4-methylbenzo[h]quinoline-2-carbaldehyde | 1350296-66-0

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 喹啉及其衍生物
• 英文名称: 4-methylbenzo[h]quinoline-2-carbaldehyde
• CAS: 1350296-66-0
• 化学式: C₁₅H₁₁NO
• 分子量: 221.258
• InChiKey: CQHBRLMGAHBBMV-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.6
• 重原子数：
  17
• 可旋转键数：
  1
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.07
• 拓扑面积：
  30
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  4-methylbenzo[h]quinoline-2-carbaldehyde 在 palladium 10% on activated carbon 、 盐酸羟胺 、 氢气 作用下， 以 甲醇 、 乙醇 为溶剂， 30.0 ℃ 、500.01 kPa 条件下， 反应 3.75h， 生成 4-methyl-2-aminomethylbenzo[h]quinoline hydrochloride
  参考文献：
  名称：

  夹钳式4-官能化2-氨基甲基苯并[h]喹啉钌催化剂的制备

  摘要：

  Reaction of 1-naphthylamine with ethyl benzoylacetate gives the corresponding benzoyl acetamide derivative 1, which undergoes cyclization to 4-phenylbenzo[h]quinolin-2(1H)-one (2) in the presence of H2SO4. Bromination with POBr3, followed by reaction with n-BuLi and DATE, gives 4-phenylbenzo[h]quinoline-2-carbaldehyde (4), which is converted to the corresponding oxime hydrochloride 5 with NH2OH center dot HCL. Hydrogenation of 5 catalyzed by 10% Pd/C (type 338) leads to 4-phenyl-2-aminomethylbenzo[h]quinoline hydrochloride (HCNNPh center dot HCl, 6) isolated in high yield. Similarly, the 4-methyl-2-aminomethylbenzo[h]quinoline derivative (HCNNMe center dot HCl, 12) is prepared starting from 1-naphthylamine and 2,2,6-trimethyl-4H-1,3-dioxin-4-one, following the route for 6. Reaction of RuCl2(PPh3)(3) with a diphosphine (PP), the HCl salt 6, and NEt3 in 2-propanol leads to the pincer complexes RuCl(CNNPh)(PP) (PP = Ph2P(CH2)(3)PPh2, 13; Ph2P(CH2)(4)PPh2, 14; 1,1'-bis(diphenylphosphino)ferrocene, 15). The methyl derivatives RuCl(CNNMe) (PP) (PP = Ph2P(CH2)(3)PPh2, 16; Ph2P(CH2)(4)PPh2, 17; 1,1'-bis(diphenylphosphino)ferrocene, 18) are obtained in a similar way using 12 in place of 6. Treatment of [RuCl2(p-cymene)](2) with rac-BINAP, 6, and NEt3 affords RuCl(CNNPh)(BINAP) (19), isolated as a mixture of two diastereoisomers (3:4 molar ratio). The chiral RuCl(CNNPh)[(S,R)-JOSIPHOS] (20) is obtained as a single isomer from [RuCl2(p-cymene)](2), (S,R)-JOSIPHOS, and 6. Complexes 13-20 efficiently catalyze the transfer hydrogenation of acetophenone in 2-propanol at reflux in the presence of NaOiPr (2 mol%) with S/C = 5000-20 000 and at high rate (TOF up to 6.7 X 10(3) min(-1)). With complexes 13, 15, 17, and 18 several ketones of commercial-grade purity have been reduced to alcohols, including the bulky RCO(tBu) (R = Me, Ph) substrates. With 20 acetophenone is reduced to (S)-1-phenylethanol with 85% ee. The pincer complexes 13-15 and 18 are also found highly active in the hydrogenation of ketones at 40 degrees C with an S/C = 10 000, under 5 bar of dihydrogen in methanol and in the presence of 2 mol % of a base (NaOH, KOH, NaOMe).

