反応 #317509

反応方程式

2-(2,6-dichlorobenzamido)pent-4-enoic acid

Water

sodium hydrogen carbonate

Thionyl chloride

→

2-(2,6-dichlorobenzamido)pent-4-enoic acid methyl ester

溶媒

methanol

反応条件

後処理

1. 1
   その他higher than 110° C.
2. 2
   workup.ADDITIONwas added
3. 3
   濃縮After concentrating the reaction solution
4. 4
   その他to remove methanol, aqueous layer
5. 5
   抽出was extracted twice with ethyl acetate
6. 6
   洗浄Organic layers were washed 3 times with water
7. 7
   乾燥once with saturated brine, and dried over anhydrous sodium sulfate
8. 8
   その他After removing anhydrous sodium sulfate
9. 9
   ろ過by filtration
10. 10
    濃縮the filtrate was concentrated
11. 11
    その他The residue was recrystallized from hexane/ethyl acetate mixed solvent

実験手順

Allylglycine (10.11 g) was dissolved in a mixed solvent of 2N aqueous sodium hydroxide solution (176 ml) and dioxane (175 ml), and 2,6-dichlorobenzoyl chloride (15.10 ml) was added dropwise thereto, followed by stirring the resulting mixture at room temperature for 10 hours. After concentrating the reaction solution to remove dioxane, water (150 ml) was added thereto and the resulting solution was washed with ether. Aqueous layer was acidified by adding 3N hydrochloric acid in small portions thereto, and extracted 3 times with ethyl acetate. Organic layers were washed with saturated brine and dried over anhydrous sodium sulfate. After removing anhydrous sodium sulfate by filtration, the filtrate was concentrated. The residue was recrystallized from hexane/ethyl acetate mixed solvent to obtain 2-(2,6-dichlorobenzamido)pent-4-enoic acid (23.48 g). (2) Under an argon atmosphere, a solution of 2-(2,6-dichlorobenzamido)pent-4-enoic acid (23.48 g) in methanol (250 ml) was cooled to 0° C. Thionyl chloride (10.70 ml) was added dropwise to the solution while keeping the reaction temperature not higher than 110° C., and thereafter the resulting mixture was stirred at room temperature for 5.5 hours. Water was added to the reaction solution, and sodium hydrogen carbonate was added thereto in small portions to neutralize it. After concentrating the reaction solution to remove methanol, aqueous layer was extracted twice with ethyl acetate. Organic layers were washed 3 times with water and once with saturated brine, and dried over anhydrous sodium sulfate. After removing anhydrous sodium sulfate by filtration, the filtrate was concentrated. The residue was recrystallized from hexane/ethyl acetate mixed solvent to obtain 2-(2,6-dichlorobenzamido)pent-4-enoic acid methyl ester (21.70 g). NMR (H1, CDCl3): δ 2.55-2.61 (1H, m), 2.68-2.75 (1H, m), 3.72 (3H, s), 4.88 (1H, td, J=7.8, 5.4 Hz), 5.06-5.13 (2H, m), 5.64-5.74 (1H, m), 6.33 (1H, brd, J=7.1 Hz), 7.17-7.26 (3H, m)

出典