반응 #56484

반응 방정식

hydrochloric acid

sodium sulfate

HSCH2CO2H

Ethyl 4-(4-oxobutyl)benzoate

1-amino-2-[1-(tetrahydro-2H-pyran-2-yloxy)cyclohexyl]ethane

→

title compound

수율 32.0%

4-{3-[3-[2-(1-Hydroxycyclohexyl)ethyl]-4-oxo-2-thiazolidinyl]propyl}benzoic Acid

수율 32.0%

용매

methanol

carbon tetrachloride

chloroform

water

반응 조건

후처리

1. 1
   workup.STIRRINGStirring
2. 2
   workup.WAITis continued for 2 hours
3. 3
   기타The solid is removed by filtration
4. 4
   세척washed with a small quantity of benzene
5. 5
   workup.ADDITIONThe combined filtrate and washings are diluted with benzene (70 ml.)
6. 6
   온도refluxed in a Dean-Stark apparatus for 16 hours
7. 7
   온도to cool to room temperature
8. 8
   세척subsequently washed with diluted hydrochloric acid and 5% sodium bicarbonate
9. 9
   건조dried over anhydrous magnesium sulfate
10. 10
    여과filtered
11. 11
    기타Evaporation in vacuo
12. 12
    기타affords an oil residue which
13. 13
    workup.STIRRINGThe resulting mixture is stirred at ambient temperature for 3 hours
14. 14
    추출extracted with ether
15. 15
    추출The ethereal extract
16. 16
    세척is washed with diluted sodium bicarbonate
17. 17
    건조dried over anhydrous magnesium sulfate
18. 18
    여과filtered
19. 19
    농축concentrated
20. 20
    기타to give an oil residue
21. 21
    세척Elution with chloroform-methanol (100:1; v:v; 630 ml.)
22. 22
    기타gives impure material
23. 23
    세척Further elution with the same eluant (300 ml.)

실험 절차

Ethyl 4-(4-oxobutyl)benzoate (4.15 g., 18.8 mmol.) is added dropwise to a stirred solution of 1-amino-2-[1-(tetrahydro-2H-pyran-2-yloxy)cyclohexyl]ethane in carbon tetrachloride (1 ml.) maintained at 25° C. The resulting mixture is stirred for 30 minutes before being treated with anhydrous sodium sulfate (4 g.). Stirring is continued for 2 hours. The solid is removed by filtration and washed with a small quantity of benzene. The combined filtrate and washings are diluted with benzene (70 ml.), treated with HSCH2CO2H (1.84 g., 20 mmole.) in one portion, and then refluxed in a Dean-Stark apparatus for 16 hours. The reaction mixture is allowed to cool to room temperature, subsequently washed with diluted hydrochloric acid and 5% sodium bicarbonate, dried over anhydrous magnesium sulfate, and filtered. Evaporation in vacuo affords an oil residue which is dissolved in methanol (50 ml.) plus concentrated hydrochloric acid (0.2 ml.). The resulting mixture is stirred at ambient temperature for 3 hours, diluted with water, and extracted with ether. The ethereal extract is washed with diluted sodium bicarbonate, dried over anhydrous magnesium sulfate, filtered, and concentrated to give an oil residue. The oil residue is then applied to a silica gel column (120 g.) with chloroform. Elution with chloroform-methanol (100:1; v:v; 630 ml.) gives impure material. Further elution with the same eluant (300 ml.) provides the title compound (2.5 g., 5.96 mmol., 32%) as a pale yellow oil, pmr (CDCl3) δ1.38 (3H, t), 3.50 (2H, s), 4.40 (2H, q), 4.72 (1H, m), 7.23 (2 H, d), 8.00 (2H, d).

출처