反応 #488994

反応方程式

tert-butyl (2-hydroxyethyl)carbamate

Sodium hydride

3-chloro-2-(chloromethyl)prop-1-ene

AcOH

→

title compound

収率 56.0%

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

収率 56.0%

溶媒

THF

dimethylformamide

反応条件

後処理

1. 1
   その他evaporated in a water aspirator in vacuo at 45-55° C.
2. 2
   温度reflux condenser
3. 3
   workup.ADDITIONThe residue was poured with water (300 mL)
4. 4
   抽出extracted with a mixture of ethylacetate (200 mL), hexane (100 mL) and chloroform (50 mL)
5. 5
   その他The organic layer was separated
6. 6
   洗浄washed with water (2×100 mL) and brine
7. 7
   抽出The combined aqueous layer was extracted with a mixture of ethylacetate (150 mL) and hexane (50 mL)
8. 8
   その他The organic layer was separated
9. 9
   洗浄washed with water (2×100 mL) and brine
10. 10
    ろ過The extracts were filtered sequentially through silica gel (25 g) and sodium sulphate (50 mL)
11. 11
    洗浄eluting with chloroform (100 mL)
12. 12
    その他The filtrate was evaporated
13. 13
    workup.DISTILLATIONthe residue was distilled in vacuo

実験手順

60% Sodium hydride in oil (26 g, 0.65 mol, 2.17 eq) was added in one portion in a stream of argon at 5° C. to a solution of 3-chloro-2-(chloromethyl)prop-1-ene (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. The reaction mixture was then neutralized with glacial AcOH (4.5 mL) and evaporated in a water aspirator in vacuo at 45-55° C. using a 15-cm reflux condenser. The residue was poured with water (300 mL) and extracted with a mixture of ethylacetate (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 ethylacetate (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 sulphate (50 mL), eluting with chloroform (100 mL). The filtrate was evaporated, and the residue was distilled in vacuo to give title compound as a colorless oil (bp 76-79° C. at 0.7 mm Hg) (35.8 g, 0.168 mol, 53%).

出典