Cesium carbonate → HCID 16041748, compound

HRID 545171Notes

Reaction equation

HRID 545171 reaction equation
Br[C:2]1[CH:3]=[C:4]2[C:30](=[CH:31][CH:32]=1)[O:29][C:7]1([CH2:12][CH2:11][N:10]([C:13]([C:15]3[CH:24]=[C:23]([O:25][CH3:26])[C:22]4[C:17](=[C:18]([O:27][CH3:28])[CH:19]=[CH:20][CH:21]=4)[N:16]=3)=[O:14])[CH2:9][CH2:8]1)[CH2:6][C:5]2=[O:33].[NH2:34][C:35]1[N:39]([CH3:40])[N:38]=[CH:37][CH:36]=1.C(P(C(C)(C)C)C1C=CC=CC=1C1C=CC=CC=1)(C)(C)C.C(=O)([O-])[O-].[Cs+].[Cs+]>O1CCOCC1.C([O-])(=O)C.[Pd+2].C([O-])(=O)C>[CH3:26][O:25][C:23]1[C:22]2[C:17](=[C:18]([O:27][CH3:28])[CH:19]=[CH:20][CH:21]=2)[N:16]=[C:15]([C:13]([N:10]2[CH2:11][CH2:12][C:7]3([CH2:6][C:5](=[O:33])[C:4]4[C:30](=[CH:31][CH:32]=[C:2]([NH:34][C:35]5[N:39]([CH3:40])[N:38]=[CH:37][CH:36]=5)[CH:3]=4)[O:29]3)[CH2:8][CH2:9]2)=[O:14])[CH:24]=1

Participants

7

Reactant 4

HCID 10796Cesium carbonateHCID 1369272-Methyl-2H-pyrazol-3-ylamineHCID 27342152-(Di-tert-butylphosphino)biphenylHCID 16041747HCID 16041747, compound

Product 1

HCID 16041748HCID 16041748, compound

Reagents, catalysts & solvents 2

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

Conditions

Temperature
120 °C

Procedure

The bromide compound (2.00 g) produced in Example 9, 5-amino-1-methyl-1H-pyrazole (456 mg), palladium acetate (175 mg), 2-(di-t-butylphosphino)biphenyl (233 mg) and cesium carbonate (1.66 g) were suspended in 1,4-dioxane (20 mL), and heated under reflux at 120° C. for 40 hours. The reaction liquid was filtered through Celite, the residue on the Celite was washed with chloroform, and the filtrate was concentrated under reduced pressure. The resulting residue was purified through silica gel column chromatography (developed with solvents of ethyl acetate/acetone=6/4 and chloroform/methanol=99/1 in order) to obtain the intended compound as a yellow amorphous solid. 1H-NMR (400 MHz, CDCl3) δ: 7.77 (1H, dd, J=8.3, 1.0 Hz), 7.49-7.43 (2H, m), 7.22 (1H, d, J=2.8 Hz), 7.17 (1H, s), 7.08 (1H, dd, J=7.8, 1.0 Hz), 6.97 (1H, dd, J=8.8, 2.8 Hz), 6.91 (1H, d, J=8.8 Hz), 5.97 (1H, d, J=2.0 Hz), 5.42 (1H, s), 4.60-4.52 (1H, m), 4.18-4.10 (1H, m), 4.07 (3H, s), 4.03 (3H, s), 3.68 (3H, s), 3.65-3.55 (1H, m), 3.40-3.29 (1H, m), 2.77 (1H, d, J=16.6 Hz), 2.71 (1H, d, J=16.6 Hz), 2.25-2.15 (1H, m), 2.10-2.02 (1H, m), 1.92-1.79 (2H, m). MS [M+H]+=528.

Workup

  1. temperatureheated
  2. customThe reaction liquid
  3. filtrationwas filtered through Celite
  4. washthe residue on the Celite was washed with chloroform
  5. concentrationthe filtrate was concentrated under reduced pressure
  6. customThe resulting residue was purified through silica gel column chromatography (developed with solvents of ethyl acetate/acetone=6/4 and chloroform/methanol=99/1 in order)

Sources & evidence

ORD record
ord-67ccc49a8181429395e1497cde90d681
Source dataset
uspto-grants-2011_05
Patent number
US07935712B2

Reaction notes

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