반응 #46937

반응 방정식

acetic anhydride

n-Butyl lithium

o-bromostyrene

bromide

dry ice isopropanol

2-bromobenzaldehyde

magnesium

o-bromostyrene

→

o-vinyl acetophenone

용매

THF

THF

THF

THF

반응 조건

후처리

1. 1
   기타Into a 3 necked 500 mL round bottom flask, equipped with a cooling condenser
2. 2
   workup.ADDITIONaddition funnel
3. 3
   workup.ADDITIONwas added via a syringe
4. 4
   기타was dripped into the flask slowly (2 hours)
5. 5
   workup.STIRRINGAfter stirred for 48 hours
6. 6
   기타the reaction mixture was quenched with brine (250 mL)
7. 7
   추출The aqueous layer was extracted with toluene (100 mL×2)
8. 8
   workup.ADDITIONThe toluene layer was diluted with hexane
9. 9
   기타to precipitate triphenylphosphine oxide
10. 10
    기타After rotary evaporating off the solvent
11. 11
    기타the crude product was purified by column chromatography (silica gel 60-200 mesh), with 100% hexane
12. 12
    기타Into a 3-necked round bottom flask fitted with condenser, self-equalizing funnel
13. 13
    workup.ADDITIONwas added
14. 14
    기타After initiation of the reaction
15. 15
    온도the mixture was refluxed for 1.5 hours
16. 16
    기타(circa 1 hour)
17. 17
    workup.STIRRINGthe mixture was stirred for 2.5 hours at −70° C
18. 18
    기타the mixture was then quenched with aqueous ammonium chloride
19. 19
    추출extracted with ethyl acetate (100 mL×2)
20. 20
    세척After washing with water
21. 21
    건조dried over sodium sulfate and removal of the solvent
22. 22
    기타yellow oil was obtained
23. 23
    기타above did not provide a clean product

실험 절차

Into a 3 necked 500 mL round bottom flask, equipped with a cooling condenser, a self equalizing addition funnel and a rubber septum, methyl triphenyl phosphonium bromide (54.5 g, 0.153 moles, Aldrich) was suspended in THF (120 mL). After flashing with nitrogen for 30 minutes, the flask was cooled to 0° C. n-Butyl lithium (61 mL, 2.5 M in hexane, 153 mmole) was added via a syringe. After stirring for 1.5 hours, a solution of 2-bromobenzaldehyde (25.0 g, 135.1 mmole) in THF (100 mL) was dripped into the flask slowly (2 hours). After stirred for 48 hours, the reaction mixture was quenched with brine (250 mL). The aqueous layer was extracted with toluene (100 mL×2). The toluene layer was diluted with hexane to precipitate triphenylphosphine oxide. After rotary evaporating off the solvent, the crude product was purified by column chromatography (silica gel 60-200 mesh), with 100% hexane as eluding solvent. First fraction, yield 11.5 g (41%). 8.8 Grams (48 mmole) of o-bromostyrene was used for the next reaction. Into a 3-necked round bottom flask fitted with condenser, self-equalizing funnel, a stopper and charged with magnesium (10 g, pre-activated), o-bromostyrene in 30 mL THF was added to cover Mg. After initiation of the reaction, the rest of bromide solution was added slowly and the mixture was refluxed for 1.5 hours. Into another 3-necked flask, acetic anhydride (10 g, 98 mmole) was dissolved in THF (30 mL) and the flask was cooled with dry ice/isopropanol. The Grignard reagent was transferred slowly (circa 1 hour) via a cannula needle and the mixture was stirred for 2.5 hours at −70° C. After allowing to warm to room temperature, the mixture was then quenched with aqueous ammonium chloride and extracted with ethyl acetate (100 mL×2). After washing with water, dried over sodium sulfate and removal of the solvent, yellow oil was obtained. Yield: 6.5 gram (93%). 1H-NMR (CDCl3, δ): 5.3 (d, 1H), 5.6 (d, 1H); 7.2 (q, 1H), 7.3 (t, 1H), 7.4 (t, 1H); 7.55 (d, 1H); 7.6 (d, 1H). 13C-NMR: 30, 116, 127, 128, 130, 132, 136, 137.5, 138, 201. Epoxidation using a method similar to that described above did not provide a clean product.

출처