Trifluoroacetic acid → HCID 22347032, compound

HRID 897764Notes

Reaction equation

HRID 897764 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-303f38cfce4947e7817e43f2028eb007
Source dataset
uspto-grants-2005_07
Patent number
US06921763B2

Reaction notes

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