3-(pyridin-2-yl)-4,5,6,7-tetrahydro-1H-indazole | 155261-30-6

• 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-(pyridin-2-yl)-4,5,6,7-tetrahydro-1H-indazole
• 英文别名: 2H-3-(pyridin-2-yl)-4,5,6,7-tetrahydroindazole；3-(2-Pyridyl)-4,5,6,7-tetrahydro-1H-indazole；3-pyridin-2-yl-4,5,6,7-tetrahydro-1H-indazole
• CAS: 155261-30-6；180975-33-1
• 化学式: C₁₂H₁₃N₃
• 分子量: 199.255
• InChiKey: RAIFOOMSJKKLDE-UHFFFAOYSA-N

物化性质

• 沸点：
  449.8±45.0 °C(Predicted)
• 密度：
  1.198±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.1
• 重原子数：
  15
• 可旋转键数：
  1
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  41.6
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  3-(pyridin-2-yl)-4,5,6,7-tetrahydro-1H-indazole 在 sodium hydroxide 、 potassium carbonate 作用下， 以 四氢呋喃 、 二甲基亚砜 为溶剂， 反应 72.0h， 生成 1-(4-Carboxyphenyl)-3-(pyridin-2-yl)-4,5,6,7-tetrahydroindazole
  参考文献：
  名称：

  Chelation-Controlled Regioselectivity in the Synthesis of Substituted Pyrazolylpyridine Ligands. 1. Bidentates

  摘要：

  En route to novel C-linked pyrazole-pyridine bidentate ligands for transition metals, a new, higher-yielding synthesis of diketone 1 was found. It was quantitatively converted to the parent, C-linked 3-(pyridin-2-yl)pyrazole 2. Condensations of 1 with five aromatic hydrazines led to in-substituted derivatives of 2 (4i-8i). With CH3NHNH2, both in and out isomers formed, but 3o could be isolated pure. In the presence of ZnCl2, CH3NHNH2 and methyl 4-hydrazinobenzoate formed the isolable 1:1 complexes (3o)ZnCl2 and (6o)ZnCl2, respectively, which were characterized by NMR and elemental analysis. The bidentate, out-substituted 3o and 6o were freed from the complexes with NH4OH. Without isolation of complexes, PhNHNH(2) and 4-hydrazinobenzoic acid were similarly used to prepare the out-substituted derivatives 4o and 5o, respectively. Nucleophilic aromatic substitution by 2 of a-bromopyridine and ethyl 4-fluorobenzoate led to the out products 8o (a novel tridentate) and 9o, respectively. Both esters 6o and 9o could be hydrolyzed to the acid 5o in higher overall yield than the direct condensation of 4-hydrazinobenzoic acid. The regiochemistries were assigned by several arguments: Only bidentate out-substituted materials were expected to form stable ZnCl2 complexes. It was also shown that 4o reacted with TiCl4. The formation of out materials in the presence of ZnCl2 could be rationalized by a preferred attack of the metal-activated, inner carbonyl of 1 by the more nucleophilic NH2 ends of the aromatic hydrazines, whereas the outer carbonyl is more reactive in the absence of ZnCl2. The formation of out materials by nucleophilic aromatic substitutions of 2 could be rationalized as proceeding through a K+ chelate intermediate that disallows access to the inner pyrazole nitrogen. These two mechanistic arguments were tied through the conversion of a product of nucleophilic aromatic substitution (9o) into a product of ZnCl2-mediated condensation (5o). The aromatic H-1-NMR signals were also diagnostic of the regiochemistries: in all cases, the pyridine H-3 doublets lay upfield of the H-4 signals for in isomers and downfield for out isomers but, in the latter case, the H-3 signals shifted upfield in the Zn complexes (and in the TiCl4 adduct of 4o). This pattern was interpreted in conformational terms and the interpretation found support in MM2 calculations: The out products, like bipyridine, prefer anti orientations of the imino nitrogens due to electronic and steric effects (calculated Delta G(syn-anti) > 3.3 kcal/mol for 3o-7o). Complexation forces a syn orientation which produces a shielding of the pyridine H-3 by a nearby CH2 group. This same shielding effect is present in either conformation of the in isomers, which are much closer in energy (calculated /Delta G(syn-anti)/ < 0.5 kcal/mol for 3i-7i). Finally, the mass spectral fragmentations could be related to the regiochemistry.

