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

HRID 1055985Notes

Reaction equation

HRID 1055985 reaction equation
[Br:1][C:2]1[CH:11]=[CH:10][CH:9]=[C:8]2[C:3]=1[N:4]=[C:5](F)[C:6]([CH3:12])=[N:7]2.[C:14]([NH2:18])([CH3:17])([CH3:16])[CH3:15]>CS(C)=O.C(Cl)Cl>[Br:1][C:2]1[CH:11]=[CH:10][CH:9]=[C:8]2[C:3]=1[N:4]=[C:5]([NH:18][C:14]([CH3:17])([CH3:16])[CH3:15])[C:6]([CH3:12])=[N:7]2

Participants

5

Reactant 2

HCID 6385Tert-ButylamineHCID 897819405-Bromo-3-fluoro-2-methylquinoxaline

Product 1

HCID 897836188-bromo-N-(tert-butyl)-3-methylquinoxalin-2-amineYield 86.3%

Reagents, catalysts & solvents 2

HCID 679Dimethyl SulfoxideSolventHCID 6344DichloromethaneSolvent

Procedure

A solution of 5-bromo-3-fluoro-2-methylquinoxaline (Example 126f; 1.5 g, 6.22 mmol) and tert-butylamine (Aldrich; 3.27 mL, 31.1 mmol) in DMSO (15 mL) was stirred at 100° C. for 2.5 h. The mixture was subsequently diluted with DCM (150 mL), and washed with saturated aq. NaHCO3 (3×15 mL). The organic layer was separated, dried over MgSO4, filtered, and concentrated. The crude material was purified on a silica gel column (18-25% EtOAc in hexanes) to give 8-bromo-N-(tert-butyl)-3-methylquinoxalin-2-amine (1.58 g, 86% yield) as an amorphous pink solid. 1H NMR (400 MHz, DMSO-d6) δ ppm 7.79-7.86 (m, 1H), 7.71 (dd, J=8.1, 1.1 Hz, 1H), 7.22 (t, J=7.9 Hz, 1H), 6.17 (s, 1H), 2.55 (s, 3H), 1.58 (s, 9H). m/z (ESI, +ve ion) 294.0/296.0 (M+H)+.

Workup

  1. washwashed with saturated aq. NaHCO3 (3×15 mL)
  2. customThe organic layer was separated
  3. dry with materialdried over MgSO4
  4. filtrationfiltered
  5. concentrationconcentrated
  6. customThe crude material was purified on a silica gel column (18-25% EtOAc in hexanes)

Sources & evidence

ORD record
ord-0c412d6b2293457abb68b0bf7cf0f1b9
Source dataset
uspto-grants-2016_07
Patent number
US09394297B2

Reaction notes

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