Water → HCID 59135100, compound

HRID 604214Notes

Reaction equation

HRID 604214 reaction equation
[C:1](B(O)O)([CH3:3])=[CH2:2].[Br:7][C:8]1[C:13]([O:14][CH3:15])=[CH:12][CH:11]=[C:10](I)[N:9]=1.C(=O)([O-])[O-].[Na+].[Na+].O>COCCOC.C(O)C.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.C(OCC)(=O)C>[Br:7][C:8]1[C:13]([O:14][CH3:15])=[CH:12][CH:11]=[C:10]([C:1]([CH3:3])=[CH2:2])[N:9]=1

Participants

9

Reactant 4

HCID 962WaterHCID 10340Sodium CarbonateHCID 10855372(Prop-1-en-2-yl)boronic acidHCID 110990402-Bromo-6-iodo-3-methoxypyridine

Product 1

HCID 59135100HCID 59135100, compoundYield 23.7%

Reagents, catalysts & solvents 4

HCID 178418397HCID 178418397, compoundCatalystHCID 702EthanolSolventHCID 80711,2-DimethoxyethaneSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
80 °C

Procedure

To 0.5M-isopropenyl magnesium bromide/tetrahydrofuran is added trimethyl borate (3.3 ml) and the mixture is stirred under nitrogen atmosphere at room temperature for 30 minutes. To the reaction solution are added 6N-hydrochloric acid and diethylether, and the mixture is separated. The organic layer is washed with a saturated brine, dried over magnesium sulfate, and concentrated under reduced pressure to give isopropenylboronic acid as a crude product (818 mg). The above crude isopropenyl boronic acid (287 mg) and 2-bromo-6-iodo-3-methoxy-pyridine (800 mg) are dissolved in a mixed solvent of 1,2-dimethoxy-ethane (8 ml) and ethanol (3.2 ml) and thereto are added a 1M-aqueous sodium carbonate solution (6.4 ml) and tetrakis(triphenylphosphine)palladium (240 mg) and the mixture is stirred under nitrogen atmosphere at 80° C. for 5 hours. To the reaction solution are added water and ethyl acetate, and the mixture is separated, and the organic layer is washed with a saturated brine, dried over magnesium sulfate, and concentrated under reduced pressure. The residue is purified by silica gel column chromatography (hexane:ethyl acetate=49:1→9:1), followed by NH-silica gel column chromatography (hexane:ethyl acetate=49:1→9:1) to give 2-bromo-6-isopropenyl-3-methoxy-pyridine (138 mg). MS (m/z): 228/230 [M+H]+

Workup

  1. customthe mixture is separated
  2. washthe organic layer is washed with a saturated brine
  3. dry with materialdried over magnesium sulfate
  4. concentrationconcentrated under reduced pressure
  5. customThe residue is purified by silica gel column chromatography (hexane:ethyl acetate=49:1→9:1)

Sources & evidence

ORD record
ord-c35c0c88704640d992c4964bc9bdf15d
Source dataset
uspto-grants-2011_03
Patent number
US07906517B2

Reaction notes

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