Reaktion #172514

Reaktionsgleichung

iodine

[3-benzyloxy-4-(2-thiophene-2-ylvinyl)phenyl]butyl[4-(tert-butyldiphenylsiloxy) butyl]amine

n-butyllithium

N,N-dimethylformamide

→

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

Ausbeute 57.6%

Lösungsmittel

ether

tetrahydrofuran

Reaktionsbedingungen

Aufarbeitung

1. 1
   workup.ADDITIONwas added dropwise
2. 2
   workup.STIRRINGAfter the mixture was stirred for 1.5 hours
3. 3
   Sonstigethe bath was removed
4. 4
   workup.ADDITIONAt −10° C., 10 ml of water was added dropwise
5. 5
   workup.ADDITIONAfter the reaction mixture was poured into 100 ml of water, extraction with ethyl acetate
6. 6
   Waschenwashing with a saturated saline solution
7. 7
   Trocknendrying over anhydrous sodium sulfate, and concentration
8. 8
   SonstigeThe residual liquid was purified by silica gel column chromatography
9. 9
   Sonstigeto give a reddish orange oily matter
10. 10
    workup.STIRRINGAfter stirred at room temperature for 30 minutes
11. 11
    Waschenthe mixture was washed with a 5% sodium bisulfite solution
12. 12
    TrocknenDrying over anhydrous magnesium sulfate and concentration
13. 13
    SonstigeThe residue was purified by silica gel column chromatography
14. 14
    Sonstigeto give 1.21 g of a red oily matter (yield: 57.6%)

Vorschrift

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%).

Quelle