6,6'-Dimethyl-3-nitro-2,2'-bipyridine | 153335-10-5

• 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: 6,6'-Dimethyl-3-nitro-2,2'-bipyridine
• CAS: 153335-10-5
• 化学式: C₁₂H₁₁N₃O₂
• 分子量: 229.238
• InChiKey: XQSPWUYSPUVQRI-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.67
• 重原子数：
  17.0
• 可旋转键数：
  2.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.17
• 拓扑面积：
  68.92
• 氢给体数：
  0.0
• 氢受体数：
  4.0

反应信息

• 作为反应物：
  描述：

  6,6'-Dimethyl-3-nitro-2,2'-bipyridine 在 palladium on activated charcoal 氢气 作用下， 以 乙醇 为溶剂， 反应 10.0h， 以92%的产率得到3-Amino-6,6'-dimethyl-2,2'-bipyridine
  参考文献：
  名称：

  Synthesis, properties and complexation studies on 3-amino-6,6′-dimethyl-2,2′-bipyridine

  摘要：

  The new unsymmetrical bipyridyl ligand 6,6'-dimethyl-3-nitro-2,2'-bipyridine was prepared via coupling of 6-methyl-2-trimethylstanniopyridine and 2-chloro-6-methyl-3-nitropyridine in the presence of [Pd(PPh3)2Cl2]. Reduction of the nitro group afforded 3-amino-6,6'-dimethyl-2,2'-bipyridine (L), a model for the central subunit of the antitumour drug streptonigrin. At low temperatures, in [H-2(6)]acetone, L is planar, held in place by a hydrogen bond from the amino group to the pyridyl nitrogen in the adjacent ring. From H-1 NMR lineshape analysis the barrier to rotation about the amino-bipyridyl bond (DELTAG(b)double dagger) was estimated to be almost-equal-to 38 kJ mol-1 at 200 K. This value is significantly lower than the barrier to rotation about the biaryl bond connecting the aryl rings. In solution, L co-ordinates to Cd(II), Cu(I) and Zn(II) as a bipyridyl ligand; in these complexes the chemical shift of the amino group protons shifts upfield to ca. Delta 5 compared to L where they resonate at delta 6.5. The crystal structure of [(CdLCl2)2] was determined by X-ray diffraction methods and refined to a residual of 0.027 for 1895 independent observed reflections. The crystals are monoclinic, space group P2(1)/n, a = 9.560(2), b = 16.886(2), c = 9.577(3) angstrom, beta = 118.37(2)degrees. The complex crystallized as a dimer in which each cadmium binds three chloride ligands and a bipyridyl ligand in a distorted trigonal-bipyramidal arrangement. The relevance of these results to the structure and properties of the antitumour drug streptonigrin is discussed.

  DOI：

  10.1039/dt9930003175
• 作为产物：
  描述：

  三甲基-(6-甲基吡啶-2-基)锡烷 、 2-氯-3-硝基-6-甲基吡啶 在 bis-triphenylphosphine-palladium(II) chloride 作用下， 以 四氢呋喃 为溶剂， 反应 28.0h， 以58%的产率得到6,6'-Dimethyl-3-nitro-2,2'-bipyridine
  参考文献：
  名称：

  Synthesis, properties and complexation studies on 3-amino-6,6′-dimethyl-2,2′-bipyridine

  摘要：

  The new unsymmetrical bipyridyl ligand 6,6'-dimethyl-3-nitro-2,2'-bipyridine was prepared via coupling of 6-methyl-2-trimethylstanniopyridine and 2-chloro-6-methyl-3-nitropyridine in the presence of [Pd(PPh3)2Cl2]. Reduction of the nitro group afforded 3-amino-6,6'-dimethyl-2,2'-bipyridine (L), a model for the central subunit of the antitumour drug streptonigrin. At low temperatures, in [H-2(6)]acetone, L is planar, held in place by a hydrogen bond from the amino group to the pyridyl nitrogen in the adjacent ring. From H-1 NMR lineshape analysis the barrier to rotation about the amino-bipyridyl bond (DELTAG(b)double dagger) was estimated to be almost-equal-to 38 kJ mol-1 at 200 K. This value is significantly lower than the barrier to rotation about the biaryl bond connecting the aryl rings. In solution, L co-ordinates to Cd(II), Cu(I) and Zn(II) as a bipyridyl ligand; in these complexes the chemical shift of the amino group protons shifts upfield to ca. Delta 5 compared to L where they resonate at delta 6.5. The crystal structure of [(CdLCl2)2] was determined by X-ray diffraction methods and refined to a residual of 0.027 for 1895 independent observed reflections. The crystals are monoclinic, space group P2(1)/n, a = 9.560(2), b = 16.886(2), c = 9.577(3) angstrom, beta = 118.37(2)degrees. The complex crystallized as a dimer in which each cadmium binds three chloride ligands and a bipyridyl ligand in a distorted trigonal-bipyramidal arrangement. The relevance of these results to the structure and properties of the antitumour drug streptonigrin is discussed.

