Trifluoroacetic acid → HCID 22347032, compound

HRID 432476Notes

Reaction equation

HRID 432476 reaction equation
[NH2:1][C:2]1[N:7]=[CH:6][N:5]=[C:4]2[N:8]([C:27]3[CH:32]=[CH:31][C:30]([N+:33]([O-:35])=[O:34])=[CH:29][CH:28]=3)[N:9]=[C:10]([C:11]3[CH:16]=[CH:15][C:14]([NH:17]C(=O)OC(C)(C)C)=[C:13]([O:25][CH3:26])[CH:12]=3)[C:3]=12.FC(F)(F)C(O)=O>ClCCl>[NH2:1][C:2]1[N:7]=[CH:6][N:5]=[C:4]2[N:8]([C:27]3[CH:28]=[CH:29][C:30]([N+:33]([O-:35])=[O:34])=[CH:31][CH:32]=3)[N:9]=[C:10]([C:11]3[CH:16]=[CH:15][C:14]([NH2:17])=[C:13]([O:25][CH3:26])[CH:12]=3)[C:3]=12

Participants

4

Reactant 2

HCID 6422Trifluoroacetic acidHCID 22347042tert-butyl N-(4-{4-amino-1-[4-nitrophenyl]-1H-pyrazolo[3,4-d]pyrimidin-3-yl}-2-methoxyphenyl)carbamate

Product 1

HCID 22347032HCID 22347032, compoundYield 94%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Conditions

Temperature
0 °C

Procedure

A suspension of tert-butyl N-(4-{4-amino-1-[4-nitrophenyl]-1H-pyrazolo[3,4-d]pyrimidin-3-yl}-2-methoxyphenyl)carbamate (0.386 g, 0.808 mmol) in dichloromethane (8 mL) at 0° C. was treated with trifluoroacetic acid (1.6 mL). The reaction mixture stirred for 20 min at 0° C., then ice bath was removed to stir at room temperature under a nitrogen atmosphere. The reaction mixture was stirred for 18 h. Solvent was removed under reduced pressure. Dichloromethane (15 mL) and sodium hydroxide 1N solution were added to the oil residue. The precipitate formed was filtered and dried over night on the lyophilizer to give 0.286 g (94%) of 4-amino-3-(4-amino-3-methoxyphenyl)-1-[4-nitrophenyl]-1H-pyrazolo[3,4-d]pyrimidine. 1H NMR (DMSO-d6, 400 MHz) δ 8.7826-8.759 (m, 2H), 8.4892-8.4296 (m, 3H), 7.1861-7.1338 (m, 2H), 6.8320-6.8121 (d, 1H, J=7.96 Hz), 5.2225 (s, 2H), 3.8672 (s, 3H); LCMS (Perkin Elmer, Pecosphere C18 column, 3 um particle size, 33×4.6 mm; 100% 50 mM ammonium Acetate in Water to 100% Acetonitrile over 5 min, 3.0 to 3.5 mil/min) tR=3.48 min M+ 377.6.

Workup

  1. customice bath was removed
  2. stirringto stir at room temperature under a nitrogen atmosphere
  3. stirringThe reaction mixture was stirred for 18 h
  4. customSolvent was removed under reduced pressure
  5. additionDichloromethane (15 mL) and sodium hydroxide 1N solution were added to the oil residue
  6. customThe precipitate formed
  7. filtrationwas filtered
  8. customdried over night on the lyophilizer

Sources & evidence

ORD record
ord-030eb38a382a4814ab74d7bdc4c8e96a
Source dataset
uspto-grants-2003_12
Patent number
US06660744B1

Reaction notes

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