Reaktion #160766

Reaktionsgleichung

ammonium chloride

sodium azide

(+/−)-6-bromo-5-methyl-3-(3-nitropyridin-4-yl)cyclohex-2-enol

potassium tert-butoxide

→

(+/−)-2-azido-6-methyl-4-(3-nitropyridin-4-yl)cyclohex-3-enol

Ausbeute 55.0%

Lösungsmittel

water

THF

Reaktionsbedingungen

Aufarbeitung

1. 1
   SonstigeQuenched
2. 2
   workup.ADDITIONby adding saturated ammonium chloride and ethyl acetate
3. 3
   TrocknenThe organic phase was dried with brine
4. 4
   Filtrationsodium sulfate, filtered
5. 5
   Einengenconcentrated
6. 6
   workup.DISSOLUTIONThe crude product was dissolved in ethanol
7. 7
   SonstigeThe dark orange reaction
8. 8
   EinengenThe reaction was concentrated
9. 9
   Sonstigeto remove the ethanol, ethyl acetate and water
10. 10
    workup.ADDITIONwere added
11. 11
    Trocknenthe organic phase was dried with sodium sulfate
12. 12
    Filtrationfiltered
13. 13
    Einengenconcentrated
14. 14
    SonstigeThe crude material was purified via silica gel column chromatography
15. 15
    Wascheneluting with ethyl acetate and hexanes (1:1)

Vorschrift

To a solution of (+/−)-6-bromo-5-methyl-3-(3-nitropyridin-4-yl)cyclohex-2-enol (1.0 equiv.) in THF (0.1M) was added potassium tert-butoxide (1.5 equiv.). The reaction turned from orange to black almost immediately. By TLC, the formation of product is clean in 30 min. Quenched by adding saturated ammonium chloride and ethyl acetate. The organic phase was dried with brine, then sodium sulfate, filtered, and concentrated. The crude product was dissolved in ethanol and water (3:1, 0.1M), and ammonium chloride (2.0 equiv) and sodium azide (2.0 equiv.) were added. The dark orange reaction was stirred at room temperature overnight. The conversion to product is clean as indicated by LC/MS. The reaction was concentrated to remove the ethanol, ethyl acetate and water were added, the organic phase was dried with sodium sulfate, filtered, and concentrated. The crude material was purified via silica gel column chromatography eluting with ethyl acetate and hexanes (1:1) to give (+/−)-2-azido-6-methyl-4-(3-nitropyridin-4-yl)cyclohex-3-enol in 55% yield. LC/MS=276.0 (M+H), LC=2.803 min.

Quelle