基双（亚氨基硝基氧））。这些配体与Ag +的络合得到[Ag（pzNN）] n，[Ag（pzIN）] 6和[Ag（pzbisIN）] n，它们含有相应的阴离子形式的配体。通过X射线晶体结构分析，[Ag（pzIN）] 6被表征为几乎平面的三角形部分的二聚体，其中吡唑酸酯起桥作用，并且金属-金属键引起三角形的二聚化。[Ag（pzbisIN）] n的特征是一条均匀的锯齿形链，由吡唑酸酯桥和具有顺式-Npz-Ag-Npz配位结构的Ag离子组成。可以根据对两种化合物确定的结构来分析观察到的反铁磁相互作用。在[Ag（pzNN）] n中观察到铁磁耦合，尽管无法确定晶体结构，但仍假定为聚合物结构。利用吡唑酸酯衍生物的独特配位多功能性，开发了使用吡唑酸酯取代的亚氨基亚硝酸盐的新型超分子结构。

  DOI：

  10.1039/b312406a
• 作为产物：
  描述：

  2,3-双(羟基氨基)-2,3-二甲基丁烷硫酸盐 在 溶剂黄146 、 sodium nitrite 作用下， 以 乙醚 、 氯仿 、 水 为溶剂， 反应 103.5h， 生成 3-pyrazolyl imino nitroxide
  参考文献：
  名称：

  1,3-偶极环加成反应合成吡唑基取代的硝酰基硝基氧

  摘要：

  基于通过 1,3-偶极环加成制备的预合成吡唑衍生物，开发了一种合成多功能吡唑基取代的硝酰基氮氧化物的新方法。通过 X 射线衍射证实了所得单自由基和双自由基的结构。

  DOI：

  10.1007/s11172-006-0093-6

文献信息

• 1,3-Dipolar cycloaddition in the synthesis of pyrazolyl-substituted nitronyl nitroxides
  作者：E. V. Tretyakov、S. E. Tolstikov、G. V. Romanenko、Yu. G. Shvedenkov、R. Z. Sagdeev、V. I. Ovcharenko

  DOI：10.1007/s11172-006-0093-6

  日期：2005.9

  A new approach to the synthesis of polyfunctional pyrazolyl-substituted nitronyl nitroxides was developed based on the presynthesized pyrazole derivatives prepared by 1,3-dipolar cycloaddition. The structures of the resulting mono-and biradicals were confirmed by X-ray diffraction.

  基于通过 1,3-偶极环加成制备的预合成吡唑衍生物，开发了一种合成多功能吡唑基取代的硝酰基氮氧化物的新方法。通过 X 射线衍射证实了所得单自由基和双自由基的结构。
• Self-assembled meso-helicates of linear trinuclear nickel(<scp>ii</scp>)–radical complexes with triple pyrazolate bridges
  作者：Susumu Yamada、Masanori Yasui、Takashi Nogami、Takayuki Ishida

  DOI：10.1039/b513618k

  日期：——

  Complexation of 3-nitronyl-nitroxide-substituted pyrazolate (pzNN) and 3-imino-nitroxide-substituted pyrazolate (pzIN) with nickel(II) gave [Ni3(pzNN)6] and [Ni3(pzIN)6], respectively. They were practically isomorphous and characterized as a linear trinuclear structure with neighboring nickel ions triply bridged by pyrazolate moieties. The space groups were P21/n but the molecules have a pseudo three-fold axis. We found polymorphs in the crystals of [Ni3(pzIN)6] depending on the solvate molecules; another space group was a cubic Pa. The opposite chirality around the inversion center at the central nickel(II) ion leads to a meso-helical symmetry in the whole molecule. The radical oxygen atoms participate in the 6-membered chelation at the terminal nickel(II) ions. Antiferromagnetic couplings were observed in both complexes, which are ascribable to interactions between the nickel and radical spins and between the nickel spins across the pyrazolate bridges.

  3-nitronyl-nitroxide-substituted pyrazolate (pzNN) 和 3-imino-nitroxide-substituted pyrazolate (pzIN) 与镍(II)络合后分别得到 [Ni3(pzNN)6] 和 [Ni3(pzIN)6]。它们实际上是同构的，并具有线性三核结构的特征，相邻的镍离子由吡唑烷基三重桥接。空间群为 P21/n，但分子具有假三折轴。我们发现[Ni3(pzIN)6]晶体的多态性取决于溶质分子；另一个空间群是立方 Pa。中心镍（II）离子反转中心周围的反手性导致整个分子具有中螺旋对称性。自由基氧原子参与了末端镍（II）离子的 6 元螯合。在这两种复合物中都观察到了反铁磁耦合，这可归因于镍自旋与自由基自旋之间以及镍自旋与吡唑烷桥之间的相互作用。
• Copper(II) complexes with pyrazolyl-substituted nitronyl and imino nitroxides
  作者：Eugene V. Tretyakov、Svyatoslav E. Tolstikov、Elena V. Gorelik、Matvey V. Fedin、Galina V. Romanenko、Artem S. Bogomyakov、Victor I. Ovcharenko