  DOI：

  10.1021/jo00086a028
• 作为产物：
  描述：

  2-吡啶甲酰氯 在 一水合肼 、 三乙胺 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 生成 3-(pyridin-2-yl)-4,5,6,7-tetrahydro-1H-indazole
  参考文献：
  名称：

  Chelation-Controlled Regioselectivity in the Synthesis of Substituted Pyrazolylpyridine Ligands. 1. Bidentates

  摘要：

  En route to novel C-linked pyrazole-pyridine bidentate ligands for transition metals, a new, higher-yielding synthesis of diketone 1 was found. It was quantitatively converted to the parent, C-linked 3-(pyridin-2-yl)pyrazole 2. Condensations of 1 with five aromatic hydrazines led to in-substituted derivatives of 2 (4i-8i). With CH3NHNH2, both in and out isomers formed, but 3o could be isolated pure. In the presence of ZnCl2, CH3NHNH2 and methyl 4-hydrazinobenzoate formed the isolable 1:1 complexes (3o)ZnCl2 and (6o)ZnCl2, respectively, which were characterized by NMR and elemental analysis. The bidentate, out-substituted 3o and 6o were freed from the complexes with NH4OH. Without isolation of complexes, PhNHNH(2) and 4-hydrazinobenzoic acid were similarly used to prepare the out-substituted derivatives 4o and 5o, respectively. Nucleophilic aromatic substitution by 2 of a-bromopyridine and ethyl 4-fluorobenzoate led to the out products 8o (a novel tridentate) and 9o, respectively. Both esters 6o and 9o could be hydrolyzed to the acid 5o in higher overall yield than the direct condensation of 4-hydrazinobenzoic acid. The regiochemistries were assigned by several arguments: Only bidentate out-substituted materials were expected to form stable ZnCl2 complexes. It was also shown that 4o reacted with TiCl4. The formation of out materials in the presence of ZnCl2 could be rationalized by a preferred attack of the metal-activated, inner carbonyl of 1 by the more nucleophilic NH2 ends of the aromatic hydrazines, whereas the outer carbonyl is more reactive in the absence of ZnCl2. The formation of out materials by nucleophilic aromatic substitutions of 2 could be rationalized as proceeding through a K+ chelate intermediate that disallows access to the inner pyrazole nitrogen. These two mechanistic arguments were tied through the conversion of a product of nucleophilic aromatic substitution (9o) into a product of ZnCl2-mediated condensation (5o). The aromatic H-1-NMR signals were also diagnostic of the regiochemistries: in all cases, the pyridine H-3 doublets lay upfield of the H-4 signals for in isomers and downfield for out isomers but, in the latter case, the H-3 signals shifted upfield in the Zn complexes (and in the TiCl4 adduct of 4o). This pattern was interpreted in conformational terms and the interpretation found support in MM2 calculations: The out products, like bipyridine, prefer anti orientations of the imino nitrogens due to electronic and steric effects (calculated Delta G(syn-anti) > 3.3 kcal/mol for 3o-7o). Complexation forces a syn orientation which produces a shielding of the pyridine H-3 by a nearby CH2 group. This same shielding effect is present in either conformation of the in isomers, which are much closer in energy (calculated /Delta G(syn-anti)/ < 0.5 kcal/mol for 3i-7i). Finally, the mass spectral fragmentations could be related to the regiochemistry.

  DOI：

  10.1021/jo00086a028

文献信息

• An Efficient Synthesis of Substituted Pyrazoles from One-Pot Reaction of Ketones, Aldehydes, and Hydrazine Monohydrochloride
  作者：Vit Lellek、Cheng-yi Chen、Wanggui Yang、Jie Liu、Xuebao Ji、Roger Faessler

  DOI：10.1055/s-0036-1591941

  日期：2018.5

  hydrazine monohydrochloride readily formed pyrazoline intermediates under mild conditions. Oxidation of pyrazolines, in situ, employing bromine afforded a wide variety of pyrazoles. The methodology offers a fast, and often chromatography-free protocol for the synthesis of 3,4,5-substituted pyrazoles in good to excellent yields. Alternatively, a more benign oxidation protocol affords 3,5-disubstituted or

  开发了一种高效、单锅且无金属的制备多克规模的 3,5-二取代和 3,4,5-三取代吡唑的方法。在温和条件下，酮、醛和肼单盐酸盐的一锅缩合容易形成吡唑啉中间体。使用溴原位氧化吡唑啉得到多种吡唑。该方法为合成 3,4,5-取代吡唑的 3,4,5-取代吡唑类化合物提供了一种快速且通常无需色谱的方案，收率非常好。或者，通过简单地在 DMSO 中在氧气下加热吡唑啉，更温和的氧化方案提供 3,5-二取代或 3,4,5-三取代的吡唑。
• Diastereoselective Synthesis, Spectroscopy, and Electrochemistry of Ruthenium(II) Complexes of Substituted Pyrazolylpyridine Ligands
  作者：Yue Luo、Pierre G. Potvin、Yu-Hong Tse、A. B. P. Lever

