1,3-Dibromo-5,5-dimethylhydantoin → 5-Bromopyrrolo[2,1-f][1,2,4]triazin-4-amine

HRID 1972729Notes

Reaction equation

HRID 1972729 reaction equation
[N:1]1[N:2]2[CH:10]=[CH:9][CH:8]=[C:3]2[C:4]([NH2:7])=[N:5][CH:6]=1.[Br:11]N1C(C)(C)C(=O)N(Br)C1=O.S([O-])([O-])(=O)=S.[Na+].[Na+]>ClCCl>[Br:11][C:8]1[CH:9]=[CH:10][N:2]2[C:3]=1[C:4]([NH2:7])=[N:5][CH:6]=[N:1]2

Participants

5

Reactant 3

HCID 64791,3-Dibromo-5,5-dimethylhydantoinHCID 24477Sodium ThiosulfateHCID 10441749Pyrrolo[2,1-f][1,2,4]triazin-4-amine

Product 1

HCID 585298655-Bromopyrrolo[2,1-f][1,2,4]triazin-4-amine

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent2×

Procedure

A suspension of pyrrolo[2,1-f][1,2,4]triazin-4-amine (0.5 g, 0.004 mol) in dichloromethane (100 mL) was stirred and cooled between −10° C. and −14° C. under nitrogen atmosphere. A solution of 1,3-dibromo-5,5-dimethylimidazolidine-2,4-dione (544 mg, 0.002 mol) in dichloromethane (100 mL) added dropwise over a 1 h. After 4 h, 100 mL of 10% aqueous sodium thiosulfate solution was added, and the mixture was stirred vigorously for a few minutes. The phases were separated, the dichloromethane phase washed with water, then brine, dried (anhydrous sodium sulfate), filtered and concentrated in vacuo. The residue was purified by MPLC (dichloromethane/ethyl acetate gradient). Purified material was triturated with dichloromethane, filtered, washed and dried under vacuum to afford 289 mg (36%) of colorless, fluffy solid. 1H-NMR (DMSO-d6): δ 8.01 (br s, 1 H), 7.82 (s, 1 H), 7.70 (d, 1 H), 6.78 (d, br s, 2 H). MS: LC/MS (+esi), m/z=212.5, 213.1 [M+H]. RT=1.34 min. Calc. for C6H5BrN4: C, 33.83; H, 2.37; Br, 37.50; N, 26.3. Found: C, 33.85; H, 2.24; Br, 38.24; N, 26.21.

Workup

  1. temperaturecooled between −10° C. and −14° C. under nitrogen atmosphere
  2. stirringthe mixture was stirred vigorously for a few minutes
  3. customThe phases were separated
  4. washthe dichloromethane phase washed with water
  5. dry with materialbrine, dried (anhydrous sodium sulfate)
  6. filtrationfiltered
  7. concentrationconcentrated in vacuo
  8. customThe residue was purified by MPLC (dichloromethane/ethyl acetate gradient)
  9. customPurified material was triturated with dichloromethane
  10. filtrationfiltered
  11. washwashed
  12. customdried under vacuum
  13. customto afford 289 mg (36%) of colorless, fluffy solid

Sources & evidence

ORD record
ord-536a7e1afd42497392868d7f58dd5757
Source dataset
uspto-grants-2013_04
Patent number
US08431695B2

Reaction notes

Loading…