Methylhydrazine → HCID 15747245, compound

HRID 2395836Notes

Reaction equation

HRID 2395836 reaction equation
[Si:1]([O:18][C@@H:19]1[C@@H:23]([CH2:24][O:25][N:26]2C(=O)C3=CC=CC=C3C2=O)[O:22][C@@H:21]([N:37]2[CH:45]=[C:43]([CH3:44])[C:41](=[O:42])[NH:40][C:38]2=[O:39])[CH2:20]1)([C:14]([CH3:17])([CH3:16])[CH3:15])([C:8]1[CH:13]=[CH:12][CH:11]=[CH:10][CH:9]=1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.CNN>C(Cl)Cl>[NH2:26][O:25][CH2:24][C@H:23]1[O:22][C@@H:21]([N:37]2[CH:45]=[C:43]([CH3:44])[C:41](=[O:42])[NH:40][C:38]2=[O:39])[CH2:20][C@@H:19]1[O:18][Si:1]([C:14]([CH3:17])([CH3:16])[CH3:15])([C:8]1[CH:13]=[CH:12][CH:11]=[CH:10][CH:9]=1)[C:2]1[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=1

Participants

4

Reactant 2

HCID 6061MethylhydrazineHCID 15747244HCID 15747244, compound

Product 1

HCID 15747245HCID 15747245, compoundYield 89%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Conditions

Temperature
0 °C

Procedure

To a stirred solution of 3'-O-(t-butyldiphenylsilyl)-5'-O-phthalimidothymidine (10 g, 16 mmol) in dry CH2Cl2 (100 ml) was added methylhydrazine (1.3 ml, 24 mmol) under argon at room temperature and solution stirred for 12 h. The solution was cooled (0° C.) and filtered. The white residue was washed with CH2Cl2 (2×25 ml) and combined filtrates were evaporated to furnish gummy residue. The residue on purification by silica gel column chromatography (elution with CH2Cl2 :MeOH, 98:2, v/v) furnished 7.03 g (89%) of 5'-O-amino-3'-O-(t-butyldiphenylsilyl)thymidine that crystallized from CH2Cl2 /MeOH mp 141°-143° C. 1H NMR (DMSO-d6) δ11.29 (s, 1, NH), 7.42-7.62 (m, 11, TBDPhH, C6H), 6.25 (dd, 1, H1', J1',2' =8.4 Hz, J1',2" =6.3 Hz), 6.02 (s, 2, NH2), 4.35 (m, 1, H4'), 4.04 (m, 1, H3'), 3.34-3.51 (m, 2, H5',5"), 2.04 (m, 2, H2', 2"), 1.73 (s, 3, CH3), 1.03 (s, 9, C(CH3)3). Anal. Calcd. for C26H33O5N3Si: C, 63.00; H, 6.71; N, 8.48. Found: C, 62.85; H, 6.67; N, 8.32.

Workup

  1. filtrationfiltered
  2. washThe white residue was washed with CH2Cl2 (2×25 ml)
  3. customwere evaporated
  4. customto furnish gummy residue
  5. customThe residue on purification by silica gel column chromatography (
  6. washelution with CH2Cl2

Sources & evidence

ORD record
ord-94da714db66e44868f2e8d1cc97fd664
Source dataset
uspto-grants-1996_02
Patent number
US05489677

Reaction notes

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