Hydrochloric Acid → 2-Amino-9-(2,3,5-tri-O-benzyl-beta-D-arabinofuranosyl)adenine

HRID 1448995Notes

Reaction equation

HRID 1448995 reaction equation
Cl.[CH2:2]([O:9][C@H:10]1[C@H:26]([O:27][CH2:28][C:29]2[CH:34]=[CH:33][CH:32]=[CH:31][CH:30]=2)[C@@H:25]([CH2:35][O:36][CH2:37][C:38]2[CH:43]=[CH:42][CH:41]=[CH:40][CH:39]=2)[O:24][C@H:11]1OC(=O)C1C=CC([N+]([O-])=O)=CC=1)[C:3]1[CH:8]=[CH:7][CH:6]=[CH:5][CH:4]=1.C([NH:47][C:48]1[N:56]=[C:55]2[C:51]([NH:52][CH:53]=[N:54]2)=[C:50]([NH:57]C(=O)C)[N:49]=1)(=O)C>C(Cl)Cl.C(Cl)CCl>[NH2:47][C:48]1[N:56]=[C:55]2[C:51]([N:52]=[CH:53][N:54]2[C@@H:11]2[O:24][C@H:25]([CH2:35][O:36][CH2:37][C:38]3[CH:43]=[CH:42][CH:41]=[CH:40][CH:39]=3)[C@@H:26]([O:27][CH2:28][C:29]3[CH:34]=[CH:33][CH:32]=[CH:31][CH:30]=3)[C@@H:10]2[O:9][CH2:2][C:3]2[CH:8]=[CH:7][CH:6]=[CH:5][CH:4]=2)=[C:50]([NH2:57])[N:49]=1

Participants

6

Reactant 3

HCID 313Hydrochloric AcidHCID 71572112,3,5-tri-O-benzyl-1-O-p-nitrobenzoyl-beta-D-arabinofuranoseHCID 13923314N,N'-(7H-Purine-2,6-diyl)diacetamide

Product 1

HCID 108969412-Amino-9-(2,3,5-tri-O-benzyl-beta-D-arabinofuranosyl)adenine

Reagents, catalysts & solvents 2

HCID 111,2-DichloroethaneSolventHCID 6344DichloromethaneSolvent

Procedure

Dry HCl gas was bubbled into a solution of 2,3,5-tri-O-benzyl-1-O-p-nitrobenzoyl-β-D-arabinofuranose (17 g, 30 mmol) in CH2Cl2 (187 ml) at -10°-0° for 21/2 hr. The precipitated p-nitrobenzoic acid was removed by filtration and washed with CH2Cl2. The CH2Cl2 solution was evaporated in vacuo. The residue, dissolved in 500 ml of ethylene chloride, was added to a mixture of 2.6-diacetamidopurine (7.03 g, 30 mmol) and molecular sieve (Linde 4A, 75 g) in 500 ml of ethylene chloride. This mixture was refluxed until all the chlorosugar was consumed (TLC) (8-11 days). The mixture was then stirred with Celite and filtered. The solid was washed with CHCl3, and the combined filtrates were evaporated to dryness in vacuo. The residue was dissolved in benzene and filtered (to remove unreacted 2,6-diacetamidopurine). The filtrate was again evaporated to dryness in vacuo and the residue dissolved in 100 ml of 1 N methanolic NaOMe. After a 3-hr reflux period, the solution was chilled, neutralized with acetic acid, and refrigerated overnight. The solid that precipitated was removed by filtration, washed with MeOH, and dried in vacuo; yield 5.6 g (34%); mp 159°-161°; TLC homogenous.

Workup

  1. customThe precipitated p-nitrobenzoic acid was removed by filtration
  2. washwashed with CH2Cl2
  3. customThe CH2Cl2 solution was evaporated in vacuo
  4. dissolutionThe residue, dissolved in 500 ml of ethylene chloride
  5. temperatureThis mixture was refluxed until all the chlorosugar
  6. customwas consumed (TLC) (8-11 days)
  7. filtrationfiltered
  8. washThe solid was washed with CHCl3
  9. customthe combined filtrates were evaporated to dryness in vacuo
  10. dissolutionThe residue was dissolved in benzene
  11. filtrationfiltered
  12. custom(to remove unreacted 2,6-diacetamidopurine)
  13. customThe filtrate was again evaporated to dryness in vacuo
  14. dissolutionthe residue dissolved in 100 ml of 1 N methanolic NaOMe
  15. temperatureAfter a 3-hr reflux period
  16. temperaturethe solution was chilled
  17. customneutralized with acetic acid, and refrigerated overnight
  18. customThe solid that precipitated
  19. customwas removed by filtration
  20. washwashed with MeOH
  21. customdried in vacuo

Sources & evidence

ORD record
ord-2d1a9d7b5af74b2ba1e69f2f23f8f45d
Source dataset
uspto-grants-1980_02
Patent number
US04188378

Reaction notes

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