反応 #48180

反応方程式

ethyl acetate

Sodium hydride

4-([1,2,4]triazol-4-ylamino)-benzonitrile

1,3-dibromopropane

→

title compound

4-[(3-Bromo-propyl)-[1,2,4]triazol-4-yl-amino]-benzonitrile

溶媒

DMSO

反応条件

後処理

1. 1
   workup.ADDITIONwas added
2. 2
   その他The mixture was transferred into a separation funnel
3. 3
   抽出extracted with water (twice 100 mL) and brine (20 mL)
4. 4
   乾燥The organic layer was dried over sodium sulphate
5. 5
   濃縮concentrated under reduced pressure (water bath temperature <30° C.)
6. 6
   workup.ADDITIONThe resulting orange oil was mixed with diethyl ether (100 mL)
7. 7
   ろ過filtered through a layer of silica (ca. 5 cm)
8. 8
   洗浄The silica was washed with more diethyl ether (ca. 100 mL)
9. 9
   その他to remove the excess of 1,3-dibromopropane
10. 10
    洗浄the crude product was washed from the silica with acetone (120 mL)
11. 11
    濃縮The acetone solution was concentrated under reduced pressure
12. 12
    その他the residue was purified by column-chromatography (eluent: ethyl acetate)

実験手順

Sodium hydride (60%, 240 mg, 6.0 mmol) was added to a solution of 4-([1,2,4]triazol-4-ylamino)-benzonitrile (926 mg, 5.0 mmol) in DMSO (25 mL) at r.t. The mixture was stirred for 1 hour at this temperature and 1,3-dibromopropane (5 mL) was added. The reaction mixture was stirred overnight and ethyl acetate (100 mL) was added. The mixture was transferred into a separation funnel and extracted with water (twice 100 mL) and brine (20 mL). The organic layer was dried over sodium sulphate and concentrated under reduced pressure (water bath temperature <30° C.). The resulting orange oil was mixed with diethyl ether (100 mL) and filtered through a layer of silica (ca. 5 cm). The silica was washed with more diethyl ether (ca. 100 mL) to remove the excess of 1,3-dibromopropane, the crude product was washed from the silica with acetone (120 mL). The acetone solution was concentrated under reduced pressure and the residue was purified by column-chromatography (eluent: ethyl acetate) to give the title compound as a white solid. Yield: 792 mg (52%). 1H-NMR (400 MHz, d6-DMSO) δ=2.01 (tt, J=7.0, 6.6 Hz, 2H), 3.64 (t, J=6.6 Hz, 2H), 3.95 (t, J=7.0 Hz, 2H), 6.62 (d, J=9.0 Hz, 2H), 7.74 (d, J=9.0 Hz, 2H), 9.02 (s, 2H). 13C-NMR (100 MHz, d6-DMSO) δ=30.38, 32.13, 52.72, 103.17, 113.83, 119.74, 134.63, 144.14, 151.65. LRMS (FAB+): 306.0 (100, [M+H]+).

出典