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

HRID 85267Notes

Reaction equation

HRID 85267 reaction equation
[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

Participants

7

Reactant 4

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

Product 1

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

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
-70 °C

Procedure

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%).

Workup

  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%)

Sources & evidence

ORD record
ord-2ae05713e8ae4ca2a15d02f9be45ffa3
Source dataset
uspto-grants-2014_09
Patent number
US08846955B2

Reaction notes

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