Dichloromethane → 7-(2-Chloro-5-methoxyphenyl)-5-methylbenzo[e][1,2,4]triazin-3-amine

HRID 449200Notes

Reaction equation

Br[C:2]1[CH:12]=[C:11]([CH3:13])[C:5]2[N:6]=[C:7]([NH2:10])[N:8]=[N:9][C:4]=2[CH:3]=1.[C:14]([O-:17])([O-])=O.[Na+].[Na+].[CH2:20]([Cl:22])Cl>COCCOC.CCO.O.C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.[Pd]>[Cl:22][C:20]1[CH:11]=[CH:12][C:2]([O:17][CH3:14])=[CH:3][C:4]=1[C:2]1[CH:12]=[C:11]([CH3:13])[C:5]2[N:6]=[C:7]([NH2:10])[N:8]=[N:9][C:4]=2[CH:3]=1

Participants

Conditions

Temperature: 100 °C

Procedure

7-bromo-5-methyl-benzo[1,2,4]triazin-3-ylamine (33.47 mmol, 1.0 equiv), 1-chloro-4-methoxy-2-boronic acid (50.21 mmol, 1.5 equiv), Pd(PPH3)4 (3.347 mmol, 0.1 equiv), and Na2CO3 (133.9 mmol, 4.0 equiv) were dissolved in DME/EtOH/water 6:1:1 and refluxed at 100° C. under an argon blanket for 4 h. The reaction was cooled to room temperature, diluted with 100 mL DCM and filtered. The precipitate that was recovered was suspended in water, filtered and rinsed with ether. The precipitate afforded 7-(2-chloro-5-methoxy-phenyl)-5-methyl-benzo[1,2,4]triazin-3-ylamine, as a green solid (8.37 g, 84% yield). Rf=0.85 (9:1 DCM/MeOH). 1H NMR (DMSO-d6): δ 3.35 (s, 6H), 7.01 (dd, J=8.8 Hz, J=3.0, 1H), 7.09 (d, J=3.0 Hz, 1H), 7.48 (d, J=8.8 Hz, 1H), 7.75 (bm, 2H). MS (ES+) m/z=303. LC retention time 3.03 min.

Workup

temperatureThe reaction was cooled to room temperature
filtrationfiltered
customThe precipitate that was recovered
filtrationfiltered
washrinsed with ether

Sources & evidence

ORD record: ord-6e09d67a69a940d69d087834418abd75
Source dataset: uspto-grants-2013_07
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US08481536B2

Reaction notes

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