Hydroxylamine, O-((4-nitrophenyl)methyl)-, hydrochloride (1:1) → HCID 54106154, compound

HRID 1647180Notes

Reaction equation

HRID 1647180 reaction equation
Cl.[N+:2]([C:5]1[CH:10]=[CH:9][C:8]([CH2:11][O:12][NH2:13])=[CH:7][CH:6]=1)([O-:4])=[O:3].[CH:14]1[N:19]=[C:18](Cl)[C:17]2[N:21]=[CH:22][N:23]([C@@H:24]3[O:28][C@H:27]([CH2:29][OH:30])[C@@H:26]([OH:31])[C@H:25]3[OH:32])[C:16]=2[N:15]=1.C(N(C(C)C)CC)(C)C>CN(C=O)C>[N+:2]([C:5]1[CH:6]=[CH:7][C:8]([CH2:11][O:12][NH:13][C:18]2[C:17]3[N:21]=[CH:22][N:23]([C:16]=3[N:15]=[CH:14][N:19]=2)[C@@H:24]2[O:28][C@H:27]([CH2:29][OH:30])[C@@H:26]([OH:31])[C@H:25]2[OH:32])=[CH:9][CH:10]=1)([O-:4])=[O:3]

Participants

5

Reactant 3

HCID 74967Hydroxylamine, O-((4-nitrophenyl)methyl)-, hydrochloride (1:1)HCID 81531DiisopropylethylamineHCID 930036-Chloropurine riboside

Product 1

HCID 54106154HCID 54106154, compound

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Procedure

The title compound was prepared according to Method A described above (R2, R3 =H) by reacting O-[(4-nitrophenyl)methyl]hydroxylamine hydrochloride (1.43 g, 7 mmol) with 6-chloropurine riboside (i.e. 9-β-D-ribofuranosyl-6-chloro-9H-purine) (1.0 g, 3.5 mmol) in DMF (40 ml) at 110° C. for 2 h with diisopropylethylamine (1.80 g, 14 mmol) present. The reaction mixture was evaporated and to the resultant residue was added saturated sodium bicarbonate solution (20 ml) and water (20 ml). Methanol was gradually added until the residue dissolved, and the solid which gradually precipitated was removed by filtration. The flitrate was concentrated to a residue which was purified by flash chromatography on silica gel. Elution with ethyl acetate/ethanol (30/1) initially, followed by a (8/1) mixture of these solvents provided a solid which was recrystallized from ethanol. The first crop of material was discarded, but the second crop was confirmed as the title compound (70 mg, 7%) mp 115°-117 ° C. TLC rf 0.20 [SiO2, ethyl acetate/methanol (9/1)]; 1H NMR (DMSO-d6)γ 3.46-3.57 (2H, m, H-5'a and H-5'b), 3.90 (1H, q, H-4'), 4.08 (1H, q, H-3'), 4.43 (1H, q, H-2'), 5.07 (1H, t, 5'-OH), 5.44, 5.74 (2H, 2d, 2'and 3'-OH), 5.82 (1H, d, H-1'), 7.67 (2H, d, Ar-H), 8.08 (1h, s, H-8), 8.22 (2H, d, Ar-H), 9.34 (1H, br s, N-H).

Workup

  1. customat 110° C.
  2. customfor 2 h
  3. customThe reaction mixture was evaporated and to the resultant residue
  4. additionwas added saturated sodium bicarbonate solution (20 ml) and water (20 ml)
  5. additionMethanol was gradually added until the residue
  6. dissolutiondissolved
  7. customthe solid which gradually precipitated
  8. customwas removed by filtration
  9. concentrationThe flitrate was concentrated to a residue which
  10. customwas purified by flash chromatography on silica gel
  11. washElution with ethyl acetate/ethanol (30/1) initially
  12. additionfollowed by a (8/1) mixture of these solvents
  13. customprovided a solid which
  14. customwas recrystallized from ethanol

Sources & evidence

ORD record
ord-ea2bc7ec23e146b1b92171d57dff30b8
Source dataset
uspto-grants-1995_07
Patent number
US05430027

Reaction notes

Loading…