Reaction #48177

Reaction equation

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

1,2-dibromoethane

ethyl acetate

→

title compound

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

Solvents

DMSO

Conditions

Workup

1. 1
   workup.ADDITIONwas added
2. 2
   OtherThe mixture was transferred into a separation funnel
3. 3
   Extractionextracted with water (twice 100 mL) and brine (20 mL)
4. 4
   DryingThe organic layer was dried over sodium sulphate
5. 5
   Concentrationconcentrated under reduced pressure (water bath temperature <30° C.)
6. 6
   workup.ADDITIONThe resulting orange oil was mixed with diethyl ether (100 mL)
7. 7
   Filtrationfiltered through a layer of silica (ca 5 cm)
8. 8
   WashThe silica was washed with more diethyl ether (ca. 100 mL)
9. 9
   Otherto remove the excess of 1,2-dibromoethane
10. 10
    Washthe crude product was washed from the silica with acetone (120 mL)
11. 11
    ConcentrationThe acetone solution was concentrated under reduced pressure
12. 12
    Otherthe residue was purified by column-chromatography (eluent: ethyl acetate)

Procedure

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 1,2-dibromoethane (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 1,2-dibromoethane; 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: 628 mg (43%). 1H-NMR (400 MHz, d6-DMSO) δ=3.61, (t, J=6.2 Hz, 2H), 4.30 (t, J=6.4 Hz, 2H), 6.64 (d, J=9.0 Hz), 7.74 (d, 9.0 Hz, 2H), 8.97 (s, 2H). LRMS (FAB+): 292.0 (100, [M+H]+).

Source