Methanol → Methyl 2-isopropenylquinoline-6-carboxylate

HRID 1094654ノート

反応式

HRID 1094654 の反応式
Br[C:2]1[CH:3]=[C:4]2[C:9](=[CH:10][CH:11]=1)[N:8]=[C:7]([C:12]([CH3:14])=[CH2:13])[CH:6]=[CH:5]2.C1(P(C2C=CC=CC=2)CCCP(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C(N(CC)CC)C.[CH3:51][OH:52].CN([CH:56]=[O:57])C>C(OCC)(=O)C.C1(C)C=CC=CC=1.C([O-])(=O)C.[Pd+2].C([O-])(=O)C>[CH3:51][O:52][C:56]([C:2]1[CH:3]=[C:4]2[C:9](=[CH:10][CH:11]=1)[N:8]=[C:7]([C:12]([CH3:14])=[CH2:13])[CH:6]=[CH:5]2)=[O:57]

参加物

8

反応物 5

HCID 887MethanolHCID 6228DimethylformamideHCID 8471TriethylamineHCID 812191,3-Bis(diphenylphosphino)propaneHCID 666370726-Bromo-2-isopropenylquinoline

生成物 1

HCID 66637151Methyl 2-isopropenylquinoline-6-carboxylate収率 82%

試薬・触媒・溶媒 2

HCID 167845palladium(II) acetate触媒HCID 21584019Toluene ethylacetate溶媒

反応条件

温度
80 °C

実験手順

A mixture of 6-bromo-2-isopropenylquinoline (200 mg, 1.45 mmol), palladium acetate (18.1 mg, 0.081 mmol), 1,3-bis(diphenylphosphino)propane (33 mg, 0.081 mmol), triethylamine (245 mg, 2.42 mmol˜0.337 ml) and methanol (1.03 g, 1.31 ml˜32.2 mmol) in dry DMF (2.5 ml) was heated at 80° C. under carbon monooxide gas (balloon) for overnight (15 hours). The mixture was diluted with ethyl acetate-toluene (8:1) (159 ml) and the precipitate was filtered through a pad of celite. The organic layer was washed with water (×2), brine, dried over sodium sulfate and concentrated in vacuo to give the crude product. The crude product was purified by column chromatography on silica gel (150 g) with hexane-ethyl acetate (15:1) to furnish the title compound (150 mg, 82%) as dark yellow solid. 1H NMR (270 MH CDCl3) δ ppm 2.36 (3H, s), 3.99 (3H, s), 5.53-5.57 (1H, m), 5.98 (1H, s), 7.73-7.78 (1H, m), 8.08-8.31 (3H, m), 8.54-8.56 (1H, m). MS (ESI): m/z 228.21 (M+H)+.

後処理

  1. filtrationthe precipitate was filtered through a pad of celite
  2. washThe organic layer was washed with water (×2), brine
  3. dry with materialdried over sodium sulfate
  4. concentrationconcentrated in vacuo
  5. customto give the crude product
  6. customThe crude product was purified by column chromatography on silica gel (150 g) with hexane-ethyl acetate (15:1)

出典と根拠

ORDレコード
ord-d320923299534cb2955edfd6857f41d9
出典データセット
uspto-grants-2012_03
特許番号
US08134004B2

反応ノート

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