  DOI：10.1021/ic950694q

  日期：1996.1.1

  Ru(bpy)Cl(3).H(2)O with 2 equiv of L provided a mixture of the three possible Ru(bpy)L(2)(2+) isomers, from which one symmetric isomer (labeled beta) was isolated pure. A trans arrangement of the pyrazole groups was deduced by (1)H-NMR and confirmed by X-ray crystallography for one such stereomer (beta-[Ru(bpy)(5)(2)](PF(6))(2), R = C(6)H(4)-4"-COOC(2)H(5)). In contrast, Ru(DMSO)(4)Cl(2) reacted with 2 equiv

  Ru（bpy）Cl（3）.H（2）O与2当量的L的一步反应提供了三种可能的Ru（bpy）L（2）（2+）异构体的混合物异构体（标记为beta）是纯净的。通过（1）H-NMR推导吡唑基的反式排列，并通过X射线晶体学确认了一种此类立体异构体（β-[Ru（bpy）（5）（2）]（PF（6））（2 ），R = C（6）H（4）-4“ -COOC（2）H（5））。相比之下，Ru（DMSO）（4）Cl（2）与2当量的L反应，然后与1当量的反应β-[Ru（bpy）（5）（2）]（PF（6））（2）的晶体数据可选择性地形成L的吡啶基是反式的其他对称异构体（标记为α） （52）H（50）N（8）O（4）F（12）P（2）Ru）在295 K辐射的Mo Kalpha（λ= 0.710 73Å）：a = 28.442（13）Å，b = 18.469（15）Å，c = 23.785（9）Å，beta = 116.76（0）度，单斜，空间群C2
• High-efficient phosphorescent iridium(III) complexes with benzimidazole ligand for organic light-emitting diodes: Synthesis, electrochemistry and electroluminescent properties
  作者：Chunxiang Li、Guanghui Zhang、Hung-Hsin Shih、Xiaoqing Jiang、Peipei Sun、Yi Pan、Chien-Hong Cheng

  DOI：10.1016/j.jorganchem.2009.03.022

  日期：2009.7

  Two phosphorescent complexes Ir(FFBI)(2)(pmp) and Ir(FFBI)(2)(pti) based on cyclometalated ligand 1-(4-fluorobenzyl)-2-(4-fluorophenyl)-1H-benzo[d]imidazole (FFBI) and ancillary ligands 2-(phenyliminomethyl) phenol (pmp) or 3-(pyridin-2-yl)-4,5,6,7-tetrahydro-2H-indazole (pti) were synthesized. The single crystal of Ir(FFBI)(2)(pmp) was obtained. The light emitting and electrochemical properties of these complexes were studied. The electroluminescent devices based on these two complexes with the structure of ITO/NPB (40 nm)/Ir complex: CBP (30 nm)/BCP (15 nm)/Alq (30 nm)/LiF (1 nm)/Al (100 nm) emitted cyan color, with high brightness and efficiencies. The maximum external quantum efficiencies reached to 6.8% and 11.6%, respectively. (C) 2009 Elsevier B.V. All rights reserved.
• Phosphorescent Osmium (II) complexes and uses thereof
  申请人：Tao Ye

  公开号：US20070001166A1

  公开（公告）日：2007-01-04

  There is disclosed herein phosphorescent compounds, uses thereof, and devices including organic light emitting diode (OLEDs) including such compounds. Compounds of interest include: wherein A is Os or Ru The anionic chelating chromophores NˆN, which are formed by connecting one pentagonal ring structure containing at least two nitrogen atoms to a hexagonal pyridine type of fragment via a direct carbon-carbon linkage. L is a neutral donor ligand; the typical example includes carbonyl, pyridine, phosphine, arsine and isocyanide; two neutral L's can also combine to produce the so-called chelating ligand such as 2,2′-bipyridine, 1,10-phenanthroline and N-heterocyclic carbene (NHC) ligand, or bidentate phosphorous ligands such as 1,2-bis(diphenylphosphino)ethane, 1,2-bis(diphenylphosphino)benzene. L can occupy either cis or trans orientation. When L occupies the trans position, the preferred structure contains both the hexagonal fragment of NˆN as well as its pentagonal fragment located at the trans position respect to their counterparts of the second NˆN chromophore. When L occupies the cis position, the preferred structure consists of the pentagonal unit of NˆN chromophores residing opposite to the L. X, 1 X 2 and X 3 independently are C or N; when X 2 is N, R 1 is omitted, when X 3 is N, R 2 is omitted, R 1 is H, C1-C8 alkyl, C1-C8 substituted phenyl or C1-C4 perfluoroalkyl, R 2 is H, F or cyano substituent, X 4 is either C or N; X 4 may locate at any position of the hexagonal ring, when X 4 is N and R 3 and R 4 are not linked to X 4 , R 3 is H, methyl or C1-C3 small alkyl, R 4 is H, methyl or C1-C3 small alkyl, or R 3 and R 4 together form an additional conjugated unit with structure
• US7759490B2
  申请人：——

  公开号：US7759490B2

  公开（公告）日：2010-07-20