Dimethylformamide → 5-[2-(4-Dibutylamino-2-methoxyphenyl)vinyl]thiophene-2-carboaldehyde

HRID 85238Notes

Reaction equation

HRID 85238 reaction equation
[CH2:1]([N:5]([CH2:21][CH2:22][CH2:23][CH3:24])[C:6]1[CH:11]=[CH:10][C:9]([CH:12]=[CH:13][C:14]2[S:15][CH:16]=[CH:17][CH:18]=2)=[C:8]([O:19][CH3:20])[CH:7]=1)[CH2:2][CH2:3][CH3:4].C([Li])CCC.CN(C)[CH:32]=[O:33]>O1CCCC1>[CH2:21]([N:5]([CH2:1][CH2:2][CH2:3][CH3:4])[C:6]1[CH:11]=[CH:10][C:9]([CH:12]=[CH:13][C:14]2[S:15][C:16]([CH:32]=[O:33])=[CH:17][CH:18]=2)=[C:8]([O:19][CH3:20])[CH:7]=1)[CH2:22][CH2:23][CH3:24]

Participants

5

Reactant 3

HCID 6228DimethylformamideHCID 68008836Dibutyl[3-methoxy-4-[2-(thiophene-2-yl)vinyl]phenyl]amineHCID 178418339Butyllithium

Product 1

HCID 866675385-[2-(4-Dibutylamino-2-methoxyphenyl)vinyl]thiophene-2-carboaldehydeYield 79.2%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Conditions

Temperature
-71.5 °C

Procedure

In a stream of argon, in 25 ml of tetrahydrofuran was dissolved 1.5 g (4.37 mmol) of dibutyl[3-methoxy-4-[2-(thiophene-2-yl)vinyl]phenyl]amine, and 4.1 ml of n-butyllithium (1.6 mol solution in hexane) (6.56 mmol) was added dropwise thereto under cooling at −70 to −73° C. After the mixture was stirred for 1 hour, 0.43 ml (5.54 mmol) of N,N-dimethylformamide was added dropwise. After the reaction mixture was stirred for 1 hour, the bath was removed and the temperature was allowed to rise. To this mixture, 10 ml of water was added dropwise. After the reaction mixture was poured into 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 200 ml of ether and 70 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. After drying over anhydrous sodium sulfate and concentration were performed, the residue was purified by silica gel column chromatography to give 1.27 g of a reddish orange crystal (yield: 79.2%).

Workup

  1. additionwas added dropwise
  2. stirringAfter the reaction mixture was stirred for 1 hour
  3. customthe bath was removed
  4. additionTo this mixture, 10 ml of water was added dropwise
  5. additionAfter the reaction mixture was poured into water, extraction with ethyl acetate
  6. washwashing with a saturated saline solution
  7. dry with materialdrying over anhydrous sodium sulfate, and concentration
  8. dissolutionThe residual liquid was dissolved in 200 ml of ether
  9. addition70 mg of iodine pieces were added
  10. stirringAfter stirred at room temperature
  11. washthe mixture was washed with a 5% sodium bisulfite solution
  12. dry with materialAfter drying over anhydrous sodium sulfate and concentration
  13. customthe residue was purified by silica gel column chromatography

Sources & evidence

ORD record
ord-d8c3ef78980e407abc946d346867d672
Source dataset
uspto-grants-2014_09
Patent number
US08846955B2

Reaction notes

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