反応 #4896

反応方程式

Hydrogen chloride

sodium 2-[(1-methyl-3-pyrrolidinyl)oxy]-3-pyridinecarboxylate

triphenylphosphine

carbon tetrachloride

→

2-(2-Chloroethyl)-2,3-dihydro-4-methylpyrido[3,2-f][1,4]-oxazepin-5(4H)-one hydrochloride

溶媒

chloroform

ethanol

反応条件

後処理

1. 1
   温度at reflux for 1.5 hr
2. 2
   その他the heat removed
3. 3
   workup.STIRRINGThe solution was stirred for 1 hour
4. 4
   温度while cooling
5. 5
   workup.ADDITION200 ml of isooctane was added
6. 6
   抽出The solution was extracted 4 times with a total of 800 ml of dilute hydrochloric acid
7. 7
   抽出extracted with chloroform
8. 8
   その他The chloroform layer was separated
9. 9
   乾燥dried over sodium sulfate
10. 10
    濃縮concentrated
11. 11
    workup.DISSOLUTIONThe residue was dissolved in a mixture of 500 ml each of isopropyl alcohol and isopropyl ether
12. 12
    その他A portion was recrystallized from isopropyl alcohol, m.p. 149°-153° C.

実験手順

Hydrogen chloride gas was bubbled into a suspension of 150 g (0.61 mole) of sodium 2-[(1-methyl-3-pyrrolidinyl)oxy]-3-pyridinecarboxylate in 1 liter of chloroform until a pH of 6 was reached. To the stirred mixture was added 350 g (1.34 mole) of triphenylphosphine and 350 g (2.3 mole) of carbon tetrachloride and the resulting cloudy solution was stirred at reflux for 1.5 hr. About 100 ml of ethanol was added and the heat removed. The solution was stirred for 1 hour while cooling and 200 ml of isooctane was added. The solution was extracted 4 times with a total of 800 ml of dilute hydrochloric acid. The acid extracts were combined, made basic with sodium hydroxide and extracted with chloroform. The chloroform layer was separated and dried over sodium sulfate and concentrated. The residue was dissolved in a mixture of 500 ml each of isopropyl alcohol and isopropyl ether and acidified with ethereal hydrogen chloride. The resulting crystals weighed 82 g (49%). A portion was recrystallized from isopropyl alcohol, m.p. 149°-153° C.

出典