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

Temperatur

-69 °C

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%).

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%)

ORD-Eintrag

ord-d6fc12b8db264e6eb5556c4d01913a61

Quelldatensatz

uspto-grants-2014_09

DOI

10.6084/m9.figshare.5104873.v1

Patentnummer

US08846955B2