N-(2-amino-5-chlorophenyl)-1H-pyrazole | 947154-37-2

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 唑类
• 英文名称: N-(2-amino-5-chlorophenyl)-1H-pyrazole
• 英文别名: 2-pyrazolyl-4-chloro-aniline；4-chloro-2-(1H-pyrazol-1-yl)aniline；4-chloro-2-pyrazol-1-ylaniline
• CAS: 947154-37-2
• 化学式: C₉H₈ClN₃
• mdl: MFCD20696720
• 分子量: 193.636
• InChiKey: OTUBGBQBWKWFDT-UHFFFAOYSA-N

物化性质

• 沸点：
  347.6±27.0 °C(Predicted)
• 密度：
  1.36±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.8
• 重原子数：
  13
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  43.8
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  N-(2-amino-5-chlorophenyl)-1H-pyrazole 、 三苯基硼烷 以 甲苯 为溶剂， 以74%的产率得到
  参考文献：
  名称：

  BORAZANs:  Tunable Fluorophores Based on 2-(Pyrazolyl)aniline Chelates of Diphenylboron

  摘要：

  The reaction between 2-pyrazolyl-4-X-anilines, H(pzAn(X)), (X = para-OMe (L1), Me (L2), H (L3), Cl (L4), CO2Et (L5), CF3 (L6), CN (L7)) and triphenylboron in boiling toluene affords the respective, highly emissive N,N'-boron chelate complexes, BPh2(pzAn(X)) (X = para-OMe (1), Me (2), H (3), Cl (4), CO2Et (5), CF3 (6), CN (7)) in high yield. The structural, electrochemical, and photophysical properties of the new boron complexes can be fine-tuned by varying the electron-withdrawing or -donating power of the para-aniline substituent (delineated by the substituent's Hammett parameter). Those complexes with electron-withdrawing para-aniline substituents such as CO2Et (5), CF3 (6), and CN (7) have more planar chelate rings, more 'quinoidal' disortion in the aniline rings, greater chemical stability, higher oxidation potentials, and more intense (phi(F) = 0.81 for 7 in toluene), higher-energy (blue) fluorescent emission compared to those with electron-donating substituents. Thus, for 1 the oxidation potential is 0.53 V versus Ag/AgCl (compared to 1.12 V for 7), and the emission is tuned to the yellow-green but at an expense in terms of lower quantum yields (phi(F) = 0.07 for 1 in toluene) and increased chemical reactivity. Density functional calculations (B3LYP/6-31G*) on PM3 energy-minimized structures of the ligands and boron complexes reproduced experimentally observed data and trends and provided further insight into the nature of the electronic transitions.

  DOI：

  10.1021/jo0705420
• 作为产物：
  描述：

  对氯苯胺 在 iron(III) chloride 、 N-碘代丁二酰亚胺 、 copper(l) iodide 、 caesium carbonate 、 (1R,2R)-(-)-N,N'-二甲基-1,2-环己二胺 、 1-丁基-3-甲基咪唑二(三氟甲基磺酰)酰亚胺 作用下， 以 水 、 甲苯 为溶剂， 反应 29.0h， 生成 N-(2-amino-5-chlorophenyl)-1H-pyrazole
  参考文献：
  名称：

  连续铁和铜催化一锅邻氨基芳基碳氢键的正胺化

  摘要：

  使用连续的铁和铜催化作用，已经开发出一种用于将芳烃与非活性N-亲核试剂进行邻位偶联的一锅法。通过三氟化铁（III）催化的碘化作用，然后进行铜（I）催化，配体辅助的偶联反应，再与N杂环，酰胺和磺酰胺基亲核试剂实现对茴香醚，苯胺和苯酚的区域选择性邻位活化。一锅两步法直接合成邻位氨基甲酸酯的合成工具3,4-二氢喹啉-2-酮的后期官能化表明了芳基CH键。这允许制备TRIM24溴结构域抑制剂和一系列新的类似物。

  DOI：

  10.1039/c9ob00712a

文献信息

• 2-Amino-5,6-difluorophenyl-1<i>H</i>-pyrazole-Directed Pd^II Catalysis: Arylation of Unactivated β-C(sp³)–H Bonds
  作者：Jinyue Yang、Xiaopan Fu、Shibiao Tang、Kezuan Deng、Lili Zhang、Xianjin Yang、Yafei Ji

  DOI：10.1021/acs.joc.9b01276

  日期：2019.8.16

  efficient and readily removable directing group. Two fluoro groups are installed at the 5- and 6-position of the anilino moiety in 2-aminophenyl-1H-pyrazole, clearly enhancing the directing ability of the auxiliary. In addition, the protocol employs Cu(OAc)2/Ag3PO4 (1.2/0.3) as additives, evidently reducing the stoichiometric amount of expensive silver salts. Furthermore, this process exhibits high β-site

  首次描述了使用2-氨基-5,6-二氟苯基-1 H-吡唑作为有效且易于去除的钯衍生物催化羧酸衍生物中未活化的β-C（sp 3）–H键与芳基碘化物的芳基化指导小组。在2-氨基苯基-1 H-吡唑的苯胺基部分的5-位和6-位安装了两个氟基团，明显增强了辅助剂的导向能力。此外，该协议使用Cu（OAc）2 / Ag 3 PO 4（1.2 / 0.3）作为添加剂，明显减少了昂贵的银盐的化学计量。此外，该方法显示出高的β-位点选择性，与含有α-氢原子的各种底物的相容性以及优异的官能团耐受性。
• Molecular Motion and Performance Enhancement of BORAZAN Fluorescent Dyes
  作者：Tyler J. Morin、Sergey V. Lindeman、James R. Gardinier

