Tert-Butylamine → 8-bromo-N-(tert-butyl)-7-fluoro-3-methylquinoxalin-2-amine

HRID 1056139Notes

Reaction equation

[Br:1][C:2]1[C:3]([F:14])=[CH:4][CH:5]=[C:6]2[C:11]=1[NH:10][C:9](=O)[C:8]([CH3:13])=[N:7]2.[C:15]([NH2:19])([CH3:18])([CH3:17])[CH3:16]>CS(C)=O>[Br:1][C:2]1[C:3]([F:14])=[CH:4][CH:5]=[C:6]2[C:11]=1[N:10]=[C:9]([NH:19][C:15]([CH3:18])([CH3:17])[CH3:16])[C:8]([CH3:13])=[N:7]2

Participants

Conditions

Temperature: 100 °C

Procedure

A glass reaction vessel was charged with 5-bromo-3-chloro-6-fluoro-2-methylquinoxaline (600) (9.705 g, 35.2 mmol) in DMSO (58.7 mL). Then tert-butylamine (Alfa Aesar; Ward Hill, Mass.) (18.51 mL, 176 mmol) was added into the mixture. The vial was sealed, then placed into a pre-heated (100° C.) oil bath and stirred 2 h. The vessel was removed from the heat source and cooled to RT. The mixture was poured into water (1100 mL) sat undisturbed 30 min, then stirred. The precipitate was collected by filtration (through a medium fritted-funnel) and the solids were washed with water. The solids were dried in a reduced-pressure oven overnight, to provide 8-bromo-N-(tert-butyl)-7-fluoro-3-methylquinoxalin-2-amine (286a) (8.27 g, 75% yield) as a tan solid. 1H NMR (400 MHz, DMSO-d6) δ ppm 7.75 (dd, J=9.00, 5.87 Hz, 1H) 7.33 (t, J=8.80 Hz, 1H) 6.30 (s, 1H) 2.54 (s, 3H) 1.59 (s, 9H). m/z (ESI, +ve) 311.9 (M+H).

Workup

customA glass reaction vessel
customThe vial was sealed
customThe vessel was removed from the heat source
temperaturecooled to RT
additionThe mixture was poured into water (1100 mL)
waitsat undisturbed 30 min
stirringstirred
filtrationThe precipitate was collected by filtration (through a medium fritted-funnel)
washthe solids were washed with water
customThe solids were dried in a reduced-pressure oven overnight

Sources & evidence

ORD record: ord-4cb984ee56f246bbbf4140be03024f7c
Source dataset: uspto-grants-2016_07
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US09394297B2

Reaction notes

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