Bromine → HCID 178497971, compound

HRID 1197938Notes

Reaction equation

HRID 1197938 reaction equation
[O:1]1C=C[CH2:3][CH:2]1[C:6]1[CH:15]=[CH:14][C:9]([C:10]([O:12][CH3:13])=[O:11])=[CH:8][CH:7]=1.BrBr.[NH2:18][C:19]1[N:24]=[C:23]([NH2:25])[CH:22]=[C:21](O)[N:20]=1.[C:27]([O-:30])(=O)[CH3:28].[Na+]>C(#N)C.O>[CH3:13][O:12][C:10](=[O:11])[C:9]1[CH:8]=[CH:7][C:6]([CH:2]([OH:1])[CH2:3][N:25]2[C:28]3[C:27]([OH:30])=[N:18][C:19]([NH2:24])=[N:20][C:21]=3[CH:22]=[CH:23]2)=[CH:15][CH:14]=1

Participants

7

Reactant 4

HCID 24408BromineHCID 517045Sodium AcetateHCID 19105512HCID 19105512, compoundHCID 178507952HCID 178507952, compound

Product 1

HCID 178497971HCID 178497971, compoundYield 47%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 6342AcetonitrileSolvent2×

Conditions

Temperature
-10 °C

Procedure

To a vigorously stirred mixture of 2.04 g (10 mmol) of methyl 4-(2,3-dihydrofuran-2-yl)benzoate in 15 mL of acetonitrile and 20 mL of water cooled to -10° C. was added dropwise a solution of 1.60 g (10 mmol) of bromine in 5 mL of acetonitrile. The mixture was stirred for 15 min after addition was complete. There was then added 1.26 g (10 mmol) of 2,4-diamino-6-hydroxypyrimidine and 2.46 g (30 mmol) of sodium acetate and the mixture was heated to about 75° C. for 2 h. After about 20 min the product began to precipitate. The mixture was cooled to room temperature and 20 mL of water was added. The product was filtered and dried, affording 2.3 g of crude product. The crude material was purified by slurry in DMF (140° C.), cooling, filtration, and reslurry in ether. Filtration of the ether suspension gave 1.54 g (47%) of the product as a white powder, mp>260° C. 1H NMR (DMSO-d6) δ2.88 (m, 2H), 3.81 (s, 3H), 4.95 (m, 1H), 5.71 (d, J=4.7 Hz, 1H), 6.03 (s, 2H), 6.21 (br d, J=1.8 Hz, 1H), 7.41 (d, J=8.3 Hz, 2H), 7.86 (d, J=8.3 Hz, 2H), 10.28 (s, 1H), 10.64 (br s, 1H); MS(FD) m/z 328 (M+). Anal. Calcd for C16H16N4O4 : C, 58.37; H, 5.04; N, 17.29. Found: C, 58.53; H, 4.91; N, 17.06.

Workup

  1. additionafter addition
  2. temperaturethe mixture was heated to about 75° C. for 2 h
  3. waitAfter about 20 min the product began
  4. customto precipitate
  5. temperatureThe mixture was cooled to room temperature
  6. addition20 mL of water was added
  7. filtrationThe product was filtered
  8. customdried
  9. customaffording 2.3 g of crude product
  10. customThe crude material was purified by slurry in DMF (140° C.)
  11. temperaturecooling
  12. filtrationfiltration
  13. filtrationFiltration of the ether suspension

Sources & evidence

ORD record
ord-fd5b20211efa460090c42786da0c87d0
Source dataset
uspto-grants-1994_01
Patent number
US05278307

Reaction notes

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