  DOI：10.1002/ejic.200800806

  日期：2009.1

  monopyrazolyl counterparts presumably due to kinetic stabilization of the chromophore imparted by the second pyrazolyl ligand. For Ph2B(pz2AnX), evidence for intramolecular motion of the diphenylboryl moiety traversing both pyrazolyl groups was detected by variable temperature 1H NMR spectroscopy. The rate increases with increasing electron-donor abilities of the para-aniline substituent.(© Wiley-VCH Verlag

  描述了使用 CuI 催化胺化制备三种 2,6-二吡唑基-4-X-苯胺 H(pz2AnX) (X = p-CF3, Cl, tBu)。H(pz2AnX) 与三苯基硼的后续反应进行苯消除，以高产率得到相应的 Ph2B(pz2AnX) 化合物。Ph2B(pz2AnX) 在固态下比先前报道的 BORAZAN 荧光团 Ph2B(pzAnX)，它们的单吡唑基对应物具有更高的发射率。与 Ph2B(pzAnX) 一样，Ph2B(pz2AnX) 中的发射颜色可以简单地通过改变对苯胺取代基来调整，其中 Ph2B(pz2AnX) 的发射相对于相应的 Ph2B(pzAnX) 衍生物发生红移。通过循环伏安法和电子吸收/发射光谱以及密度泛函计算 (B3LYP/6-31G*) 研究了电子特性。与单吡唑基对应物相比，二吡唑基衍生物对溶剂分解表现出更高的稳定性和更高的光致发光量子产率（尽管发射红移），这可能是由于第二个吡唑基配体赋予生色团的动力学稳定性。对于
• One-pot <i>ortho</i>-amination of aryl C–H bonds using consecutive iron and copper catalysis
  作者：Martyn C. Henry、Rochelle McGrory、Réka J. Faggyas、Mohamed A. B. Mostafa、Andrew Sutherland

  DOI：10.1039/c9ob00712a

  日期：——

  sequential iron and copper catalysis. Regioselective ortho-activation of anisoles, anilines and phenols was achieved through iron(III) triflimide catalysed iodination, followed by a copper(I)-catalysed, ligand-assisted coupling reaction with N-heterocycle, amide and sulfonamide-based nucleophiles. The synthetic utility of this one-pot, two-step method for the direct amination of ortho-aryl C–H bonds was

  使用连续的铁和铜催化作用，已经开发出一种用于将芳烃与非活性N-亲核试剂进行邻位偶联的一锅法。通过三氟化铁（III）催化的碘化作用，然后进行铜（I）催化，配体辅助的偶联反应，再与N杂环，酰胺和磺酰胺基亲核试剂实现对茴香醚，苯胺和苯酚的区域选择性邻位活化。一锅两步法直接合成邻位氨基甲酸酯的合成工具3,4-二氢喹啉-2-酮的后期官能化表明了芳基CH键。这允许制备TRIM24溴结构域抑制剂和一系列新的类似物。
• BORAZANs:  Tunable Fluorophores Based on 2-(Pyrazolyl)aniline Chelates of Diphenylboron
  作者：Brendan J. Liddle、Rosalice M. Silva、Tyler J. Morin、Felipe P. Macedo、Ruchi Shukla、Sergey V. Lindeman、James R. Gardinier

  DOI：10.1021/jo0705420

  日期：2007.7.1

  The reaction between 2-pyrazolyl-4-X-anilines, H(pzAn(X)), (X = para-OMe (L1), Me (L2), H (L3), Cl (L4), CO2Et (L5), CF3 (L6), CN (L7)) and triphenylboron in boiling toluene affords the respective, highly emissive N,N'-boron chelate complexes, BPh2(pzAn(X)) (X = para-OMe (1), Me (2), H (3), Cl (4), CO2Et (5), CF3 (6), CN (7)) in high yield. The structural, electrochemical, and photophysical properties of the new boron complexes can be fine-tuned by varying the electron-withdrawing or -donating power of the para-aniline substituent (delineated by the substituent's Hammett parameter). Those complexes with electron-withdrawing para-aniline substituents such as CO2Et (5), CF3 (6), and CN (7) have more planar chelate rings, more 'quinoidal' disortion in the aniline rings, greater chemical stability, higher oxidation potentials, and more intense (phi(F) = 0.81 for 7 in toluene), higher-energy (blue) fluorescent emission compared to those with electron-donating substituents. Thus, for 1 the oxidation potential is 0.53 V versus Ag/AgCl (compared to 1.12 V for 7), and the emission is tuned to the yellow-green but at an expense in terms of lower quantum yields (phi(F) = 0.07 for 1 in toluene) and increased chemical reactivity. Density functional calculations (B3LYP/6-31G*) on PM3 energy-minimized structures of the ligands and boron complexes reproduced experimentally observed data and trends and provided further insight into the nature of the electronic transitions.