反応 #44025

反応方程式

sodium carbonate

acetone dicarboxylic acid

sodium acetate

propionaldehyde

benzylamine hydrochloride

→

product 123

1-benzyl-2,6-diethylpiperidin-4-one

溶媒

CH2Cl2

water

water

CH2Cl2

反応条件

後処理

1. 1
   その他A 1 L, 3-necked round-bottom flask, equipped with a mechanical stirrer
2. 2
   温度reflux condenser
3. 3
   workup.ADDITIONthermometer and addition funnel
4. 4
   workup.STIRRINGstirred at 5° C. for 30 min
5. 5
   workup.STIRRINGThe reaction mixture was stirred at 5° C. for 1 hour
6. 6
   温度to warm up to rt
7. 7
   workup.STIRRINGstirred for 70 hours
8. 8
   その他The organic layer was separated
9. 9
   抽出the aqueous layer was extracted with CH2Cl2 (300 mL)
10. 10
    洗浄The combined extracts were washed with sat. aq. sodium bicarbonate (200 mL), water (200 mL), brine (200 mL)
11. 11
    乾燥dried over anhydrous Na2SO4
12. 12
    ろ過The solution was filtered
13. 13
    その他evaporated
14. 14
    その他to give a brown liquid, ca. 57 g
15. 15
    ろ過filtered through a plug of basic alumina (ca. 3×2 in)
16. 16
    洗浄washing with CH2Cl2 (1 L)
17. 17
    その他The combined filtrates were evaporated

実験手順

A 1 L, 3-necked round-bottom flask, equipped with a mechanical stirrer, reflux condenser, thermometer and addition funnel was charged with a solution of propionaldehyde (25.3 g, 0.4 mol) in water (150 mL) and stirred. The solution was cooled in an ice-bath to 5° C. The solution was treated with benzylamine hydrochloride (37.2 g, 0.26 mol) and stirred at 5° C. for 30 min. Solid acetone dicarboxylic acid 89 (31.6 g, 0.2 mol) was added at 5° C., followed within 5 min with a solution of sodium acetate (7.65 g, 0.093 mol) in water (60 mL). The reaction mixture was stirred at 5° C. for 1 hour and then allowed to warm up to rt and stirred for 70 hours. CH2Cl2 (350 mL) was added and the pH of the mixture was adjusted to 9 by cautious addition of solid sodium carbonate. The organic layer was separated and the aqueous layer was extracted with CH2Cl2 (300 mL). The combined extracts were washed with sat. aq. sodium bicarbonate (200 mL), water (200 mL), brine (200 mL) and dried over anhydrous Na2SO4. The solution was filtered and evaporated to give a brown liquid, ca. 57 g. This was diluted with CH2Cl2 (100 mL) and filtered through a plug of basic alumina (ca. 3×2 in), washing with CH2Cl2 (1 L). The combined filtrates were evaporated to give the product 123 as a light orange liquid, 50.1 g, which was used without further purification.

出典