2-chloro-5-(MethoxyMethoxy)pyridine → 5-(Methoxymethoxy)-2-(2-methylprop-1-enyl)pyridine

HRID 1697253Notes

Reaction equation

HRID 1697253 reaction equation
Cl[C:2]1[CH:7]=[CH:6][C:5]([O:8][CH2:9][O:10][CH3:11])=[CH:4][N:3]=1.[CH3:12][C:13]([CH3:17])=[CH:14][Mg]Br>C1COCC1.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.Cl[Pd]Cl.[Fe+2]>[CH3:11][O:10][CH2:9][O:8][C:5]1[CH:6]=[CH:7][C:2]([CH:12]=[C:13]([CH3:17])[CH3:14])=[N:3][CH:4]=1

Participants

5

Reactant 2

HCID 587641932-chloro-5-(MethoxyMethoxy)pyridineHCID 178448304HCID 178448304, compound

Product 1

HCID 672709975-(Methoxymethoxy)-2-(2-methylprop-1-enyl)pyridine

Reagents, catalysts & solvents 2

HCID 178418228Bis(cyclopenta-1,4-dien-1-yl(diphenyl)phosphane);dichloropalladium;iron(2+)CatalystHCID 8028TetrahydrofuranSolvent2×

Procedure

A solution of 2-chloro-5-(methoxymethoxy)pyridine (0.620 g, 3.6 mmol) and 1,1′-bis(diphenylphosphino)ferrocene-palladium dichloride (0.13 g, 0.18 mmol) in THF (7 mL) was cooled to 0° C. 2-methyl-1-propenylmagnesium bromide, (0.5 M in THF) (9.3 ml, 4.6 mmol) was added slowly and the reaction was allowed to stir 12 hrs at RT. The reaction was quenched by the addition of a 10:1 aqueous sat. ammonium chloride/ammonium hydroxide solution and extracted into ethyl acetate. The combined organic layers were washed with 10:1 aqueous sat. ammonium chloride/ammonium hydroxide solution, water, brine, dried over sodium sulfate and concentrated. The crude product was purified by filtration through a plug of silica gel (2:1 Hexanes/EtOAc) to afford the title product. MS m/z: 194.1 (100%, M+1).

Workup

  1. customThe reaction was quenched by the addition of a 10:1 aqueous sat. ammonium chloride/ammonium hydroxide solution
  2. extractionextracted into ethyl acetate
  3. washThe combined organic layers were washed with 10:1 aqueous sat. ammonium chloride/ammonium hydroxide solution, water, brine
  4. dry with materialdried over sodium sulfate
  5. concentrationconcentrated
  6. filtrationThe crude product was purified by filtration through a plug of silica gel (2:1 Hexanes/EtOAc)

Sources & evidence

ORD record
ord-f6d7c12218ee4fcfacce061a6ca9cfd3
Source dataset
uspto-grants-2012_04
Patent number
US08163909B2

Reaction notes

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