Iodine → 5-[2-[2-Benzyloxy-4-[butyl[4-(tert-butyldiphenylsiloxy) butyl]amino]phenyl]vinyl]thiophene-2-carboaldehyde

HRID 85332Notes

Reaction equation

HRID 85332 reaction equation
[CH2:1]([O:8][C:9]1[CH:10]=[C:11]([N:22]([CH2:45][CH2:46][CH2:47][CH3:48])[CH2:23][CH2:24][CH2:25][CH2:26][O:27][Si:28]([C:41]([CH3:44])([CH3:43])[CH3:42])([C:35]2[CH:40]=[CH:39][CH:38]=[CH:37][CH:36]=2)[C:29]2[CH:34]=[CH:33][CH:32]=[CH:31][CH:30]=2)[CH:12]=[CH:13][C:14]=1[CH:15]=[CH:16][C:17]1[S:18][CH:19]=[CH:20][CH:21]=1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.C([Li])CCC.CN(C)[CH:56]=[O:57].II>O1CCCC1.CCOCC>[CH2:1]([O:8][C:9]1[CH:10]=[C:11]([N:22]([CH2:45][CH2:46][CH2:47][CH3:48])[CH2:23][CH2:24][CH2:25][CH2:26][O:27][Si:28]([C:41]([CH3:42])([CH3:43])[CH3:44])([C:29]2[CH:34]=[CH:33][CH:32]=[CH:31][CH:30]=2)[C:35]2[CH:36]=[CH:37][CH:38]=[CH:39][CH:40]=2)[CH:12]=[CH:13][C:14]=1[CH:15]=[CH:16][C:17]1[S:18][C:19]([CH:56]=[O:57])=[CH:20][CH:21]=1)[C:2]1[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=1

Participants

7

Reactant 4

HCID 807IodineHCID 6228DimethylformamideHCID 68009023[3-Benzyloxy-4-(2-thiophene-2-ylvinyl)phenyl]butyl[4-(tert-butyldiphenylsiloxy) butyl]amineHCID 178418339Butyllithium

Product 1

HCID 866676105-[2-[2-Benzyloxy-4-[butyl[4-(tert-butyldiphenylsiloxy) butyl]amino]phenyl]vinyl]thiophene-2-carboaldehydeYield 57.6%

Reagents, catalysts & solvents 2

HCID 3283Diethyl EtherSolventHCID 8028TetrahydrofuranSolvent

Conditions

Temperature
-69 °C

Procedure

In a stream of argon, in 20 ml of tetrahydrofuran was dissolved 2.02 g (3.0 mmol) of [3-benzyloxy-4-(2-thiophene-2-ylvinyl)phenyl]butyl[4-(tert-butyldiphenylsiloxy) butyl]amine, and 2.8 ml of n-butyllithium (1.6 mol solution in hexane) (4.48 mmol) was added dropwise thereto under cooling at −66 to −72° C. After the mixture was stirred for 35 minutes, 0.3 ml (3.9 mmol) of N,N-dimethylformamide was added dropwise thereto. After the mixture was stirred for 1.5 hours, the bath was removed and the temperature was allowed to rise. At −10° C., 10 ml of water was added dropwise. After the reaction mixture was poured into 100 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 reddish orange oily matter. Next, 1.43 g of the oily matter was dissolved in 150 ml of ether and 50 mg of iodine was added thereto. After stirred at room temperature for 30 minutes, the mixture was washed with a 5% sodium bisulfite solution and then with a saturated saline solution. Drying over anhydrous magnesium sulfate and concentration were performed. The residue was purified by silica gel column chromatography to give 1.21 g of a red oily matter (yield: 57.6%).

Workup

  1. additionwas added dropwise
  2. stirringAfter the mixture was stirred for 1.5 hours
  3. customthe bath was removed
  4. additionAt −10° C., 10 ml of water was added dropwise
  5. additionAfter the reaction mixture was poured into 100 ml of water, extraction with ethyl acetate
  6. washwashing with a saturated saline solution
  7. dry with materialdrying over anhydrous sodium sulfate, and concentration
  8. customThe residual liquid was purified by silica gel column chromatography
  9. customto give a reddish orange oily matter
  10. stirringAfter stirred at room temperature for 30 minutes
  11. washthe mixture was washed with a 5% sodium bisulfite solution
  12. dry with materialDrying over anhydrous magnesium sulfate and concentration
  13. customThe residue was purified by silica gel column chromatography
  14. customto give 1.21 g of a red oily matter (yield: 57.6%)

Sources & evidence

ORD record
ord-d6fc12b8db264e6eb5556c4d01913a61
Source dataset
uspto-grants-2014_09
Patent number
US08846955B2

Reaction notes

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