3-Amino-6,6'-dimethyl-2,2'-bipyridine | 153335-11-6

• 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: 3-Amino-6,6'-dimethyl-2,2'-bipyridine
• 英文别名: 6-Methyl-2-(6-methylpyridin-2-yl)pyridin-3-amine
• CAS: 153335-11-6
• 化学式: C₁₂H₁₃N₃
• 分子量: 199.255
• InChiKey: DFURERDHGWIAKA-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.6
• 重原子数：
  15
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.17
• 拓扑面积：
  51.8
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  copper(II) bis(trifluoromethanesulfonate) 、 3-Amino-6,6'-dimethyl-2,2'-bipyridine 以 乙腈 为溶剂， 生成 (3-amino-6,6'-dimethyl-2,2'-bipyridine)copper(II)bis(triflate)
  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：

  2-氯-3-硝基-6-甲基吡啶 在 palladium on activated charcoal bis-triphenylphosphine-palladium(II) chloride 、 氢气 作用下， 以 四氢呋喃 、 乙醇 为溶剂， 反应 38.0h， 生成 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

文献信息

• METHOD FOR PRODUCING ARYLHYDROXYLAMINE
  申请人：Wako Pure Chemical Industries, Ltd.

  公开号：EP2154125A1

  公开（公告）日：2010-02-17

  PROBLEM To provide a method for producing an arylhydroxylamine compound efficiently and safely under mild conditions. MEANS FOR SOLVING THE PROBLEM The present invention relates to a method for producing an arylhydroxylamine compound, which comprises contacting a nitroaryl compound with a hydrogen source in the coexistence of a platinum catalyst supported on amino group-coordinated silica and a poisoning agent.

  问题 提供一种在温和条件下高效、安全地生产芳基羟胺化合物的方法。 解决问题的方法 本发明涉及一种生产芳基羟胺化合物的方法，该方法包括在氨基配位二氧化硅上支撑的铂催化剂和中毒剂共存的条件下，使硝基芳基化合物与氢源接触。
• Copper(II) bipyridyl and iminopyridyl analogoues of streptonigrin
  作者：Georgina V. Long、Margaret M. Harding、Peter Turner、Trevor W. Hambley

  DOI：10.1039/dt9950003905

  日期：——

  The crystal structures of (3-amino-6,6'-dimethyl-2,2'-bipyridine)dichlorocopper(II) [CuL(1)Cl(2)], and aqua[3-imido-6-(methoxycarbonyl)-2,2'-bipryidine-6'-carboxylato]copper(II), [CuL(3)(H2O)], have been determined. The complex [CuL(1)Cl(2)] crystallizes in space group Pnma with a=19.434(3), b=7.427(2). c=9.403(1) Angstrom and Z=4. The structure has been refined to a final R value of 0.057 based on 680 independent reflections. The copper(ii) centre exhibits tetrahedral co-ordination to the bipyridyl nitrogens of L(1) and two chlorine atoms. Crystals of [CuL(3)(H2O)] were grown from a solution of 3-amino-6,6'-bis(methoxycarbonyl)-2,2'-bypyridine (L(2)) and excess Cu-II The complex crystallizes in space group P2(1)/n with a=3.724(2), b=14,375(3), c=22.953(5) Angstrom, beta=90.72(3)degrees and Z=4. The structure has been refined to a final R value of 0.061 based on 944 independent reflections. The Cu-II centre is square planar with a slight tetrahedral deformation, and co-ordinates to an imino nitrogen. adjacent pyridyl nitrogen, carboxylate oxygen and a water molecule. The implications of these results on the types of complexes formed by streptonigrin are discussed.
• US8455690B2
  申请人：——

  公开号：US8455690B2

  公开（公告）日：2013-06-04
• 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.