Cesium carbonate → HCID 59173418, compound

HRID 220096Notes

Reaction equation

HRID 220096 reaction equation
[NH2:1][C:2]1[N:6]([C:7]2[N:12]=[CH:11][N:10]=[C:9]([NH:13][CH3:14])[CH:8]=2)[N:5]=[C:4]([CH3:15])[CH:3]=1.[C:16]([O:20][C:21](=[O:31])[NH:22][C:23]1[CH:28]=[CH:27][C:26]([CH3:29])=[C:25](Br)[CH:24]=1)([CH3:19])([CH3:18])[CH3:17].C([O-])([O-])=O.[Cs+].[Cs+].C1(P(C2C=CC=CC=2)C2C3OC4C(=CC=CC=4P(C4C=CC=CC=4)C4C=CC=CC=4)C(C)(C)C=3C=CC=2)C=CC=CC=1>CC([O-])=O.CC([O-])=O.[Pd+2].O1CCOCC1>[CH3:29][C:26]1[CH:25]=[CH:24][C:23]([NH:22][C:21](=[O:31])[O:20][C:16]([CH3:18])([CH3:17])[CH3:19])=[CH:28][C:27]=1[NH:1][C:2]1[N:6]([C:7]2[CH:8]=[C:9]([NH:13][CH3:14])[N:10]=[CH:11][N:12]=2)[N:5]=[C:4]([CH3:15])[CH:3]=1

Participants

7

Reactant 4

HCID 10796Cesium carbonateHCID 6360441,1'-(9,9-Dimethyl-9H-xanthene-4,5-diyl)bis(1,1-diphenylphosphine)HCID 58764366tert-Butyl (3-bromo-4-methylphenyl)carbamateHCID 591733071018473-23-8

Product 1

HCID 59173418HCID 59173418, compound

Reagents, catalysts & solvents 2

HCID 167845palladium(II) acetateCatalystHCID 312751,4-DioxaneSolvent

Conditions

Temperature
120 °C

Procedure

To a high pressure tube is added 6-(5-amino-3-methyl-1H-pyrazol-1-yl)-N-methylpyrimidin-4-amine 29 (2.0 g, 9.8 mmol), 3-bromo-4-methylphenyl carbamic acid tert-butyl ester 37 (2.4 g, 10.8 mmol), Pd(OAc)2 (132 mg, 0.59 mmol), Cs2CO3 (3.5 g, 10.8 mmol), 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene (340 mg, 0.59 mmol) and 1,4-dioxane (30 mL). The mixture is flushed with N2 at 0° C. for a few minutes, then heated to 120° C. for 2 days. The mixture is poured into water and extracted with EtOAc. The organic layer is separated, dried with MgSO4, then concentrated in vacuo. The residue is purified by flash chromatography [silica gel, hexane:EtOAc/5:5] to provide tert-butyl 4-methyl-3-(3-methyl-1-(6-(methylamino)-pyrimidin-4-yl)-1H-pyrazol-5-ylamino)phenylcarbamate 38.

Workup

  1. customThe mixture is flushed with N2 at 0° C. for a few minutes
  2. additionThe mixture is poured into water
  3. extractionextracted with EtOAc
  4. customThe organic layer is separated
  5. dry with materialdried with MgSO4
  6. concentrationconcentrated in vacuo
  7. customThe residue is purified by flash chromatography [silica gel, hexane:EtOAc/5:5]

Sources & evidence

ORD record
ord-57452b269d174418bf3a0636d3ad5d55
Source dataset
uspto-grants-2012_06
Patent number
US08202876B2

Reaction notes

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