  DOI：

  10.1021/acs.organomet.5b00978
• 作为产物：
  描述：

  alpha-萘基乙酰代乙酰苯胺 在 正丁基锂 、 硫酸 、 三溴氧磷 作用下， 以 四氢呋喃 、 甲苯 为溶剂， 反应 1.75h， 生成 4-methylbenzo[h]quinoline-2-carbaldehyde
  参考文献：
  名称：

  [EN] BENZO[H]QUINOLINE LIGANDS AND COMPLEXES THEREOF
  [FR] LIGANDS DE BENZO[H]QUINOLÉINE ET COMPLEXES DE CEUX-CI

  摘要：

  本发明提供了取代的三齿苯并[h]喹啉配体及其配合物。该发明还提供了配体和相应配合物的制备方法，以及使用配合物进行催化反应的过程。

  公开号：

  WO2016193761A1

文献信息

• Preparation of a Family of 10-Hydroxybenzo[<i>h</i>]quinoline Analogues via a Modified Sanford Reaction and Their Excited State Intramolecular Proton Transfer Properties
  作者：Joanna Piechowska、Daniel T. Gryko

  DOI：10.1021/jo202072d

  日期：2011.12.16

  acetoxylation of a sterically and electronically demanding library of analogues of benzo[h]quinoline. The optimal conditions for the insertion of an OAc group were identified after examining various reaction parameters (solvent, oxidant, catalyst, temperature, time). The conditions identified (Pd(OAc)2, PhI(OAc)2, MeCN, 150 °C, 16 h), combined with the hydrolysis of acetates, resulted in the formation of hydroxybenzoquinolines

  我们已经开发出一种高度优化的方法，该方法可以对空间和电子上要求较高的苯并[ h ]喹啉类似物进行氧化乙酰氧基化。通过检查各种反应参数（溶剂，氧化剂，催化剂，温度，时间），确定了OAc基团插入的最佳条件。确定的条件（Pd（OAc）2，PhI（OAc）2，MeCN，150°C，16 h），再加上乙酸酯的水解，导致羟基苯并喹啉的形成，产率为27-59％，而所有先前发表的方法均无效。该合成与各种功能（酯，醛，碳-碳三键）兼容，最重要的是，它可用于位阻类似物以及在各个位置具有给电子和吸电子取代基的化合物。所有获得的化合物均表现出激发态的分子内质子转移（ESIPT），表现为较小的荧光量子产率和较大的斯托克斯位移（8300–9660 cm –1）。八个10-羟基苯并[ h的结构变化的影响对]喹啉类似物的吸收和发射性质进行了详细研究。
• Processes for preparing and using ruthenium and osmium complexes
  申请人：JOHNSON MATTHEY PUBLIC LIMITED COMPANY

  公开号：US10428098B2

  公开（公告）日：2019-10-01

  The present invention relates to improved processes for the preparation of ruthenium or osmium complexes comprising acetate ligands, in particular, ruthenium complexes.

  本发明涉及制备包含醋酸配体的钌或锇络合物，特别是钌络合物的改进工艺。
• PROCESS
  申请人：Johnson Matthey Public Limited Company

  公开号：EP3303353B1

  公开（公告）日：2022-01-12
• BENZO[H]QUINOLINE LIGANDS AND COMPLEXES THEREOF
  申请人：JOHNSON MATTHEY PUBLIC LIMITED COMPANY

  公开号：US20180169641A1

  公开（公告）日：2018-06-21

  The present invention provides substituted tridentate benzo[h]quinoline ligands and complexes thereof. The invention also provides the preparation of the ligands and the respective complexes, as well as to processes for using the complexes in catalytic reactions.
• [EN] PROCESS<br/>[FR] PROCÉDÉ
  申请人：JOHNSON MATTHEY PLC

  公开号：WO2016193762A1

  公开（公告）日：2016-12-08

  The present invention relates to improved processes for the preparation of ruthenium or osmium complexes comprising acetate ligands, in particular, ruthenium complexes.