Ammonium formate → 6-Bromoisoquinolin-3-Amine

HRID 598892Notes

Reaction equation

Br[C:2]1[C:11]2[C:6](=[CH:7][C:8]([Br:12])=[CH:9][CH:10]=2)[CH:5]=[C:4]([NH2:13])[N:3]=1.C([O-])=O.[NH4+]>CN(C=O)C.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]>[Br:12][C:8]1[CH:7]=[C:6]2[C:11](=[CH:10][CH:9]=1)[CH:2]=[N:3][C:4]([NH2:13])=[CH:5]2

Participants

Conditions

Temperature: 50 °C

Procedure

A mixture of 1,6-dibromoisoquinolin-3-amine (13.5 g, 45 mmol), ammonium formate (10.8 g, 172 mmol) and tetrakis(triphenylphosphine)palladium (0) (3.45 g, 3.0 mmol) in 50 mL of DMF were sealed in a 350 mL screw-cap flask and heated at 50° C. for 48 hours. To the reaction was added tetrakis(triphenylphosphine)palladium (0) (950 mg) and ammonium formate (3.0 g), and the mixture was heated at 50° C. for 48 hours. The mixture was cooled to room temperature and the solid was filtered, washed with a minimal amount of DMF, washed with Et2O and dried in vacuo at 50° C. to give the product as a yellow amorphous solid (10.4 g, 90%) LCMS (API-ES) m/z: 222.9, 224.9 [M+1]. 1H NMR (300 MHz, DMSO-d6) δ ppm 8.81 (s, 1H), 7.80 (d, J=1.6 Hz, 1H), 7.73 (d, J=8.8 Hz, 1H), 7.22 (dd, J=8.6, 1.9 Hz, 1H), 6.55 (s, 1H), 6.12 (s, 2H).

Workup

customwere sealed in a 350 mL
customscrew-cap flask
temperaturethe mixture was heated at 50° C. for 48 hours
temperatureThe mixture was cooled to room temperature
filtrationthe solid was filtered
washwashed with a minimal amount of DMF
washwashed with Et2O
customdried in vacuo at 50° C.

Sources & evidence

ORD record: ord-629992dd5c9a485ab5dbfb9a29ab8656
Source dataset: uspto-grants-2011_03
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US07897619B2

Reaction notes

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