Potassium Fluoride → HCID 131736421, compound

HRID 1056219Notes

Reaction equation

HRID 1056219 reaction equation
[Br:1][C:2]1[CH:3]=[CH:4][CH:5]=[C:6]2[C:11]=1[N:10]=[C:9]([NH:12][C:13]([CH3:16])([CH3:15])[CH3:14])[C:8](Cl)=[N:7]2.[Br:18][C:19]1[CH:28]=[CH:27][CH:26]=[C:25]2[C:20]=1[N:21]=[C:22](Cl)[C:23]([NH:29][C:30]([CH3:33])([CH3:32])[CH3:31])=[N:24]2.[F-:35].[K+]>CS(C)=O.C(Cl)Cl>[Br:1][C:2]1[CH:3]=[CH:4][CH:5]=[C:6]2[C:11]=1[N:10]=[C:9]([NH:12][C:13]([CH3:16])([CH3:15])[CH3:14])[C:8]([F:35])=[N:7]2.[Br:18][C:19]1[CH:28]=[CH:27][CH:26]=[C:25]2[C:20]=1[N:21]=[C:22]([F:35])[C:23]([NH:29][C:30]([CH3:33])([CH3:32])[CH3:31])=[N:24]2

Participants

6

Reactant 3

HCID 522689Potassium FluorideHCID 89783537HCID 89783537, compound2×HCID 89784748HCID 89784748, compound

Product 1

HCID 131736421HCID 131736421, compoundYield 64%

Reagents, catalysts & solvents 2

HCID 679Dimethyl SulfoxideSolventHCID 6344DichloromethaneSolvent

Conditions

Temperature
90 °C

Procedure

A mixture of Intermediate 304a (as a ˜2.5:1 mixture of 8-bromo-N-(tert-butyl)-3-chloroquinoxalin-2-amine and 5-bromo-N-(tert-butyl)-3-chloroquinoxalin-2-amine (407 mg, 0.6 mmol) and KF (113 mg, 1.94 mmol) in DMSO (1.3 mL) was heated to 90° C. for 24 h. The reaction mixture was diluted with DCM (100 mL), added to a separatory funnel, and washed with saturated aq. NaHCO3 (2×75 mL) before the organic layer was separated, dried over Na2SO4, and concentrated to give an inseparable mixture (˜2.5:1) of 8-bromo-N-(tert-butyl)-3-fluoroquinoxalin-2-amine/5-bromo-N-(tert-butyl)-3-fluoroquinoxalin-2-amine (343a) (124 mg, 0.41 mmol, 64% yield) as a yellow oil. 1H NMR (400 MHz, CDCl3) δ ppm 1.57 (s, 9H) 1.63 (s, 18H) 5.22 (br. s., 0H) 5.25 (br. s., 1H) 7.20 (t, J=7.92 Hz, 1H) 7.37 (t, J=8.02 Hz, 1H) 7.61-7.65 (m, 2H) 7.67 (d, J=8.41 Hz, 1H) 7.83 (d, J=7.63 Hz, 1H). 19F NMR (376 MHz, CDCl3) δ ppm −82.18 (s, 2F) −80.01 (s, 1F). MS (ESI, pos. ion) m/z: 298.0/300.0 (M+1).

Workup

  1. additionadded to a separatory funnel
  2. washwashed with saturated aq. NaHCO3 (2×75 mL) before the organic layer
  3. customwas separated
  4. dry with materialdried over Na2SO4
  5. concentrationconcentrated

Sources & evidence

ORD record
ord-2063ed4953694c02bb617b1ed29234f6
Source dataset
uspto-grants-2016_07
Patent number
US09394297B2

Reaction notes

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