Iodine → HCID 86667579, compound

HRID 85286Notes

Reaction equation

HRID 85286 reaction equation
[CH2:1]([N:5]([CH2:23][CH2:24][CH2:25][CH3:26])[C:6]1[CH:11]=[CH:10][C:9]([CH:12]=[CH:13][CH:14]=[CH:15][C:16]2[S:17][CH:18]=[CH:19][CH:20]=2)=[C:8]([O:21][CH3:22])[CH:7]=1)[CH2:2][CH2:3][CH3:4].C([Li])CCC.CN(C)[CH:34]=[O:35].II>O1CCCC1.CCOCC.C(OCC)(=O)C.O>[CH2:23]([N:5]([CH2:1][CH2:2][CH2:3][CH3:4])[C:6]1[CH:11]=[CH:10][C:9]([CH:12]=[CH:13][CH:14]=[CH:15][C:16]2[S:17][C:18]([CH:34]=[O:35])=[CH:19][CH:20]=2)=[C:8]([O:21][CH3:22])[CH:7]=1)[CH2:24][CH2:25][CH3:26]

Participants

9

Reactant 4

HCID 807IodineHCID 6228DimethylformamideHCID 86667578HCID 86667578, compoundHCID 178418339Butyllithium

Product 1

HCID 86667579HCID 86667579, compoundYield 80.1%

Reagents, catalysts & solvents 4

HCID 962WaterSolvent2×HCID 3283Diethyl EtherSolventHCID 8028TetrahydrofuranSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
-69 °C

Procedure

In a stream of argon, in 13 ml of tetrahydrofuran was dissolved 0.83 g (2.25 mmol) of dibutyl[3-methoxy-4-[4-(thiophene-2-yl)-1,3-butadienyl]phenyl]amine, and 2.1 ml of n-butyllithium (1.6 mol solution in hexane) (3.36 mmol) was added dropwise thereto under cooling at −68 to −70° C. After the mixture was stirred for 30 minutes, 0.21 ml (2.87 mmol) of N,N-dimethylformamide was added dropwise thereto. The reaction mixture was stirred for 1.5 hours and the temperature was allowed to rise. To this mixture, 5 ml of water was added dropwise. After the reaction mixture was poured into 50 ml of water, extraction with ethyl acetate, washing with a saturated saline solution, drying over anhydrous sodium sulfate, and concentration were performed. The residual liquid was purified by silica gel column chromatography to give a dark reddish brown oily matter. After this oily matter was dissolved in 100 ml of ether, 600 mg of iodine was added thereto and the mixture was stirred. 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 715 mg of a dark reddish brown liquid (yield: 80.1%).

Workup

  1. additionwas added dropwise
  2. stirringThe reaction mixture was stirred for 1.5 hours
  3. washwashing with a saturated saline solution
  4. dry with materialdrying over anhydrous sodium sulfate, and concentration
  5. customThe residual liquid was purified by silica gel column chromatography
  6. customto give a dark reddish brown oily matter
  7. stirringthe mixture was stirred
  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

Sources & evidence

ORD record
ord-63979f3a24fa453283f06c7afe9e803f
Source dataset
uspto-grants-2014_09
Patent number
US08846955B2

Reaction notes

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