2,4-Dibromopyridine → HCID 118092569, compound

HRID 2207346Notes

Reaction equation

HRID 2207346 reaction equation
Br[C:2]1[CH:7]=[C:6]([Br:8])[CH:5]=[CH:4][N:3]=1.Br[Zn][CH2:11][CH2:12][C:13]([O:15][CH2:16][CH3:17])=[O:14]>C1COCC1.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>[Br:8][C:6]1[CH:5]=[CH:4][N:3]=[C:2]([CH2:11][CH2:12][C:13]([O:15][CH2:16][CH3:17])=[O:14])[CH:7]=1

Participants

5

Reactant 2

HCID 8171042,4-DibromopyridineHCID 178471817HCID 178471817, compound

Product 1

HCID 118092569HCID 118092569, compound

Reagents, catalysts & solvents 2

HCID 178418397HCID 178418397, compoundCatalystHCID 8028TetrahydrofuranSolvent

Conditions

Temperature
85 °C

Procedure

Nitrogen was bubbled through a solution of 2,4-dibromopyridine (0.25 g, 1.06 mmol) in THF (2 ml) for ˜10 minutes. Tetrakis(triphenylphosphine)palladium(0) (0.122 g, 0.106 mmol) was added and the flask sealed with a septa. Bromo (3-ethoxy-3-oxopropyl)zinc (3.17 ml, 1.58 mmol) was added slowly via syringe and the reaction mixture was heated at 85° C. for 16 hours. Upon cooling, the reaction mixture was partitioned between DCM and brine. The organic layer was dried (Na2SO4), concentrated under reduced pressure and the residue was purified by silica gel chromatography (gradient elution with EtOAc/Hexanes 7 to 60%) to give ethyl 3-(4-bromopyridin-2-yl)propanoate as a pale yellow oil. MS ESI calc'd. for C10H13BrNO2 [M+H]+ 258 and 260. found 258 and 260. 1H NMR (500 MHz, CDCl3) δ 8.33 (d, J=5.1 Hz, 1H), 7.39 (bs, 1H), 7.30 (dd, J=5.2, 1.7 Hz, 1H), 4.12 (q, J=6.7 Hz, 2H), 3.08 (t, J=6.5 Hz, 2H), 2.79 (t, J=6.4 Hz, 2H), 1.23 (t, J=6.8 Hz, 3H).

Workup

  1. customthe flask sealed with a septa
  2. temperatureUpon cooling
  3. customthe reaction mixture was partitioned between DCM and brine
  4. dry with materialThe organic layer was dried (Na2SO4)
  5. concentrationconcentrated under reduced pressure
  6. customthe residue was purified by silica gel chromatography (gradient elution with EtOAc/Hexanes 7 to 60%)

Sources & evidence

ORD record
ord-4cb1bff119624e60a9f275f8b63a72bf
Source dataset
uspto-grants-2016_06
Patent number
US09376418B2

Reaction notes

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