Triphenylphosphine → 2,6-Dibromo-3-(but-3-enyloxy)pyridine

HRID 2279269

Reaction equation

HRID 2279269 reaction equation
[Br:1][C:2]1[C:7]([OH:8])=[CH:6][CH:5]=[C:4]([Br:9])[N:3]=1.[CH2:10](O)[CH2:11][CH:12]=[CH2:13].C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.CC(OC(/N=N/C(OC(C)C)=O)=O)C>C1COCC1.C(OCC)(=O)C>[Br:1][C:2]1[C:7]([O:8][CH2:13][CH2:12][CH:11]=[CH2:10])=[CH:6][CH:5]=[C:4]([Br:9])[N:3]=1

Participants

7

Reactant 4

HCID 11776TriphenylphosphineHCID 693893-Buten-1-olHCID 810772,6-Dibromopyridin-3-olHCID 5363146Diisopropyl azodicarboxylate

Product 1

HCID 584840892,6-Dibromo-3-(but-3-enyloxy)pyridineYield 85%

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolventHCID 8857Ethyl AcetateSolvent

Procedure

To a stirred mixture of 2,6-dibromopyridin-3-ol (47.3 g, 0.188 mol) and but-3-en-1-ol (13.8 g, 0.191 mol) in anhydrous THF (200 mL) at 0° C. was added PPh3 (59.4 g, 0.226 mol), followed by diisopropylazo dicarboxylate (DIAD, 41.77 g, 0.207 mol). The mixture was heated at reflux for 1 hour and then concentrated in vacuo to give a dark brown oil. The oil was dissolved in Ethyl acetate, washed with saturated NaHCO3 solution and brine, dried with Na2SO4, and concentrated in vacuo. Petroleum (300 mL) was added to the crude product mixture. The white solid was removed by filtration, and the filtrate was purified by silica gel chromatography (petroleum/Ethyl acetate, 30/1) to afford compound the title compound as oil (49 g, 85%). 1H NMR (400 Mz, DMSO-d6): δ: 2.62-2.59 (m, 2H); 4.07-4.03 (t, J=6, 2H); 5.22-5.11 (m, 1H); 5.96-5.83 (m, 1H); 7.01 (d, J=7.2); 7.33 (d, J=9.3, 1 H).

Workup

  1. temperatureThe mixture was heated
  2. temperatureat reflux for 1 hour
  3. concentrationconcentrated in vacuo
  4. customto give a dark brown oil
  5. washwashed with saturated NaHCO3 solution and brine
  6. dry with materialdried with Na2SO4
  7. concentrationconcentrated in vacuo
  8. additionPetroleum (300 mL) was added to the crude product mixture
  9. customThe white solid was removed by filtration
  10. customthe filtrate was purified by silica gel chromatography (petroleum/Ethyl acetate, 30/1)

Sources & evidence

ORD record
ord-b4fbd99d67ee40979e362b5315a63116
Source dataset
uspto-grants-2015_09
Patent number
US09133218B2

Linked notes

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