Methyl iodide → Methyl 3-methyl-6-[(1-methylethyl)sulfonyl]-7-(methyloxy)-2-[3-(trifluoromethyl)phenyl]-4-quinolinecarboxylate

HRID 245202ノート

反応式

HRID 245202 の反応式
Br[C:2]1[CH:3]=[C:4]2[C:9](=[CH:10][C:11]=1[O:12][CH3:13])[N:8]=[C:7]([C:14]1[CH:19]=[CH:18][CH:17]=[C:16]([C:20]([F:23])([F:22])[F:21])[CH:15]=1)[C:6]([CH3:24])=[C:5]2[C:25]([O:27][CH3:28])=[O:26].[CH:29]([S:32]([O-:34])=[O:33])([CH3:31])[CH3:30].[Na+].IC>CS(C)=O.C(Cl)Cl.O.[Cu]I>[CH3:24][C:6]1[C:7]([C:14]2[CH:19]=[CH:18][CH:17]=[C:16]([C:20]([F:22])([F:21])[F:23])[CH:15]=2)=[N:8][C:9]2[C:4]([C:5]=1[C:25]([O:27][CH3:28])=[O:26])=[CH:3][C:2]([S:32]([CH:29]([CH3:31])[CH3:30])(=[O:34])=[O:33])=[C:11]([O:12][CH3:13])[CH:10]=2

参加物

8

反応物 3

HCID 6328Methyl iodideHCID 23685748Sodium propane-2-sulfinateHCID 67384067Methyl 6-bromo-3-methyl-7-(methyloxy)-2-[3-(trifluoromethyl)phenyl]-4-quinolinecarboxylate

生成物 1

HCID 67383265Methyl 3-methyl-6-[(1-methylethyl)sulfonyl]-7-(methyloxy)-2-[3-(trifluoromethyl)phenyl]-4-quinolinecarboxylate収率 90.1%

試薬・触媒・溶媒 4

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)触媒HCID 679Dimethyl Sulfoxide溶媒HCID 962Water溶媒HCID 6344Dichloromethane溶媒

反応条件

温度
120 °C

実験手順

To a solution of methyl 6-bromo-3-methyl-7-(methyloxy)-2-[3-(trifluoromethyl)phenyl]-4-quinolinecarboxylate (10.0 g, 22.01 mmol) in dimethyl sulfoxide (200 mL) was added copper(I) iodide (8.39 g, 44.0 mmol) and sodium isopropanesulfinate (5.73 g, 44.0 mmol). The mixture was evacuated, purged with N2 three times, and heated at 120° C. overnight. The mixture was cooled to room temperature, treated with iodomethane (4.13 mL, 66.0 mmol), and stirred for 1 h. The reaction mixture was diluted with methylene chloride (150 mL) and water (150 mL), stirred for 30 min, and filtered through Celite®. The filtrate was extracted with methylene chloride, and the organic phase was washed with brine, dried over Na2SO4, filtered, and concentrated. The material was purified via column chromatography (ISCO, 0-30% ethyl acetate/methylene chloride) to give methyl 3-methyl-6-[(1-methylethyl)sulfonyl]-7-(methyloxy)-2-[3-(trifluoromethyl)phenyl]-4-quinolinecarboxylate (9.55 g, 90% yield). 1H NMR (400 MHz, DMSO-d6) δ8.24 (s, 1H), 7.99-8.05 (m, 2H), 7.91 (s, 1H), 7.76-7.84 (m, 2H), 4.09 (s, 6H), 3.83 (quin, J=6.84 Hz, 1H), 2.37 (s, 3H), 1.21 (s, 3H), 1.20 (s, 3H); MS (m/z) 482.1 (M+H+).

後処理

  1. customThe mixture was evacuated
  2. custompurged with N2 three times
  3. temperatureThe mixture was cooled to room temperature
  4. stirringstirred for 30 min
  5. filtrationfiltered through Celite®
  6. extractionThe filtrate was extracted with methylene chloride
  7. washthe organic phase was washed with brine
  8. dry with materialdried over Na2SO4
  9. filtrationfiltered
  10. concentrationconcentrated
  11. customThe material was purified via column chromatography (ISCO, 0-30% ethyl acetate/methylene chloride)

出典と根拠

ORDレコード
ord-f60dd02d0952439f95e08ed0b9e7553d
出典データセット
uspto-grants-2014_02
特許番号
US08658636B2

反応ノート

読み込み中…