Sodium Carbonate → O6-benzyl-2-fluorohypoxanthine

HRID 1416913Notes

Reaction equation

HRID 1416913 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-f9f73bb46fe442548ac2c0603fe04d09
Source dataset
uspto-grants-1999_06
Patent number
US05916894

Reaction notes

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