  DOI：

  10.1039/dt9930003175

文献信息

• 3-Amino-6,6′-bis(methoxycarbonyl)-2,2′-bipyridine, a model for the central chelation unit of streptonigrin
  作者：Georgina V. Long、Margaret M. Harding、Ming C. L. Xie、Irmi E. Buys、Trevor W. Hambley

  DOI：10.1039/dt9950000951

  日期：——

  amino group and the pyridyl nitrogen in the adjacent ring. The same conformation is observed in solution. The effect of solvent, temperature and concentration of zinc(II) on the types of complexes formed by 3-amino-6,6′-dimethyl-2,2′-bipyridine (L1) and L2 was studied. For L1 the 2 : 1 complex is more stable than the 1 : 1 complex. Substantial stabilization of the 1 : 1 complex of L2 occurs due to

  已经确定了3-氨基-6,6'-双（甲氧基羰基）-2,2'-联吡啶（L 2）的合成，晶体结构和溶液构象。对于2218次独立观察到的反射，晶体结构被细化为0.046的残差。晶体是单斜晶体，空间群P 2 1 / c，a = 9.229（2），b = 10.342（2），c = 13.650（2）Å，β= 90.92（2）°。由于相邻环中氨基和吡啶氮之间的分子内氢键，两个吡啶环几乎共面。在溶液中观察到相同的构象。溶剂，锌的温度和浓度的影响（二））研究了由3-氨基-6,6'-二甲基-2,2'-联吡啶（L 1）和L 2形成的络合物的类型。对于L 1 2：1的复合物比1更稳定的：1络合物。由于在6,6'位置上的酯基团的配位，使得L 2的1：1络合物基本上稳定。讨论了这些结果与抗肿瘤药链霉菌素的结构和性质的相关性。
• Synthesis, properties and complexation studies on 3-amino-6,6′-dimethyl-2,2′-bipyridine
  作者：Georgina V. Long、Sue E. Boyd、Margaret M. Harding、Irmi E. Buys、Trevor W. Hambley

  DOI：10.1039/dt9930003175

  日期：——

  The new unsymmetrical bipyridyl ligand 6,6'-dimethyl-3-nitro-2,2'-bipyridine was prepared via coupling of 6-methyl-2-trimethylstanniopyridine and 2-chloro-6-methyl-3-nitropyridine in the presence of [Pd(PPh3)2Cl2]. Reduction of the nitro group afforded 3-amino-6,6'-dimethyl-2,2'-bipyridine (L), a model for the central subunit of the antitumour drug streptonigrin. At low temperatures, in [H-2(6)]acetone, L is planar, held in place by a hydrogen bond from the amino group to the pyridyl nitrogen in the adjacent ring. From H-1 NMR lineshape analysis the barrier to rotation about the amino-bipyridyl bond (DELTAG(b)double dagger) was estimated to be almost-equal-to 38 kJ mol-1 at 200 K. This value is significantly lower than the barrier to rotation about the biaryl bond connecting the aryl rings. In solution, L co-ordinates to Cd(II), Cu(I) and Zn(II) as a bipyridyl ligand; in these complexes the chemical shift of the amino group protons shifts upfield to ca. Delta 5 compared to L where they resonate at delta 6.5. The crystal structure of [(CdLCl2)2] was determined by X-ray diffraction methods and refined to a residual of 0.027 for 1895 independent observed reflections. The crystals are monoclinic, space group P2(1)/n, a = 9.560(2), b = 16.886(2), c = 9.577(3) angstrom, beta = 118.37(2)degrees. The complex crystallized as a dimer in which each cadmium binds three chloride ligands and a bipyridyl ligand in a distorted trigonal-bipyramidal arrangement. The relevance of these results to the structure and properties of the antitumour drug streptonigrin is discussed.