Sodium Hydroxide → 9-(2,3,5-Tri-O-benzyl-beta-D-arabinofuranosyl)-2-fluoroadenine

HRID 1448997Notes

Reaction equation

HRID 1448997 reaction equation
N[C:2]1[N:10]=[C:9]2[C:5]([N:6]=[CH:7][N:8]2[C@@H:11]2[O:31][C@H:30]([CH2:32][O:33][CH2:34][C:35]3[CH:40]=[CH:39][CH:38]=[CH:37][CH:36]=3)[C@@H:21]([O:22][CH2:23][C:24]3[CH:29]=[CH:28][CH:27]=[CH:26][CH:25]=3)[C@@H:12]2[O:13][CH2:14][C:15]2[CH:20]=[CH:19][CH:18]=[CH:17][CH:16]=2)=[C:4]([NH2:41])[N:3]=1.[H+].[B-](F)(F)(F)[F:44].N([O-])=O.[Na+].NC1N=C2C(NC=N2)=C(N)N=1.[OH-].[Na+]>O1CCCC1>[CH2:14]([O:13][C@H:12]1[C@H:21]([O:22][CH2:23][C:24]2[CH:29]=[CH:28][CH:27]=[CH:26][CH:25]=2)[C@@H:30]([CH2:32][O:33][CH2:34][C:35]2[CH:40]=[CH:39][CH:38]=[CH:37][CH:36]=2)[O:31][C@H:11]1[N:8]1[CH:7]=[N:6][C:5]2[C:9]1=[N:10][C:2]([F:44])=[N:3][C:4]=2[NH2:41])[C:15]1[CH:20]=[CH:19][CH:18]=[CH:17][CH:16]=1

Participants

7

Reactant 5

HCID 14798Sodium HydroxideHCID 28118Tetrafluoroboric acid2×HCID 309762,6-DiaminopurineHCID 108969412-Amino-9-(2,3,5-tri-O-benzyl-beta-D-arabinofuranosyl)adenineHCID 23668193Sodium Nitrite2×

Product 1

HCID 109627089-(2,3,5-Tri-O-benzyl-beta-D-arabinofuranosyl)-2-fluoroadenine

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

To a solution of 2-amino-9-(2,3,5-tri-O-benzyl-β-D-arabinofuranosyl)adenine (14.5 g, 26.2 mmol) in a mixture of 500 ml tetrahydrofuran and 1 l. of 48% fluoboric acid at -15° in a 4-l. beaker equipped with a mechanical stirrer was added dropwise in 20 min a saturated aqueous solution of NaNO2 (7.2 g, 105 mmol). The addition of NaNO2 (5.4 g, 78.6 mmol) was repeated three times after which none of the 2-aminoadenine remained (TLC). The fluoroboric acid was neutralized with 50% NaOH keeping the temperature between -40 and 0°. The solution was extracted four times with CHCl3 (300 ml, 250 ml, and two 200-ml portions). The CHCl3 extract was washed with saturated NaCl solution and then dried over MgSO4 before it was evaporated to dryness in vacuo. The residual oil was dissolved in a liter of ethanolic NH3 (saturated at 0° ), and the solution was allowed to stand for three days at 0° before it was evaporated to dryness. The residue was recrystallized from 100 ml EtOH; yield 4.7 g. Additional material was recovered from the filtrate by recrystallization and preparative TLC. The total yield was 5.8 g (40%).

Workup

  1. customat -15°
  2. custombeaker equipped with a mechanical stirrer
  3. customthe temperature between -40 and 0°
  4. extractionThe solution was extracted four times with CHCl3 (300 ml, 250 ml, and two 200-ml portions)
  5. extractionThe CHCl3 extract
  6. washwas washed with saturated NaCl solution
  7. dry with materialdried over MgSO4 before it
  8. customwas evaporated to dryness in vacuo
  9. dissolutionThe residual oil was dissolved in a liter of ethanolic NH3 (saturated at 0° )
  10. customwas evaporated to dryness
  11. customThe residue was recrystallized from 100 ml EtOH
  12. customAdditional material was recovered from the filtrate by recrystallization and preparative TLC

Sources & evidence

ORD record
ord-0c622c255ebf454eaf3d72cfb5e37c36
Source dataset
uspto-grants-1980_02
Patent number
US04188378

Reaction notes

Loading…