Reaction #2045069

Reaction equation

5-Amino-8-hydroxy-2-methylquinoline

sodium azide

sodium nitrite

→

13

Yield 66.0%

5-Azido-8-hydroxy-2-methylquinoline

Yield 66.0%

Solvents

hydrochloric acid

water

water

water

Conditions

Workup

1. 1
   workup.STIRRINGThe mixture was stirred for 20 min
2. 2
   workup.STIRRINGstirred at 0° C. for a further 1.5 h
3. 3
   Temperatureto warm to room temperature over 24 h in the dark
4. 4
   ExtractionIsolation by extraction with diethyl ether
5. 5
   Othergave a dark brown solid, which
6. 6
   Otherwas recrystallized from light petroleum

Procedure

5-Amino-8-hydroxy-2-methylquinoline (12; 723 mg, 4.2 mmol) was dissolved in a solution of concentrated hydrochloric acid (0.4 mL) and water (5 mL), cooled to −3° C. in a salt-ice bath, stirred for 10 min, then treated dropwise with a cold solution of sodium nitrite (0.50 g, 7.2 mmol) in water (5 mL). The mixture was stirred for 20 min, then treated dropwise with sodium azide (0.60 g, 9.2 mmol) in water (40 mL), stirred at 0° C. for a further 1.5 h, then allowed to warm to room temperature over 24 h in the dark. Isolation by extraction with diethyl ether gave a dark brown solid, which was recrystallized from light petroleum to yield 13 as light brown crystals (554 mg, 66%). 1H NMR (500 MHz, CD3OD) δ ppm: 3.31 (s, 3H), 7.06 (d, J=8.5 Hz, 1H), 7.15 (d, J=8.5 Hz, 1H), 7.36 (d, J=8.5 Hz, 1H), 8.21 (d, J=8.5 Hz, 1H). 13C NMR (125 MHz, CD3OD) δ ppm: 24.9, 111.8, 115.6, 121.6, 123.7, 127.9, 132.6, 139.6, 151.1, 159.7. HRMS (ESI): calcd for C10H8N4O [M+H]+: 201.0771, found: 201.0773.

Source