Cesium carbonate → HCID 57731560, compound

HRID 2234694Notes

Reaction equation

HRID 2234694 reaction equation
[NH2:1][C:2]1[CH:12]=[CH:11][C:10]([Br:13])=[CH:9][C:3]=1[C:4]([N:6]([CH3:8])[CH3:7])=[O:5].C(=O)([O-])[O-].[Cs+].[Cs+].Br[C:21]1[CH:22]=[N:23][CH:24]=[N:25][CH:26]=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(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>[Br:13][C:10]1[CH:11]=[CH:12][C:2]([NH:1][C:21]2[CH:22]=[N:23][CH:24]=[N:25][CH:26]=2)=[C:3]([CH:9]=1)[C:4]([N:6]([CH3:7])[CH3:8])=[O:5]

Participants

6

Reactant 3

HCID 10796Cesium carbonateHCID 783445-BromopyrimidineHCID 509995122-Amino-5-bromo-N,N-dimethylbenzamide

Product 1

HCID 57731560HCID 57731560, compoundYield 80%

Reagents, catalysts & solvents 2

HCID 6360441,1'-(9,9-Dimethyl-9H-xanthene-4,5-diyl)bis(1,1-diphenylphosphine)CatalystHCID 9811564Bis(dibenzylideneacetone)palladiumCatalyst

Conditions

Temperature
100 °C

Procedure

A vial is charged with 120 mg (0.49 mmol) of 2-amino-5-bromo-N,N-dimethyl-benzamide, 11.4 mg (12 μmol) of tris(dibenzylideneacetone)dipalladium(0), 15.9 mg (27 μmol) of 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene (XantPhos), 290 mg (0.89 mmol) of cesium carbonate, and 159 mg (1.00 mmol) of 5-bromo-pyrimidine. The vial is flushed with nitrogen and 2 mL of anhydrous 1,4-dioxane are added. The vial is sealed and heated to 100° C. for 17 h. The resulting mixture is diluted with methanol and dichloromethane and filtered over a 0.45 μm PTFE syringe filter. The filtrate is evaporated and the residue purified by flash chromatography on silica gel using a gradient of ethyl acetate containing 10% v/v of methanol in hexanes to afford 115.6 mg (0.39 mmol, 80%) of 5-bromo-N,N-dimethyl-2-(pyrimidin-5-ylamino)-benzamide as an ivory solid. 1H-NMR (500 MHz, d6-DMSO): δ 8.66 (s, 1H), 8.48 (s, 2H), 8.13 (s, br., 1H), 7.51 (dd, 1H), 7.43 (d, 1H), 7.23 (d, 1H), 2.86 (s, 3H), 2.81 (s, 3H); MS: m/z 321.0+323.0 (M+H+).

Workup

  1. customThe vial is flushed with nitrogen and 2 mL of anhydrous 1,4-dioxane
  2. additionare added
  3. customThe vial is sealed
  4. additionThe resulting mixture is diluted with methanol and dichloromethane
  5. filtrationfiltered over a 0.45 μm PTFE syringe
  6. filtrationfilter
  7. customThe filtrate is evaporated
  8. customthe residue purified by flash chromatography on silica gel using a gradient of ethyl acetate containing 10% v/v of methanol in hexanes

Sources & evidence

ORD record
ord-d37b97362f7542b28cb2f29040e1cfd2
Source dataset
uspto-grants-2010_05
Patent number
US07709645B2

Reaction notes

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