2-Hydroxy-4-methyl-benzochinolin(7:8) | 1210-07-7

• 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: 2-Hydroxy-4-methyl-benzochinolin(7:8)
• 英文别名: 4-methyl-benzo[h]quinolin-2-ol；4-Methyl-benzo[h]chinolin-2-ol；4-methyl-1H-benzo[h]quinolin-2-one
• CAS: 1210-07-7
• 化学式: C₁₄H₁₁NO
• 分子量: 209.247
• InChiKey: ZMXBCQZLZQUSEA-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.5
• 重原子数：
  16
• 可旋转键数：
  0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.07
• 拓扑面积：
  29.1
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  2-Hydroxy-4-methyl-benzochinolin(7:8) 在 正丁基锂 、 palladium 10% on activated carbon 、 盐酸羟胺 、 氢气 、 三溴氧磷 作用下， 以 四氢呋喃 、 甲醇 、 乙醇 、 正己烷 、 异丙醇 、 甲苯 为溶剂， -65.0~120.0 ℃ 、500.01 kPa 条件下， 反应 5.5h， 生成 RuCl(4-methyl-2-aminomethylbenzo[h]quinoline-H )(1,3-bis(diphenylphosphino)propane)
  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 硫酸 作用下， 以 neat (no solvent) 为溶剂， 反应 1.0h， 以93%的产率得到2-Hydroxy-4-methyl-benzochinolin(7:8)
  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

• Substituent effects on absorption and fluorescence spectra of carbostyrils
  作者：Walter M.F. Fabian、Karlheinz S. Niederreiter、Georg Uray、Wolfgang Stadlbauer

  DOI：10.1016/s0022-2860(98)00616-4

  日期：1999.3

  Abstract Absorption and fluorescence spectra as well as quantum yields of a series of differently substituted carbostyrils (quinolin-2(1H)-ones) are reported. Especially for compounds containing donor substituents in position 6, substantial bathochromic shifts (comparable to analogous coumarins) of both absorption as well as fluorescence transitions are obtained. High absorption intensities and quantum

  摘要 报告了一系列不同取代的喹诺酮 (quinolin-2(1H)-ones) 的吸收光谱和荧光光谱以及量子产率。特别是对于在 6 位含有供体取代基的化合物，获得了吸收和荧光跃迁的显着红移（与类似香豆素相当）。7 供体取代异构体具有高吸收强度和量子产率。半经验分子轨道计算（AM1 表示结构，ZINDO 表示电子跃迁能）被证明是预测这些化合物的吸收和荧光特性的合适工具。从头算和密度泛函计算确定内酰胺形式作为母体喹啉-2(1H)-one 的主要互变异构体。
• [EN] BENZO[H]QUINOLINE LIGANDS AND COMPLEXES THEREOF<br/>[FR] LIGANDS DE BENZO[H]QUINOLÉINE ET COMPLEXES DE CEUX-CI
  申请人：JOHNSON MATTHEY PLC

  公开号：WO2016193761A1

  公开（公告）日：2016-12-08

  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.

  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。
• 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.