反応 #160766

反応方程式

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

収率 55.0%

溶媒

water

THF

反応条件

後処理

1. 1
   その他Quenched
2. 2
   workup.ADDITIONby adding saturated ammonium chloride and ethyl acetate
3. 3
   乾燥The organic phase was dried with brine
4. 4
   ろ過sodium sulfate, filtered
5. 5
   濃縮concentrated
6. 6
   workup.DISSOLUTIONThe crude product was dissolved in ethanol
7. 7
   その他The dark orange reaction
8. 8
   濃縮The reaction was concentrated
9. 9
   その他to remove the ethanol, ethyl acetate and water
10. 10
    workup.ADDITIONwere added
11. 11
    乾燥the organic phase was dried with sodium sulfate
12. 12
    ろ過filtered
13. 13
    濃縮concentrated
14. 14
    その他The crude material was purified via silica gel column chromatography
15. 15
    洗浄eluting with ethyl acetate and hexanes (1:1)

実験手順

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.

出典