반응 #56736

반응 방정식

(R)-glycidyl tosylate

NaH

2-allyloxy-4-nitrophenol

phenol

→

2-(2-Allyloxy-4-nitrophenoxymethyl)-oxirane

반응 조건

후처리

1. 1
   세척washed with 500 mL of hexane
2. 2
   workup.ADDITION1 L of DMF was added
3. 3
   기타prepared in the previous step
4. 4
   온도the mixture heated at 70-75° C. under nitrogen overnight
5. 5
   온도Upon cooling
6. 6
   기타the DMF was removed in vacuum
7. 7
   세척This was washed with 500 mL portions of 2 N HCl, saturated sodium bicarbonate and saturated brine
8. 8
   건조dried over sodium sulfate
9. 9
   여과The mixture was filtered
10. 10
    농축concentrated to an oil in vacuum and column
11. 11
    기타chromatographed on silica gel using 1:1 hexane/methylene chloride as eluent
12. 12
    기타The impure material was recrystallized from 1.2 L of 10% ethyl acetate/hexane
13. 13
    기타to give 34 g of pure (homogeneous on silica gel tlc with 1:1 hexane/methylene chloride) (R)-2-(2-allyloxy-4-nitrophenoxymethyl)-oxirane (m.p. 64° C.)

실험 절차

20 g (0.50 mole) of 60% NaH/mineral oil was placed in a two-liter flask and washed with 500 mL of hexane. 1 L of DMF was added, followed by 77 g (0.40 mole) of the 2-allyloxy-4-nitrophenol prepared in the previous step. Addition of the phenol was performed in portions under argon. After stirring the mixture for 30 minutes at room temperature under argon, 108 g (0.48 moles) of (R)-glycidyl tosylate was added and the mixture heated at 70-75° C. under nitrogen overnight. Upon cooling, the DMF was removed in vacuum and replaced with one liter of methylene chloride. This was washed with 500 mL portions of 2 N HCl, saturated sodium bicarbonate and saturated brine and dried over sodium sulfate. The mixture was filtered, concentrated to an oil in vacuum and column chromatographed on silica gel using 1:1 hexane/methylene chloride as eluent. This gave 43 g of product contaminated with traces of the two starting materials, followed by 21 g of pure product as a pale yellow solid. The impure material was recrystallized from 1.2 L of 10% ethyl acetate/hexane to give 34 g of pure (homogeneous on silica gel tlc with 1:1 hexane/methylene chloride) (R)-2-(2-allyloxy-4-nitrophenoxymethyl)-oxirane (m.p. 64° C.).

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