Reaktion #1274190

Reaktionsgleichung

NaH

trimethylsulfonium iodide

4-formyl-2-methoxy-5-methylbenzonitrile

→

2-methoxy-5-methyl-4-(oxiran-2-yl)benzonitrile

Lösungsmittel

THF

DMSO

THF

Reaktionsbedingungen

Aufarbeitung

1. 1
   SonstigeThe resulting reaction mixture
2. 2
   workup.STIRRINGwas stirred at 0° C. under N2 for 1 hr
3. 3
   Temperaturit was warmed gradually to room temperature
4. 4
   workup.STIRRINGstirred at that temperature for 12 hr
5. 5
   SonstigeThe starting material was consumed
6. 6
   TemperaturThe reaction mixture was cooled to 0° C.
7. 7
   Sonstigequenched with dropwise addition of water
8. 8
   ExtraktionThe mixture was extracted with ethyl acetate (2×200 ml)
9. 9
   WaschenThe combined organic layers were washed with water, brine
10. 10
    Trocknendried (MgSO4)
11. 11
    Filtrationfiltered
12. 12
    EinengenThe filtrate was concentrated in vacuo
13. 13
    SonstigeThe residue was purified via column chromatography (silica gel, 10-30% EtOAc-hexanes)

Vorschrift

To a cool solution of NaH (1.20 g, 30.0 mmol) in THF (300 ml) was added dropwise a solution of trimethylsulfonium iodide (8.74 g, 42.8 mmol) in DMSO (80 mL). The resulting mixture was stirred at 0° C. under N2 for 20 min. The solution of 4-formyl-2-methoxy-5-methylbenzonitrile (5.00 g, 28.5 mmol) in THF (60 mL) was added. The resulting reaction mixture was stirred at 0° C. under N2 for 1 hr, and then it was warmed gradually to room temperature and stirred at that temperature for 12 hr. The starting material was consumed as indicated by TLC (25% ethyl acetate/hexanes). The reaction mixture was cooled to 0° C. and quenched with dropwise addition of water. The mixture was extracted with ethyl acetate (2×200 ml). The combined organic layers were washed with water, brine, then dried (MgSO4) and filtered. The filtrate was concentrated in vacuo. The residue was purified via column chromatography (silica gel, 10-30% EtOAc-hexanes) to afford 2-methoxy-5-methyl-4-(oxiran-2-yl)benzonitrile. 1H NMR (CDCl3, 500 MHz) δ 7.35 (s, 1H), 6.88 (s, 1H), 4.01 (s, 1H), 3.92 (s, 3H), 3.25 (s, 1H), 2.65 (d, J=2.6 Hz, 1H), 2.37 (s, 3H); LC/MS: (IE, m/z) [M+1]+=190.0; tR=2.85 min.

Quelle