  DOI：10.1016/j.poly.2007.11.003

  日期：2008.2

  It was established that the reactions of pyrazol-3-yl-substituted nitronyl nitroxide (HL') and pyrazol73-yl-substituted imino nitroxide (HL3) with Cu(II) acetate lead to self-assembly of the Cu-4(OH)(2)(OAc)(4)(DMF)(2)(L-1)(2) tetranuclear and Cu-2(OAc)(2)(H2O)(2)(L-3)(2) dinuclear complexes, respectively. The reaction of Cu(II) acetate with 5-ethoxycarbonyl-pyrazol-3-yl-substituted nitronyl nitroxide (HL2) gave unexpected solid Cu-2(H2O)(2)(L-6)(2) center dot 2DMF, in which L-6 is a deprotonated 5-carboxy-pyrazol-3-yl-substituted nitronyl nitroxide, formed as a result of cleavage of an ester bond in the starting HL2. A similar transformation of the paramagnetic ligand was observed in the reaction of Cu(II) acetate with 5-ethoxycarbonyl-pyrazol-3-yl-substituted imino nitroxide (HL4). It led to the formation Of Cu-2(DMF)(2)(L-7)(2), where L-7 is deprotonated 2-(5-carboxy-lH-pyrazol-3-yl)-4,4,5,5-tetramethyl-4,5-dihydro-1H-imidazole 3-oxide. An X-ray diffraction study indicated that in Cu-4(OH)(2)(OAc)(4)(DMF)(2)(L-1)(2) and Cu-2(OAc)(2)(H2O)(2)(L-3)(2), the L-1 and L-3 paramagnetic ligands perform the bridging cyclic tridentate function, while in Cu-2(H2O)(2)(L-6)(2)center dot 2DMF and Cu-2(DMF)(2)(L-7)(2), the paramagnetic L-6 and diamagnetic L-7 are bridging bicyclic tetradentate ligands. The magnetic behavior of complexes with coordinated nitronyl nitroxide - Cu-4(OH)(2)(OAc)(4)(DMF)(2)(L-1)(2) and Cu-2(H2O)(2)(L-6)(2) center dot 2DMF is dictated by the dominant antiferromagnetic exchange interactions, which is confirmed by quantum-chemical data. The magnetic susceptibility of Cu-2(OAC)(2)(H2O)(2)(L-3)(2) reflects the competition between the antiferromagnetic and ferromagnetic components, of which the latter is due to electron coupling in the Cu(II) <- N=C-N (center dot) under bar O exchange channels. EPR data confirm the results received from static magnetic measurements for multispin solids. (c) 2007 Elsevier Ltd. All rights reserved.
• Erratum to “Copper(II) complexes with pyrazolyl-substituted nitronyl and imino nitroxides” [Polyhedron 27 (2008) 739–740]
  作者：Eugene V. Tretyakov、Svyatoslav E. Tolstikov、Elena V. Gorelik、Matvey V. Fedin、Galina V. Romanenko、Artem S. Bogomyakov、Victor I. Ovcharenko

  DOI：10.1016/j.poly.2008.01.011

  日期：2008.6
• Supramolecular triangular and linear arrays of metal–radical solids using pyrazolato-silver(<scp>i</scp>) motifs
  作者：Susumu Yamada、Takayuki Ishida、Takashi Nogami

  DOI：10.1039/b312406a

  日期：——

  New chelating radical ligands pzNNH, pzINH, and pzbisINH (3-pyrazolyl nitronyl nitroxide, 3-pyrazolyl imino nitroxide, and pyrazole-3,5-diyl bis(imino nitroxide), respectively) were prepared. Complexation of these ligands with Ag+ gave [Ag(pzNN)]n, [Ag(pzIN)]6, and [Ag(pzbisIN)]n containing the corresponding anionic forms of the ligands. From the X-ray crystal structure analysis, [Ag(pzIN)]6 was characterized

  制备了新的螯合自由基配体pzNNH，pzINH和pzbisINH（分别为3-吡唑基硝酰基硝基氧，3-吡唑基亚氨基硝基氧和吡唑-3,5-二基双（亚氨基硝基氧））。这些配体与Ag +的络合得到[Ag（pzNN）] n，[Ag（pzIN）] 6和[Ag（pzbisIN）] n，它们含有相应的阴离子形式的配体。通过X射线晶体结构分析，[Ag（pzIN）] 6被表征为几乎平面的三角形部分的二聚体，其中吡唑酸酯起桥作用，并且金属-金属键引起三角形的二聚化。[Ag（pzbisIN）] n的特征是一条均匀的锯齿形链，由吡唑酸酯桥和具有顺式-Npz-Ag-Npz配位结构的Ag离子组成。可以根据对两种化合物确定的结构来分析观察到的反铁磁相互作用。在[Ag（pzNN）] n中观察到铁磁耦合，尽管无法确定晶体结构，但仍假定为聚合物结构。利用吡唑酸酯衍生物的独特配位多功能性，开发了使用吡唑酸酯取代的亚氨基亚硝酸盐的新型超分子结构。