Diisopropylamine → Methyl 3-bromo-5-(prop-1-en-2-yl)benzoate

HRID 888402Notes

Reaction equation

HRID 888402 reaction equation
[Br:1][C:2]1[CH:3]=[C:4]([CH:9]=[C:10](I)[CH:11]=1)[C:5]([O:7][CH3:8])=[O:6].[C:13](B1OC(C)(C)C(C)(C)O1)([CH3:15])=[CH2:14].C(NC(C)C)(C)C.C(=O)(O)[O-].[Na+]>C(#N)C.O.C([O-])(=O)C.[Pd+2].C([O-])(=O)C.C1C=C(S([O-])(=O)=O)C=C(P(C2C=CC=C(S([O-])(=O)=O)C=2)C2C=CC=C(S([O-])(=O)=O)C=2)C=1.[Na+].[Na+].[Na+]>[Br:1][C:2]1[CH:3]=[C:4]([CH:9]=[C:10]([C:13]([CH3:15])=[CH2:14])[CH:11]=1)[C:5]([O:7][CH3:8])=[O:6]

Participants

9

Reactant 4

HCID 7912DiisopropylamineHCID 516892Sodium BicarbonateHCID 109974264,4,5,5-Tetramethyl-2-(prop-1-en-2-yl)-1,3,2-dioxaborolaneHCID 21942573Methyl 3-bromo-5-iodobenzoate

Product 1

HCID 68498655Methyl 3-bromo-5-(prop-1-en-2-yl)benzoateYield 91.4%

Reagents, catalysts & solvents 4

HCID 167845palladium(II) acetateCatalystHCID 6099338Trisodium 3,3',3''-phosphinetriyltris(benzene-1-sulphonate)CatalystHCID 962WaterSolventHCID 6342AcetonitrileSolvent

Conditions

Temperature
80 °C

Procedure

To a solution of methyl 3-bromo-5-iodobenzoate (2.50 g, 7.33 mmol) in acetonitrile (22.0 mL) and water (7.33 mL) was 2-isopropenyl-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (1.378 mL, 7.33 mmol), palladium(II) acetate (41.0 mg, 0.183 mmol), 3,3′3″-phosphinidynetris(benzenesulfonic acid)trisodium salt (313 mg, 0.550 mmol) and diisopropylamine (2.61 mL, 18.33 mmol) and the mixture was heated to 80° C. After 2.5 h, the reaction was allowed to cool to ambient temperature and saturated aqueous sodium bicarbonate was added. The mixture was extracted with ethyl acetate (3×). The combined organic extracts were washed with brine, dried over magnesium sulfate, filtered and concentrated. Purification by silica gel chromatography (100% hexanes→80% hexanes/ethyl acetate) gave the title compound (1.71 g).

Workup

  1. temperatureto cool to ambient temperature
  2. extractionThe mixture was extracted with ethyl acetate (3×)
  3. washThe combined organic extracts were washed with brine
  4. dry with materialdried over magnesium sulfate
  5. filtrationfiltered
  6. concentrationconcentrated
  7. customPurification by silica gel chromatography (100% hexanes→80% hexanes/ethyl acetate)

Sources & evidence

ORD record
ord-4a17ddc0f48f40c898e60ba4ea6e8829
Source dataset
uspto-grants-2012_08
Patent number
US08247401B2

Reaction notes

Loading…