Cesium carbonate → HCID 58958588, compound

HRID 915583Notes

Reaction equation

HRID 915583 reaction equation
[NH2:1][C:2]1[N:6]([CH3:7])[N:5]=[C:4]([C:8]([CH3:11])([CH3:10])[CH3:9])[CH:3]=1.Br[C:13]1[CH:22]=[CH:21][C:20]([O:23][CH3:24])=[CH:19][C:14]=1[C:15]([O:17][CH3:18])=[O:16].C(=O)([O-])[O-].[Cs+].[Cs+].C1C=CC(P(C2C(C3C(P(C4C=CC=CC=4)C4C=CC=CC=4)=CC=C4C=3C=CC=C4)=C3C(C=CC=C3)=CC=2)C2C=CC=CC=2)=CC=1>C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd].C1(C)C=CC=CC=1>[C:8]([C:4]1[CH:3]=[C:2]([NH:1][C:13]2[CH:22]=[CH:21][C:20]([O:23][CH3:24])=[CH:19][C:14]=2[C:15]([O:17][CH3:18])=[O:16])[N:6]([CH3:7])[N:5]=1)([CH3:11])([CH3:10])[CH3:9]

Participants

7

Reactant 4

HCID 10796Cesium carbonateHCID 634876Binap, (A+-)-HCID 27352873-tert-Butyl-1-methyl-1H-pyrazol-5-amineHCID 2776849Methyl 2-bromo-5-methoxybenzoate

Product 1

HCID 58958588HCID 58958588, compoundYield 38.7%

Reagents, catalysts & solvents 2

HCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 1140TolueneSolvent

Conditions

Temperature
110 °C

Procedure

To a 100 mL oven dried flask, was added 5-amino-3-tert-butyl-1-methylpyrazole (2.00 g. 13.1 mmol), methyl 2-bromo-5-methoxybenzoate (2.67 g, 10.9 mmol), cesium carbonate (4.96 g, 15.2 mmol), Pd2(dba)3 (337 mg, 0.33 mmol), BINAP (338 mg, 0.54 mmol), and toluene (35 mL). The reaction mixture was degassed, placed under an N2 atmosphere, and then stirred at 110° C. for 16 h. The reaction mixture was cooled to rt, and ethyl acetate (30 mL) was added. The mixture was filtered, the filter cake washed with EtOAc (10 mL), and the filtrate concentrated under reduced pressure. The residue was purified by silica gel flash chromatography (eluent: 10 to 30% EtOAc in hexane) to give the title compound as a light yellow oil (1.34 g, 38%). 1H NMR (400 MHz, CDCl3) δ 1.28 (s, 9H), 3.63 (s, 3H), 3.78 (s, 3H), 3.94 (s, 3H), 5.97 (s, 1H), 6.82 (d, 1H), 7.10 (dd, 1H), 7.47 (d, 1H).

Workup

  1. customTo a 100 mL oven dried flask
  2. customThe reaction mixture was degassed
  3. temperatureThe reaction mixture was cooled to rt
  4. additionethyl acetate (30 mL) was added
  5. filtrationThe mixture was filtered
  6. washthe filter cake washed with EtOAc (10 mL)
  7. concentrationthe filtrate concentrated under reduced pressure
  8. customThe residue was purified by silica gel flash chromatography (eluent: 10 to 30% EtOAc in hexane)

Sources & evidence

ORD record
ord-72241cd364c64a92985a30c1740f9ba7
Source dataset
uspto-grants-2007_09
Patent number
US07265144B2

Reaction notes

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