Hydrazine hydrate (1:1) → 9-(3,5-Di-O-benzoyl-beta-L-xylofuranosyl)adenine

HRID 928699Notes

Reaction equation

HRID 928699 reaction equation
C([O:4][C@H:5]1[C@H:9]([O:10][C:11](=[O:18])[C:12]2[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=2)[C@H:8]([CH2:19][O:20][C:21](=[O:28])[C:22]2[CH:27]=[CH:26][CH:25]=[CH:24][CH:23]=2)[O:7][C@@H:6]1[N:29]1[CH:37]=[N:36][C:35]2[C:30]1=[N:31][CH:32]=[N:33][C:34]=2[NH2:38])(=O)C.O.NN>N1C=CC=CC=1>[C:11]([O:10][C@@H:9]1[C@H:8]([CH2:19][O:20][C:21](=[O:28])[C:22]2[CH:23]=[CH:24][CH:25]=[CH:26][CH:27]=2)[O:7][C@H:6]([N:29]2[CH:37]=[N:36][C:35]3[C:30]2=[N:31][CH:32]=[N:33][C:34]=3[NH2:38])[C@H:5]1[OH:4])(=[O:18])[C:12]1[CH:13]=[CH:14][CH:15]=[CH:16][CH:17]=1

Participants

4

Reactant 2

HCID 24654Hydrazine hydrate (1:1)HCID 104366059-(2-O-acetyl-3,5-di-O-benzoyl-beta-L-xylofuranosyl)adenine

Product 1

HCID 667172129-(3,5-Di-O-benzoyl-beta-L-xylofuranosyl)adenineYield 68%

Reagents, catalysts & solvents 1

HCID 1049PyridineSolvent

Procedure

A solution of 9-(2-O-acetyl-3,5-di-O-benzoyl-β-L-xylofuranosyl)adenine 2 [Ref.: Gosselin, G.; Bergogne, M.-C.; Imbach, J.-L., “Synthesis and Antiviral Evaluation of β-L-Xylofuranosyl Nucleosides of the Five Naturally Occurring Nucleic Acid Bases”, Journal of Heterocyclic Chemistry, 1993, 30 (October-November), 1229-1233] (8.30 g, 16.05 mmol) and hydrazine hydrate 98% (234 mL, 48.5 mmol) in a mixture of pyridine/glacial acetic acid (4/1, v/v, 170 mL) was stirred at room temperature for 22 h. The reaction was quenched by adding acetone (40 mL) and stirring was continued for one additional hour. The reaction mixture was reduced to one half of its volume, diluted with water (250 mL) and extracted with chloroform (2×150 mL). The organic layer was washed successively with an aqueous saturated solution of NaHCO3 (3×100 mL) and water (3×100 mL), dried, filtered, concentrated and co-evaporated with toluene and methanol. The residue was purified by silica gel column chromatography (0-3% MeOH in dichloromethane) to give 3 (5.2 g, 68%) precipitated from diisopropylic ether: 1H NMR (DMSO-d6): δ 4.5-4.9 (m, 4H, H-2′, H-4′, H-5′ and H-5″), 5.64 (t, 1H, H-3′, J2′,3′=J3′,4′=3.5 Hz), 6.3 (br s, 1H, OH-2′), 6.45 (d, 1H, H-1′, J1′,2′=4.6 Hz), 7.3 (br s, 2H, NH2-6), 7.4-7.9 (m, 10H, 2 benzoyls), 8.07 and 8.34 (2s, 2H, H-2 and H-8); ms: matrix G/T, (FAB) m/z 476 [M+H]+, 136 [BH2]+, (FAB−) m/z 474 [M−H]−, 134 [B]−; UV (95% ethanol): λmax 257 nm (ε 16400), 230 nm (ε 29300), λmin 246 nm (ε 14800); [α]D20 64 (c 1.07, CHCl3). Anal. Calcd for C24H21N5O4 (M=475.45): C, 60.43; H, 4.45; N, 14.73. Found: C, 60.41; H, 4.68; N, 14.27.

Workup

  1. customThe reaction was quenched
  2. additionby adding acetone (40 mL)
  3. stirringstirring
  4. additiondiluted with water (250 mL)
  5. extractionextracted with chloroform (2×150 mL)
  6. washThe organic layer was washed successively with an aqueous saturated solution of NaHCO3 (3×100 mL) and water (3×100 mL)
  7. customdried
  8. filtrationfiltered
  9. concentrationconcentrated and co-evaporated with toluene and methanol
  10. customThe residue was purified by silica gel column chromatography (0-3% MeOH in dichloromethane)

Sources & evidence

ORD record
ord-2279665a5d9c41c39042c9f35d9a1caa
Source dataset
uspto-grants-2016_03
Patent number
US09290533B2

Reaction notes

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