4-hydrazino-2-methylmercapto-7-(2,3,5-tri-O-benzyl-beta-D-arabinofuranosyl)-7H-pyrrolo[2,3-d]pyrimidine → 7-(2,3,5-tri-O-benzyl-beta-D-arabinofuranosyl)-7H-pyrrolo[2,3-d]pyrimidin-4-amine

HRID 223162Notes

Reaction equation

HRID 223162 reaction equation
[NH:1]([C:3]1[C:4]2[CH:13]=[CH:12][N:11]([C@@H:14]3[O:34][C@H:33]([CH2:35][O:36][CH2:37][C:38]4[CH:43]=[CH:42][CH:41]=[CH:40][CH:39]=4)[C@@H:24]([O:25][CH2:26][C:27]4[CH:32]=[CH:31][CH:30]=[CH:29][CH:28]=4)[C@@H:15]3[O:16][CH2:17][C:18]3[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=3)[C:5]=2[N:6]=[C:7](SC)[N:8]=1)N>[Ni].C(O)C>[CH2:17]([O:16][C@H:15]1[C@H:24]([O:25][CH2:26][C:27]2[CH:28]=[CH:29][CH:30]=[CH:31][CH:32]=2)[C@@H:33]([CH2:35][O:36][CH2:37][C:38]2[CH:43]=[CH:42][CH:41]=[CH:40][CH:39]=2)[O:34][C@H:14]1[N:11]1[C:5]2[N:6]=[CH:7][N:8]=[C:3]([NH2:1])[C:4]=2[CH:13]=[CH:12]1)[C:18]1[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=1

Participants

4

Reactant 1

HCID 228216904-hydrazino-2-methylmercapto-7-(2,3,5-tri-O-benzyl-beta-D-arabinofuranosyl)-7H-pyrrolo[2,3-d]pyrimidine

Product 1

HCID 130762157-(2,3,5-tri-O-benzyl-beta-D-arabinofuranosyl)-7H-pyrrolo[2,3-d]pyrimidin-4-amineYield 76.6%

Reagents, catalysts & solvents 2

HCID 935NickelCatalyst2×HCID 702EthanolSolvent

Procedure

A mixture of 48 g of 4-hydrazino-2-methylmercapto-7-(2,3,5-tri-O-benzyl-β-D-arabinofuranosyl)-7H-pyrrolo[2,3-d]pyrimidine, 500 ml of ethanol, and 100 g of Raney nickel suspension is stirred and heated under reflux for one hour. An additional 100 g of Raney nickel is added and stirring and heating is continued for two hours. The hot suspension is filtered and the filter cake is washed with ethyl acetate. The combined dried filtrates are evaporated in vacuo to 43 g of dark syrup. Chromatography of this material over silica gel with ethyl acetate provides 33 g of pure 7-(2,3,5-tri-O-benzyl-β-D-arabinofuranosyl)-7H-pyrrolo[2,3-d]pyrimidin-4-amine. The same compound may also be obtained by hydrogenolysis of 4-hydrazine-7-(2,3,5-tri-O-benzyl-β-D-arabinofuranosyl)-7H-pyrrolo[2,3-d]pyrimidine with Raney nickel.

Workup

  1. temperatureheated
  2. temperatureunder reflux for one hour
  3. stirringstirring
  4. temperatureheating
  5. filtrationThe hot suspension is filtered
  6. washthe filter cake is washed with ethyl acetate
  7. customare evaporated in vacuo to 43 g of dark syrup

Sources & evidence

ORD record
ord-c05a8ca4f0764224b385d38e2b123d09
Source dataset
uspto-grants-1982_10
Patent number
US04352795

Reaction notes

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