Sodium Carbonate → O6-benzyl-2-fluorohypoxanthine

HRID 565268Notes

Reaction equation

HRID 565268 reaction equation
[CH:1]1[CH:2]=[CH:3][C:4]([CH2:7][O:8][C:9]2[C:10]3[N:14]=[CH:13][NH:12][C:11]=3[N:15]=[C:16](N)[N:17]=2)=[CH:5][CH:6]=1.[H+].[B-](F)(F)(F)[F:21].N([O-])=O.[Na+].C(=O)([O-])[O-].[Na+].[Na+]>O>[CH:1]1[CH:2]=[CH:3][C:4]([CH2:7][O:8][C:9]2[C:10]3[NH:14][CH:13]=[N:12][C:11]=3[N:15]=[C:16]([F:21])[N:17]=2)=[CH:5][CH:6]=1

Participants

6

Reactant 4

HCID 10340Sodium CarbonateHCID 28118Tetrafluoroboric acid4×HCID 23668193Sodium Nitrite3×HCID 178508945HCID 178508945, compound

Product 1

HCID 563585O6-benzyl-2-fluorohypoxanthine

Reagents, catalysts & solvents 1

HCID 962WaterSolvent

Procedure

O6-Benzylguanine (1.21 g, 5 mmol) was added to 100 mL of 48% fluoboric acid at −20° C. Sodium nitrite (1.23 g, 35 mmole) was dissolved in water (5 mL) and 2.5 mL of this sodium nitrite solution was added slowly to the cold fluoboric acid solution. The resulting mixture was stirred for 1 h at or below −15° C. Additional fluoboric acid (25 mL) was added followed by an additional 2.5 mL of the aqueous sodium nitrite solution. After stirring for an additional 1 h below −15° C., fluoboric acid (25 mL) was again added and stirring was continued for 1 h. The resulting solution was neutralized with saturated aqueous sodium carbonate solution at −20° C. and was allowed to warm to room temperature. A white precipitate that formed was collected by filtration and was washed with water and dried under vacuum to afford crude 4c: yield, 0.52 g, 43%. An analytical sample was prepared by chromatography on a Sephadex LH-20 column (3×80 cm) eluted with methanol/water (1:1) at 1 mL/min. The desired 4c eluted in fractions 66-77: mp 182-183° C. (184-185° C.; Robins and Robins, J. Org. Chem., 34, 2160-2163 (1969)); UV (pH 1) λmax 256 nm (ε=1.117×104); (pH 6.9) 257 (1.078×104) (pH 13) 264 (1.063×104); 1H NMR δ 5.60 (s, 2H, ArCH2), 7.37-7.57 (m, 5H, ArH), 8.40 (s, 1H, H-8), 13.60 (s, 1H, NH, exchanges with D2O), 19F NMR δ 23.54 downfield from trifluoroacetic acid standard; MS (EI) calcd. m/z for C12H9FN4O 244.0760, found 244.0756; Anal. (C12H9FN4O.2/3 H2O) C, H, N.

Workup

  1. stirringAfter stirring for an additional 1 h below −15° C.
  2. stirringstirring
  3. waitwas continued for 1 h
  4. customA white precipitate that formed
  5. filtrationwas collected by filtration
  6. washwas washed with water
  7. customdried under vacuum

Sources & evidence

ORD record
ord-98ffcf0446744bea8c27f7161f2fd853
Source dataset
uspto-grants-2001_01
Patent number
US06172070B2

Reaction notes

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