Cesium carbonate → Ethyl-8-(4-Methyl-piperazin-1-yl)-4-oxo-4H-chromene-2-carboxylic acid

HRID 2414479Notes

Reaction equation

Br[C:2]1[CH:3]=[CH:4][CH:5]=[C:6]2[C:11]=1[O:10][C:9]([C:12]([O:14]CC)=[O:13])=[CH:8][C:7]2=[O:17].[CH3:18][N:19]1[CH2:24][CH2:23][NH:22][CH2:21][CH2:20]1.[C:25]1(P(C2C=CC=CC=2)C2C=CC3C(=CC=CC=3)C=2C2C3C(=CC=CC=3)C=CC=2P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=C[CH:26]=1.C(=O)([O-])[O-].[Cs+].[Cs+]>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]>[CH2:25]([C:8]1[C:7](=[O:17])[C:6]2[C:11](=[C:2]([N:22]3[CH2:23][CH2:24][N:19]([CH3:18])[CH2:20][CH2:21]3)[CH:3]=[CH:4][CH:5]=2)[O:10][C:9]=1[C:12]([OH:14])=[O:13])[CH3:26]

Participants

Conditions

Temperature: 80 °C

Procedure

Ethyl 8-bromo-4-oxo-4H-chromene-2-carboxylate as prepared in Reference Example 1c (Davies, Stephen et al., J. Chem. Soc. Perkin Trans I p 2597, 1987) (3.0 g, 10.1 mmol) was azeotroped with anhydrous toluene then the white solid was dissolved in 100 mL anhydrous toluene and transferred to the reaction vessel. The mixture was subjected to vacuum/argon (×2) and the following were added in order (positive argon pressure): N-methylpiperazine (1.3 ml, 11.1 mmol), 2,2′-bis(diphenylphosphino)-1,1′-binaphthyl (0.75 g, 1.2 mmol), tris(dibenzylideneacetone)dipalladium(0) (0.48 g, 0.5 mmol) then cesium carbonate (4.6 g, 14.1 mmol). The mixture was again subjected to vacuum/argon and was heated at 80° C. overnight.

Workup

customwas azeotroped with anhydrous toluene
dissolutionthe white solid was dissolved in 100 mL anhydrous toluene
additionthe following were added in order (positive argon pressure)

Sources & evidence

ORD record: ord-f063a33e07334cecbb09e2b23d8c3849
Source dataset: uspto-grants-2004_11
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US06812225B2

Reaction notes

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