反応 #46937

反応方程式

acetic anhydride

n-Butyl lithium

o-bromostyrene

bromide

dry ice isopropanol

2-bromobenzaldehyde

magnesium

o-bromostyrene

→

o-vinyl acetophenone

溶媒

THF

THF

THF

THF

反応条件

後処理

1. 1
   その他Into 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
   その他was dripped into the flask slowly (2 hours)
5. 5
   workup.STIRRINGAfter stirred for 48 hours
6. 6
   その他the reaction mixture was quenched with brine (250 mL)
7. 7
   抽出The aqueous layer was extracted with toluene (100 mL×2)
8. 8
   workup.ADDITIONThe toluene layer was diluted with hexane
9. 9
   その他to precipitate triphenylphosphine oxide
10. 10
    その他After rotary evaporating off the solvent
11. 11
    その他the crude product was purified by column chromatography (silica gel 60-200 mesh), with 100% hexane
12. 12
    その他Into a 3-necked round bottom flask fitted with condenser, self-equalizing funnel
13. 13
    workup.ADDITIONwas added
14. 14
    その他After initiation of the reaction
15. 15
    温度the mixture was refluxed for 1.5 hours
16. 16
    その他(circa 1 hour)
17. 17
    workup.STIRRINGthe mixture was stirred for 2.5 hours at −70° C
18. 18
    その他the mixture was then quenched with aqueous ammonium chloride
19. 19
    抽出extracted with ethyl acetate (100 mL×2)
20. 20
    洗浄After washing with water
21. 21
    乾燥dried over sodium sulfate and removal of the solvent
22. 22
    その他yellow oil was obtained
23. 23
    その他above did not provide a clean product

実験手順

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.

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