反応 #11455

反応方程式

carbamate

tert-butyl 3-aminopropylcarbamate

2,4-dichloro-5,6-dimethyl-3-nitropyridine

triethylamine

→

tert-butyl 3-[(2-chloro-5,6-dimethyl-3-nitropyridin-4-yl)amino]propylcarbamate

収率 77.2%

溶媒

N,N-dimethylformamide

N,N-dimethylformamide

反応条件

後処理

1. 1
   温度was heated to 55° C
2. 2
   温度to cool to ambient temperature overnight
3. 3
   濃縮concentrated under reduced pressure
4. 4
   workup.DISSOLUTIONThe residue was dissolved in ethyl acetate (3 L)
5. 5
   洗浄Each aliquot was washed with water (2×1 L)
6. 6
   抽出they were extracted with ethyl acetate
7. 7
   乾燥dried over sodium sulfate
8. 8
   濃縮concentrated under reduced pressure
9. 9
   その他to provide 181 g of crude product
10. 10
    その他This material was recrystallized from acetonitrile

実験手順

A solution of tert-butyl 3-aminopropylcarbamate (121.39 g, 697 mmol) in N,N-dimethylformamide (200 mL) was slowly added to a solution of 2,4-dichloro-5,6-dimethyl-3-nitropyridine (110 g, 498 mmol) and triethylamine (104 mL, 746 mmol) in N,N-dimethylformamide (900 mL). After stirring at ambient temperature for 20 hours the reaction mixture was heated to 55° C. At 24 hours 0.1 equivalents of the carbamate was added. The reaction mixture was allowed to cool to ambient temperature overnight and then concentrated under reduced pressure. The residue was dissolved in ethyl acetate (3 L). The solution was divided into 3 aliquots (1 L each). Each aliquot was washed with water (2×1 L). The pH of the aqueous washes was adjusted to 10 with potassium carbonate and then they were extracted with ethyl acetate. All of the ethyl acetate layers were combined, dried over sodium sulfate and then concentrated under reduced pressure to provide 181 g of crude product. This material was recrystallized from acetonitrile to provide 138 g of tert-butyl 3-[(2-chloro-5,6-dimethyl-3-nitropyridin-4-yl)amino]propylcarbamate as a yellow solid.

出典