Tert-butyl {2-fluoro-5-[methyl(5-nitro-4-thiocyanatopyrimidin-2-yl)amino]phenyl}carbamate → Tert-butyl {5-[(2-amino[1,3]thiazolo[5,4-d]pyrimidin-5-yl)(methyl)amino]-2-fluorophenyl}carbamate

HRID 1800696Notes

Reaction equation

HRID 1800696 reaction equation
[F:1][C:2]1[CH:7]=[CH:6][C:5]([N:8]([CH3:21])[C:9]2[N:14]=[C:13]([S:15][C:16]#[N:17])[C:12]([N+:18]([O-])=O)=[CH:11][N:10]=2)=[CH:4][C:3]=1[NH:22][C:23](=[O:29])[O:24][C:25]([CH3:28])([CH3:27])[CH3:26]>C(O)(=O)C>[NH2:17][C:16]1[S:15][C:13]2[N:14]=[C:9]([N:8]([CH3:21])[C:5]3[CH:6]=[CH:7][C:2]([F:1])=[C:3]([NH:22][C:23](=[O:29])[O:24][C:25]([CH3:28])([CH3:27])[CH3:26])[CH:4]=3)[N:10]=[CH:11][C:12]=2[N:18]=1

Participants

3

Reactant 1

HCID 86646077Tert-butyl {2-fluoro-5-[methyl(5-nitro-4-thiocyanatopyrimidin-2-yl)amino]phenyl}carbamate

Product 1

HCID 86646078Tert-butyl {5-[(2-amino[1,3]thiazolo[5,4-d]pyrimidin-5-yl)(methyl)amino]-2-fluorophenyl}carbamateYield 46%

Reagents, catalysts & solvents 1

HCID 176Acetic AcidSolvent

Conditions

Temperature
80 °C

Procedure

To a solution of the above-mentioned crude product of tert-butyl {2-fluoro-5-[methyl(5-nitro-4-thiocyanatopyrimidin-2-yl)amino]phenyl}carbamate in acetic acid (70 mL) was added reduced iron (4.28 g, 76.7 mmol), and the mixture was stirred at 80° C. for 3 hr. The insoluble material was filtered off, and the filtrate was concentrated under reduced pressure. To the obtained residue was added 0.5N aqueous sodium hydroxide solution (100 mL), and the mixture was extracted with ethyl acetate (200 mL, 30 mL). The combined organic layer was washed with saturated brine (30 mL), and dried over anhydrous sodium sulfate. The insoluble material was filtered off, and the filtrate was concentrated under reduced pressure. The obtained residue was washed with tetrahydrofuran to give the title compound (1.95 g, 46%) as a pale-purple solid.

Workup

  1. filtrationThe insoluble material was filtered off
  2. concentrationthe filtrate was concentrated under reduced pressure
  3. additionTo the obtained residue was added 0.5N aqueous sodium hydroxide solution (100 mL)
  4. extractionthe mixture was extracted with ethyl acetate (200 mL, 30 mL)
  5. washThe combined organic layer was washed with saturated brine (30 mL)
  6. dry with materialdried over anhydrous sodium sulfate
  7. filtrationThe insoluble material was filtered off
  8. concentrationthe filtrate was concentrated under reduced pressure
  9. washThe obtained residue was washed with tetrahydrofuran

Sources & evidence

ORD record
ord-7800fe0044804c50b045192ddc227e3e
Source dataset
uspto-grants-2013_01
Patent number
US08344135B2

Reaction notes

Loading…