تفاعل #470708

معادلة التفاعل

4-heptanone

n-butylamine

lithium hydroxide

dimethyl methoxymethylenemalonate

→

1-butyl-5-ethyl-2-oxo-6-propyl-1,2-dihydro-pyridine-3-carboxylic acid

المذيبات

water

water

water

THF

ظروف التفاعل

المعالجة

1. 1
   استخلاصthe mixture was extracted with ethyl acetate
2. 2
   غسيلAfter the organic layer had been washed with water
3. 3
   تجفيفdried with anhydrous sodium sulfate
4. 4
   أخرىthe solvent was removed by distillation under reduced pressure
5. 5
   workup.DISSOLUTIONThe obtained oily matter was dissolved in 2-methoxyethyl ether (40 mL)
6. 6
   درجة الحرارةheated
7. 7
   أخرىAfter the solvent had been removed by distillation under reduced pressure
8. 8
   workup.ADDITIONin mixing ratio
9. 9
   أخرىthat of 2:1), and a ark reddish-brown oily substance was obtained
10. 10
    غسيلwashed with diethyl ether
11. 11
    workup.ADDITIONAfter 2M hydrochloric acid had been added to the water layer
12. 12
    استخلاصthe water layer was extracted with ethyl acetate
13. 13
    غسيلThe organic layer was washed with water
14. 14
    تجفيفdried with anhydrous sodium sulfate
15. 15
    أخرىThe solvent was removed by distillation under reduced pressure
16. 16
    أخرىa pale yellow solid (AA03, 1.68 g, 18%) was obtained

الإجراء التجريبي

Under the nitrogen gas atmosphere, a solution of 4-heptanone (5.0 mM, 35.75 mmol), n-butylamine (4.25 mL, 4.29 mmol), and three drops of concentrated hydrochloric acid was stirred for 18.5 hours at room temperature. After that, water was added and the mixture was extracted with ethyl acetate. After the organic layer had been washed with water and then dried with anhydrous sodium sulfate, the solvent was removed by distillation under reduced pressure. The obtained oily matter was dissolved in 2-methoxyethyl ether (40 mL), and heated and stirred with dimethyl methoxymethylenemalonate (5.66 g, 32.5 mmol) at 120° C. for 3 hours. After the solvent had been removed by distillation under reduced pressure, the residue was refined with silica gel (100 g) column chromatography (ethyl acetate-hexane of 1:1 in mixing ratio and then that of 2:1), and a ark reddish-brown oily substance was obtained. The substance was dissolved in THF (20 mL) without purification, and a 1M lithium hydroxide aqueous solution (15.18 mL) and water (4.82 mL) were added, and then the mixture was stirred for 2 hours at room temperature. After that, the mixture was diluted with water and washed with diethyl ether. After 2M hydrochloric acid had been added to the water layer to acidify it, the water layer was extracted with ethyl acetate. The organic layer was washed with water and then dried with anhydrous sodium sulfate. The solvent was removed by distillation under reduced pressure and a pale yellow solid (AA03, 1.68 g, 18%) was obtained.

المصدر