D-Psicose → 3-[5-amino-1-(1,1-dimethylethyl)-3-methyl-1H-pyrazol-4-yl]-5-fluoro-2-(methyloxy)phenol

HRID 253285Notes

Reaction equation

HRID 253285 reaction equation
[CH3:1][C:2]([N:5]1[C:9]([NH2:10])=[C:8]([C:11]2[CH:16]=[C:15]([F:17])[CH:14]=[C:13]([O:18]CC3C=CC=CC=3)[C:12]=2[O:26][CH3:27])[C:7]([CH3:28])=[N:6]1)([CH3:4])[CH3:3].OCC1(OC[C@@H](O)[C@@H](O)[C@H]1O)O>C1COCC1.C(OCC)(=O)C.[Pd]>[NH2:10][C:9]1[N:5]([C:2]([CH3:3])([CH3:4])[CH3:1])[N:6]=[C:7]([CH3:28])[C:8]=1[C:11]1[C:12]([O:26][CH3:27])=[C:13]([OH:18])[CH:14]=[C:15]([F:17])[CH:16]=1

Participants

5

Reactant 2

HCID 441036D-PsicoseHCID 668909321-(1,1-dimethylethyl)-4-(5-fluoro-2-(methyloxy)-3-[{phenylmethyl)oxy]phenyl}-3-methyl-1H-pyrazol-5-amine

Product 1

HCID 668904023-[5-amino-1-(1,1-dimethylethyl)-3-methyl-1H-pyrazol-4-yl]-5-fluoro-2-(methyloxy)phenolYield 93.1%

Reagents, catalysts & solvents 2

HCID 23938PalladiumCatalystHCID 21939870Tetrahydrofuran ethyl acetateSolvent

Procedure

A solution of 1-(1,1-dimethylethyl)-4-(5-fluoro-2-(methyloxy)-3-[{phenylmethyl)oxy]phenyl}-3-methyl-1H-pyrazol-5-amine (25 g, 0.0652 mol) in a mixture of THF-ethyl acetate (1:1, 300 mL) was hydrogenated over 10% Pd—C (2.5 g) at 40 Psi for 2 h. The catalyst was filtered off, and the filtrate was concentrated. The resulting crude was triturated with diethyl ether; a white solid was precipitated. It was collected by filtration, washed with an additional portion of diethyl ether and dried in vacuo to give 17.8 g of 3-[5-amino-1-(1,1-dimethylethyl)-3-methyl-1H-pyrazol-4-yl]-5-fluoro-2-(methyloxy)phenol (93%). 1H NMR (400 MHz, DMSO-d6): δ 9.63 (s, 1H), 6.56 (dd, 1H), 6.38 (dd, 1H), 4.44 (s, 2H), 3.37 (s, 3H), 1.98 (s, 3H), 1.56 (s, 9H); MS (EI) for C15H20FN3O2: 294 (MH+)

Workup

  1. filtrationThe catalyst was filtered off
  2. concentrationthe filtrate was concentrated
  3. customThe resulting crude was triturated with diethyl ether
  4. customa white solid was precipitated
  5. filtrationIt was collected by filtration
  6. washwashed with an additional portion of diethyl ether
  7. customdried in vacuo

Sources & evidence

ORD record
ord-7c2e37733f3f48868e0ecbff95e57d95
Source dataset
uspto-grants-2011_01
Patent number
US07872014B2

Reaction notes

Loading…