Hydrogen Peroxide → 2,4-dimethoxy-5-(1-methyl-1H-indol-2-yl)benzaldehyde

HRID 10743

反応式

HRID 10743 の反応式
[CH3:1][N:2]1[C:10]2[C:5](=[CH:6][CH:7]=[CH:8][CH:9]=2)[CH:4]=[CH:3]1.[Li]C(C)(C)C.B(CC)(CC)CC.Br[C:24]1[C:25]([O:34][CH3:35])=[CH:26][C:27]([O:32][CH3:33])=[C:28]([CH:31]=1)[CH:29]=[O:30].[OH-].[Na+].OO>C1COCC1.Cl[Pd](Cl)([P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1>[CH3:33][O:32][C:27]1[CH:26]=[C:25]([O:34][CH3:35])[C:24]([C:3]2[N:2]([CH3:1])[C:10]3[C:5]([CH:4]=2)=[CH:6][CH:7]=[CH:8][CH:9]=3)=[CH:31][C:28]=1[CH:29]=[O:30]

参加物

9

反応物 6

HCID 784Hydrogen PeroxideHCID 7357TriethylboraneHCID 117811-MethylindoleHCID 14798Sodium HydroxideHCID 6683465-Bromo-2,4-dimethoxybenzaldehydeHCID 178418306HCID 178418306、化合物

生成物 1

HCID 219810062,4-dimethoxy-5-(1-methyl-1H-indol-2-yl)benzaldehyde収率 25%

試薬・触媒・溶媒 2

HCID 178418476HCID 178418476、化合物触媒HCID 8028Tetrahydrofuran溶媒

実験手順

Ex-116A: To a solution of N-methyl indole (1.3 g, 10 mmol) in 50 ml THF, t-BuLi (1.7 m in THF, 7.1 ml, 12 mmol) was slowly added at 0° C. under nitrogen. The mixture was stirred at room temperature for 1 hr, BEt3 (1.0 M in THF, 12 ml, 12 mmol) was added, and the mixture stirred for another 1 hr at room temperature. Then, PdCl2(PPh3)2 (0.35 g, 0.5 mmol) and 5-bromo-2,4-dimethoxybenzaldehyde (3.7 g, 15 mmol) were added, and the mixture was heated to about 60° C. for 30 minutes. The reaction mixture was poured into 50 ml 10% NaOH and treated with 30% H2O2 and then stirred for 10 minutes. The mixture was extracted with EtOAc and combined organic phase was washed with H2O and brine, dried over MgSO4, and absorbed to small amount of silica gel. Column chromatography (EtOAc:Hexane, 1:2) gave 0.72 g (25%) 2,4-dimethoxy-5-(1-methyl-1H-indol-2-yl)-benzaldehyde. 1H-NMR (CDCl3) δ 10.33 (s, 1H), 7.84 (s, 1H), 7.60 (d, J=8 Hz, 1H), 7.31 (d, J=8 Hz, 1H), 7.18–7.24 (m, 1H), 7.07–7.12 (m, 1H), 6.53 (s, 1H), 6.46 (s, 1H), 4.00 (s, 3H), 3.89 (s, 3H), 3.53 (s, 3H). HRMS (EI) Calcd. for C18H17NO3: 295.1208. Found: 295.1202.

後処理

  1. stirringthe mixture stirred for another 1 hr at room temperature
  2. temperaturethe mixture was heated to about 60° C. for 30 minutes
  3. stirringstirred for 10 minutes
  4. extractionThe mixture was extracted with EtOAc and combined organic phase
  5. washwas washed with H2O and brine
  6. dry with materialdried over MgSO4
  7. customabsorbed to small amount of silica gel

出典と根拠

ORDレコード
ord-b835e6a7a7f3491a9842d10f3e2224da
出典データセット
uspto-grants-2006_08
特許番号
US07094801B2

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