Reaktion #485274

Reaktionsgleichung

sodium sulfide

Et3N

diol

[4-(allyloxy)-2-(hydroxymethyl)phenyl]methanol

Methanesulfonyl chloride

→

desired product

Ausbeute 23.1%

5-(allyloxy)-1,3-dihydro-2-benzothiophene

Ausbeute 23.1%

Lösungsmittel

water

DCM

Reaktionsbedingungen

Aufarbeitung

1. 1
   Sonstigeto reach room temperature
2. 2
   SonstigeThe reaction was then quenched by the addition of water
3. 3
   SonstigeThe DCM layer was separated
4. 4
   Extraktionthe aqueous layer was re-extracted with DCM (50 mL)
5. 5
   WaschenThe combined organic fractions were washed with water (50 mL)
6. 6
   Trocknendried (MgSO4)
7. 7
   Einengenconcentrated to a volume of ca. 30 mL
8. 8
   workup.ADDITIONBenzyltriethylammonium chloride (1 g) was added
9. 9
   workup.STIRRINGThe mixture was stirred rapidly under a nitrogen atmosphere for 15 h
10. 10
    SonstigeThe organic layer was separated
11. 11
    Extraktionthe aqueous layer was re-extracted with DCM (50 mL)
12. 12
    TrocknenThe combined organic layers were dried (MgSO4)
13. 13
    Sonstigeevaporated to a yellow oil
14. 14
    SonstigeFlash chromatography afforded two fractions
15. 15
    Sonstigecrystallisation of the dimeric material which
16. 16
    Sonstigewas removed by filtration

Vorschrift

Crude diol from stage (i) (3.5 g, 18 mmol) was dissolved in DCM (60 mL) and treated with Et3N (10 mL, 72 mmol) and the solution was cooled to 0° C. Methanesulfonyl chloride (4.2 mL, 54 mmol) was added dropwise and the solution was stirred for 1 h being allowed to reach room temperature. The reaction was then quenched by the addition of water followed by 2M HCl (50 mL). The DCM layer was separated and the aqueous layer was re-extracted with DCM (50 mL). The combined organic fractions were washed with water (50 mL), dried (MgSO4) and concentrated to a volume of ca. 30 mL. Benzyltriethylammonium chloride (1 g) was added followed by a solution of sodium sulfide (5 g, 91 mmol) in water (50 mL). The mixture was stirred rapidly under a nitrogen atmosphere for 15 h. The organic layer was separated and the aqueous layer was re-extracted with DCM (50 mL). The combined organic layers were dried (MgSO4) and evaporated to a yellow oil. Flash chromatography afforded two fractions; the first was pure product and the second product contaminated with dimeric material. Trituration of the second fraction caused crystallisation of the dimeric material which was removed by filtration. The filtrate was combined with the first chromatography fraction to afford the desired product (800 mg, 23%); δH (CDCl3, 400 MHz) 4.16 (2H, s), 4.19 (2H, s), 4.48 (2H, m), 5.26 (1H, d), 5.37 (1H, d), 5.95-6.06 (1H, m), 6.74 (2H, m), 7.09 (1H, d).

Quelle