Diisopropylamine → HCID 66690551, compound

HRID 592306Notes

Reaction equation

HRID 592306 reaction equation
Br[C:2]1[CH:3]=[C:4]([CH:9]=[C:10]([N+:13]([O-:15])=[O:14])[C:11]=1[OH:12])[C:5]([O:7][CH3:8])=[O:6].[F:16][C:17]1[CH:22]=[CH:21][C:20](B(O)O)=[CH:19][CH:18]=1.[Na+].[Na+].[Na+].P(C1C=C(S([O-])(=O)=O)C=CC=1)(C1C=C(S([O-])(=O)=O)C=CC=1)C1C=C(S([O-])(=O)=O)C=CC=1.C(NC(C)C)(C)C>C([O-])(=O)C.[Pd+2].C([O-])(=O)C.C(OCC)(=O)C.O.CN(C)C=O>[F:16][C:17]1[CH:22]=[CH:21][C:20]([C:2]2[C:11]([OH:12])=[C:10]([N+:13]([O-:15])=[O:14])[CH:9]=[C:4]([C:5]([O:7][CH3:8])=[O:6])[CH:3]=2)=[CH:19][CH:18]=1

Participants

9

Reactant 4

HCID 7912DiisopropylamineHCID 2856454-Fluorophenylboronic acidHCID 6099338Trisodium 3,3',3''-phosphinetriyltris(benzene-1-sulphonate)HCID 14985559Methyl 3-bromo-4-hydroxy-5-nitrobenzoate

Product 1

HCID 66690551HCID 66690551, compoundYield 40.8%

Reagents, catalysts & solvents 4

HCID 167845palladium(II) acetateCatalystHCID 962WaterSolventHCID 6228DimethylformamideSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
80 °C

Procedure

To a solution of methyl 3-bromo-4-hydroxy-5-nitrobenzoate (1.0 g, 3.62 mmol), (4-fluorophenyl)-boronic acid (0.76 g, 5.43 mmol), 3,3′,3″-phosphinidynetris (benzensulfonic acid) trisodium salt (0.17 mg, 0.27 mmol), palladium(II) acetate (20.0 mg, 0.09 mmol) and diisopropylamine (0.52 mL, 3.62 mmol) were added N,N-dimethylformamide (13.6 mL) and water (4.5 mL). The mixture was heated to 80° C. After 18 h, the mixture was cooled to ambient temperature and ethyl acetate was added. The organic layer was washed with water (3×), brine, dried over magnesium sulfate, filtered and concentrated. Purification by silica gel chromatography (100% hexanes→25% hexanes/ethyl acetate). Another purification using reverse phase HPLC (C-18, 95% water/acetonitrile→5% water/acetonitrile with 0.1% trifluoroacetic acid) gave the title compound (0.43 g). LC-MS [M+1]=291.9.

Workup

  1. temperaturethe mixture was cooled to ambient temperature
  2. washThe organic layer was washed with water (3×), brine
  3. dry with materialdried over magnesium sulfate
  4. filtrationfiltered
  5. concentrationconcentrated
  6. customPurification by silica gel chromatography (100% hexanes→25% hexanes/ethyl acetate)
  7. customAnother purification

Sources & evidence

ORD record
ord-f2ac043724bb4f43a44de1dd8925c20d
Source dataset
uspto-grants-2016_01
Patent number
US09238647B2

Reaction notes

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