Water → 5-[2-(8-methoxy-2,3,6,7-tetrahydro-1H,5H-benzo[ij]quinolizine-9-yl) vinyl]thiophene-2-carboaldehyde

HRID 85267ノート

反応式

HRID 85267 の反応式
[CH3:1][O:2][C:3]1[C:14]2=[C:15]3[N:10]([CH2:11][CH2:12][CH2:13]2)[CH2:9][CH2:8][CH2:7][C:6]3=[CH:5][C:4]=1[CH:16]=[CH:17][C:18]1[S:19][CH:20]=[CH:21][CH:22]=1.C([Li])CCC.CN(C)[CH:30]=[O:31].O>O1CCCC1.C(OCC)(=O)C>[CH3:1][O:2][C:3]1[C:14]2=[C:15]3[N:10]([CH2:11][CH2:12][CH2:13]2)[CH2:9][CH2:8][CH2:7][C:6]3=[CH:5][C:4]=1[CH:16]=[CH:17][C:18]1[S:19][C:20]([CH:30]=[O:31])=[CH:21][CH:22]=1

参加物

7

反応物 4

HCID 962Water2 回HCID 6228DimethylformamideHCID 680093408-methoxy-9-[2-(thiophene-2-yl)vinyl]-2,3,6,7-tetrahydro-1H,5H-benzo[ij]quinolizineHCID 178418339Butyllithium

生成物 1

HCID 866675595-[2-(8-methoxy-2,3,6,7-tetrahydro-1H,5H-benzo[ij]quinolizine-9-yl) vinyl]thiophene-2-carboaldehyde収率 35.5%

試薬・触媒・溶媒 2

HCID 8028Tetrahydrofuran溶媒HCID 8857Ethyl Acetate溶媒

反応条件

温度
-70 °C

実験手順

In a stream of argon, in 25 ml of tetrahydrofuran was dissolved 1.29 g (4.14 mmol) of 8-methoxy-9-[2-(thiophene-2-yl)vinyl]-2,3,6,7-tetrahydro-1H,5H-benzo[ij]quinolizine, and 3.9 ml of n-butyllithium (1.6 mol solution in hexane) (6.24 mmol) was added dropwise thereto under cooling at −70° C. After the mixture was stirred for 1 hour, 0.43 g (5.88 mmol) of N,N-dimethylformamide was added dropwise thereto. The reaction mixture was stirred for 1 hour and the temperature was allowed to rise. To this mixture, 10 ml of water was added dropwise. After the reaction mixture was added to water, extraction with ethyl acetate, washing with a saturated saline solution, drying over anhydrous sodium sulfate, and concentration were performed. The residual liquid was dissolved in 300 ml of ether and 50 mg of iodine pieces were added thereto. After stirred at room temperature, the mixture was washed with a 5% sodium bisulfite solution and then with a saturated saline solution. Drying over anhydrous sodium sulfate and concentration were performed. The residue was purified by silica gel column chromatography to give 496 mg of a dark reddish brown oily matter (yield: 35.5%).

後処理

  1. additionwas added dropwise
  2. stirringThe reaction mixture was stirred for 1 hour
  3. washwashing with a saturated saline solution
  4. dry with materialdrying over anhydrous sodium sulfate, and concentration
  5. dissolutionThe residual liquid was dissolved in 300 ml of ether
  6. addition50 mg of iodine pieces were added
  7. stirringAfter stirred at room temperature
  8. washthe mixture was washed with a 5% sodium bisulfite solution
  9. dry with materialDrying over anhydrous sodium sulfate and concentration
  10. customThe residue was purified by silica gel column chromatography
  11. customto give 496 mg of a dark reddish brown oily matter (yield: 35.5%)

出典と根拠

ORDレコード
ord-2ae05713e8ae4ca2a15d02f9be45ffa3
出典データセット
uspto-grants-2014_09
特許番号
US08846955B2

反応ノート

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