Ammonium formate → HCID 178481007, compound

HRID 897596Notes

Reaction equation

HRID 897596 reaction equation
C([O:8][C:9]1[CH:14]=[CH:13][C:12]([C:15]2[C:23]3[C:18](=[N:19][CH:20]=[N:21][C:22]=3[NH2:24])[N:17]([C@H:25]3[CH2:30][CH2:29][C@H:28]([N:31]4[CH2:36][CH2:35][N:34]([CH3:37])[CH2:33][CH2:32]4)[CH2:27][CH2:26]3)[N:16]=2)=[CH:11][CH:10]=1)C1C=CC=CC=1.C([O-])=O.[NH4+]>C(O)C.[Pd]>[NH2:24][C:22]1[N:21]=[CH:20][N:19]=[C:18]2[N:17]([C@H:25]3[CH2:30][CH2:29][C@H:28]([N:31]4[CH2:32][CH2:33][N:34]([CH3:37])[CH2:35][CH2:36]4)[CH2:27][CH2:26]3)[N:16]=[C:15]([C:12]3[CH:13]=[CH:14][C:9]([OH:8])=[CH:10][CH:11]=3)[C:23]=12

Participants

5

Reactant 2

HCID 2723923Ammonium formate2×HCID 178481009HCID 178481009, compound

Product 1

HCID 178481007HCID 178481007, compoundYield 75%

Reagents, catalysts & solvents 2

HCID 23938PalladiumCatalyst2×HCID 702EthanolSolvent

Conditions

Temperature
80 °C

Procedure

A solution of trans-3-[4-(benzyloxy)phenyl]-1-[4-(4-methylpiperazino)cyclohexyl]-1H-pyrazolo[3,4-d]pyrimidin-4-amine (0.806 g, 1.62 mmol) in absolute ethanol (40 mL) was treated with palladium 10 wt. % on activated carbon (0.161 g, 0.324 mmol) and ammonium formate (0.511 g, 8.1 mmol). The reaction mixture was stirred at 80° C. for 3 h, very little product was seen by thin layer chromatography. Palladium 10 wt. % on activated carbon (0.161 g, 0.324 mmol) was added and stirred for an additional hour, still very little product detected. Ammonium formate (0.204 g, 3.24 mmol) was added and stirred over night. The reaction mixture was filtered through a pad of celite, which was washed with ethanol (500 mL). The organic layer was removed under reduced pressure. The resulting solid was triturated with ethyl acetate, and dried over night under high vacuum to give 0.491 g (75%) of trans-4-{4-amino-1-[4-(4-methylpiperazino)cyclohexyl]-1H-pyrazolo[3,4-d]pyrimidin-3-yl}phenol. 1H NMR (DMSO-d6, 400 MHz) δ 9.74 (s, 1H), 8.2 (s, 1H), 7.46-7.44 (d, 2H, J=8 Hz), 6.92-6.90 (d, 2H, J=8 Hz), 4.64-4.58 (m, 1H), 2.67-2.50 (m, 5H), 2.39-2.34 (m, 4H), 2.17 (s, 3H), 2.06-1.92 (m, 6H), 1.50-1.42 (m, 2H); HPLC Waters 2690 Alliance HPLC (Symmetry Shield RP18 3.5 μm, 2.1×50 mm; 5%-95% acetonitrile-0.1 M ammonium acetate over 15 min, 0.5 mL/min) Rt 3.337 min (96%).

Workup

  1. stirringstirred for an additional hour
  2. stirringstirred over night
  3. filtrationThe reaction mixture was filtered through a pad of celite, which
  4. washwas washed with ethanol (500 mL)
  5. customThe organic layer was removed under reduced pressure
  6. customThe resulting solid was triturated with ethyl acetate
  7. customdried over night under high vacuum

Sources & evidence

ORD record
ord-fe24664a25004339ba8f816952dba03e
Source dataset
uspto-grants-2005_07
Patent number
US06921763B2

Reaction notes

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