1,2-Dimethoxyethane → 2-Bromo-6-(prop-1-en-2-yl)pyridine

HRID 1028582Notes

Reaction equation

HRID 1028582 reaction equation
Br[C:2]1[CH:7]=[CH:6][CH:5]=[C:4]([Br:8])[N:3]=1.[C:9](B(O)O)([CH3:11])=[CH2:10].COCCOC.C([O-])([O-])=O.[Na+].[Na+]>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.CCO>[Br:8][C:4]1[CH:5]=[CH:6][CH:7]=[C:2]([C:9]([CH3:11])=[CH2:10])[N:3]=1

Participants

7

Reactant 4

HCID 80711,2-DimethoxyethaneHCID 10340Sodium CarbonateHCID 122742,6-DibromopyridineHCID 10855372(Prop-1-en-2-yl)boronic acid

Product 1

HCID 221642832-Bromo-6-(prop-1-en-2-yl)pyridine

Reagents, catalysts & solvents 2

HCID 178418397HCID 178418397, compoundCatalystHCID 702EthanolSolvent

Conditions

Temperature
100 °C

Procedure

In a tube were placed 2,6-dibromopyridine (100 mg, 0.422 mmol), isopropenylboronic acid (40 mg, 0.464 mmol), DME (1.5 mL), EtOH (500 μL), and 1M aqueous Na2CO3 (1 mL, 1.0 mmol). The mixture was degassed with N2. Next, Pd(PPh3)4 (37 mg, 0.032 mmol) was added and the mixture was degassed again with N2. The tube was sealed and heated at 100° C. for 1 hour. The reaction was then cooled to room temperature, diluted with EtOAc (50 mL), and washed with water and brine (15 mL each). The organic layer was dried over Na2SO4, filtered, and concentrated. Purification of the residue by flash chromatography on silica gel (5% EtOAc/hexanes) afforded 2-bromo-6-isopropenylpyridine. Rf=0.45 (15% EtOAc/hexanes). LCMS=200.0 (M+1)+. 1H NMR (CDCl3, 500 MHz) δ 7.49 (t, J=7.8 Hz, 1H), 7.39 (d, J=7.8 Hz, 1H), 7.34 (d, J=8.0 Hz, 1H), 5.93 (s, 1H), 5.32 (m, 1H), 2.17 (s, 3H).

Workup

  1. customIn a tube were placed
  2. customThe mixture was degassed with N2
  3. customthe mixture was degassed again with N2
  4. customThe tube was sealed
  5. temperatureThe reaction was then cooled to room temperature
  6. additiondiluted with EtOAc (50 mL)
  7. washwashed with water and brine (15 mL each)
  8. dry with materialThe organic layer was dried over Na2SO4
  9. filtrationfiltered
  10. concentrationconcentrated
  11. customPurification of the residue by flash chromatography on silica gel (5% EtOAc/hexanes)

Sources & evidence

ORD record
ord-892fe1edb4194a0ea556f7022497f613
Source dataset
uspto-grants-2014_05
Patent number
US08735435B2

Reaction notes

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