4-Bromo-2-fluoro-1-nitrobenzene → HCID 86661419, compound

HRID 628574Notes

Reaction equation

Br[C:2]1[CH:7]=[CH:6][C:5]([N+:8]([O-:10])=[O:9])=[C:4]([F:11])[CH:3]=1.[N+:12]([C:15]1[CH:21]=[C:20](B2OC(C)(C)C(C)(C)O2)[CH:19]=[CH:18][C:16]=1[NH2:17])([O-:14])=[O:13]>COCCOC.O>[F:11][C:4]1[CH:3]=[C:2]([C:20]2[CH:19]=[CH:18][C:16]([NH2:17])=[C:15]([N+:12]([O-:14])=[O:13])[CH:21]=2)[CH:7]=[CH:6][C:5]=1[N+:8]([O-:10])=[O:9]

Participants

Conditions

Temperature: 130 °C

Procedure

4-Bromo-2-fluoro-1-nitrobenzene (500 mg, 2.27 mmol), 2-nitro-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)aniline (660 mg, 2.50 mmol) and K2CO2 (940 mg, 6.81 mmol) were suspended in DME-H2O (4:1, 15 mL) and purged with nitrogen. The solution was degassed by sonication before Pd(dppf)Cl2 (185 mg, 10 mol %) was added. The mixture was heated to 130° C. for 10 min under microwave irradiation. The cooled mixture was partitioned between EtOAc and H2O. The aqueous layer was extracted with EtOAc (2×50 mL). The combined organic extracts were washed with brine, dried (MgSO4), filtered and concentrated. The resulting black solid was absorbed onto silica and purified by column chromatography (4:1 to 1:1 petrol-EtOAc) to give the product as an orange solid (285 mg, 45%).

Workup

custompurged with nitrogen
customThe solution was degassed by sonication before Pd(dppf)Cl2 (185 mg, 10 mol %)
additionwas added
customThe cooled mixture was partitioned between EtOAc and H2O
extractionThe aqueous layer was extracted with EtOAc (2×50 mL)
washThe combined organic extracts were washed with brine
dry with materialdried (MgSO4)
filtrationfiltered
concentrationconcentrated
customThe resulting black solid was absorbed onto silica
custompurified by column chromatography (4:1 to 1:1 petrol-EtOAc)

Sources & evidence

ORD record: ord-02edcea09dea4c84ae3cf49ac2ec0851
Source dataset: uspto-grants-2016_04
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US09314456B2

Reaction notes

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