반응 #488964

반응 방정식

tert-butyl (2-hydroxyethyl)carbamate

Sodium hydride

3-chloro-2-chloromethyl-1-propene

AcOH

→

title compound

수율 59.0%

tert-Butyl 6-Methylene-1,4-oxazepane-4-carboxylate

수율 59.0%

용매

THF

dimethylformamide

반응 조건

후처리

1. 1
   기타evaporated in water
2. 2
   기타at 45-55° C.
3. 3
   온도reflux condenser
4. 4
   workup.ADDITIONThe residue was poured with water (300 mL)
5. 5
   추출extracted with a mixture of ethyl acetate (200 mL), hexane (100 mL) and chloroform (50 mL)
6. 6
   기타The organic layer was separated
7. 7
   세척washed with water (2×100 mL) and brine
8. 8
   추출The combined aqueous layer was extracted with a mixture of ethyl acetate (150 mL) and hexane (50 mL)
9. 9
   기타The organic layer was separated
10. 10
    세척washed with water (2×100 mL) and brine
11. 11
    여과The extracts were filtered sequentially through silica gel (25 g) and sodium sulfate (50 mL)
12. 12
    세척eluting with chloroform (100 mL)
13. 13
    기타The filtrate was evaporated
14. 14
    workup.DISTILLATIONthe residue was distilled in vacuum

실험 절차

60% Sodium hydride in oil (26 g, 0.65 mol, 2.17 eq) was added in one portion in argon flow at 5° C. to a solution of 3-chloro-2-chloromethyl-1-propene (35 mL, 0.3 mol, 1 eq) in dimethylformamide (500 mL). Then a solution of tert-butyl (2-hydroxyethyl)carbamate (48.3 g, 0.3 mol, 1 eq) in THF (500 mL) was added, and the reaction mixture was heated to 25° C. and stirred at this temperature for 2 h. Then the reaction mixture was neutralized with glacial AcOH (4.5 mL) and evaporated in water aspirator vacuum at 45-55° C. using a 15-cm reflux condenser. The residue was poured with water (300 mL) and extracted with a mixture of ethyl acetate (200 mL), hexane (100 mL) and chloroform (50 mL). The organic layer was separated and washed with water (2×100 mL) and brine. The combined aqueous layer was extracted with a mixture of ethyl acetate (150 mL) and hexane (50 mL). The organic layer was separated and washed with water (2×100 mL) and brine. The extracts were filtered sequentially through silica gel (25 g) and sodium sulfate (50 mL) eluting with chloroform (100 mL). The filtrate was evaporated, and the residue was distilled in vacuum to give title compound as a colorless oil (bp 76-79° C. at 0.7 mmHg) (35.8 g, 0.177 mol, 56%)

출처