Sodium Dithionite → HCID 59846511, compound

HRID 1363150Notes

Reaction equation

HRID 1363150 reaction equation
S(S([O-])=O)([O-])=O.[Na+].[Na+].C(=O)(O)[O-].[Na+].[F:14][C:15]1[CH:42]=[CH:41][CH:40]=[C:39]([F:43])[C:16]=1[CH2:17][NH:18][C:19]1[C:24]([N+:25]([O-])=O)=[CH:23][N:22]=[C:21]([NH:28][C:29]2[CH:34]=[C:33]([F:35])[CH:32]=[CH:31][C:30]=2[N+:36]([O-])=O)[N:20]=1>O.C1COCC1>[F:43][C:39]1[CH:40]=[CH:41][CH:42]=[C:15]([F:14])[C:16]=1[CH2:17][NH:18][C:19]1[C:24]([NH2:25])=[CH:23][N:22]=[C:21]([NH:28][C:29]2[CH:34]=[C:33]([F:35])[CH:32]=[CH:31][C:30]=2[NH2:36])[N:20]=1

Participants

6

Reactant 3

HCID 24489Sodium DithioniteHCID 516892Sodium BicarbonateHCID 59846361HCID 59846361, compound

Product 1

HCID 59846511HCID 59846511, compound

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 8028TetrahydrofuranSolvent

Procedure

A freshly prepared solution of sodium hydrosulfite (tech, 100 mg) and sodium bicarbonate (50 mg) in H2O (5 mL) was added to a solution of N4-(2,6-difluorobenzyl)-N2-(5-fluoro-2-nitrophenyl)-5-nitropyrimidine-2,4-diamine (75) (24 mg) in THF (5 mL). The mixture was stirred vigorously for 30 min and extracted with DCM (3×). The combined organics were washed with brine, dried, filtered and concentrated to yield the intermediate N4-(2,6-difluorobenzyl)-N2-(2-amino-5-fluorophenyl)pyrimidine-2,4,5-triamine (76) for use in the next step. A catalytic amount of para-toluene sulfonic acid monohydrate was added to a solution of the intermediate and trimethyl orthoformate (1 mL) in MeOH (2 mL), after 2 hr conc. HCl (1 mL) was added and the mixture was heated at 50° C. for 4 hr. The reaction solvents were removed and the crude material was purified via preparative HPLC to give 9-(2,6-Difluorobenzyl)-2-(6-fluoro-1H-benzo[d]imidazol-1-yl)-9H-purine (78) as the TFA salt in low yield (0.8 mg) MH+=404, 1H NMR (5% CD3OD/CDCl3) δ 9.1 (s, 1H), 9.0 (s, 1H), 8.3 (d, 1H), 8.2 (s, 1H), 7.6 (m, 1H), 7.0 (t, 1H), 6.9 (m, 2H), 5.5 (s, 2H) ppm, 19F NMR δ−76.6 (s, TFA), −114.5 (m), −117.1 (m).

Workup

  1. extractionextracted with DCM (3×)
  2. washThe combined organics were washed with brine
  3. customdried
  4. filtrationfiltered
  5. concentrationconcentrated

Sources & evidence

ORD record
ord-9c796bbfe9164b42aa0849107eb80350
Source dataset
uspto-grants-2011_02
Patent number
US07884109B2

Reaction notes

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