Dichloromethane → 2-Neopentylpyridine

HRID 1991538Notes

Reaction equation

HRID 1991538 reaction equation
Br[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][N:3]=1.ClCCl.[Cl-].[CH2:12]([Zn+])[C:13]([CH3:16])([CH3:15])[CH3:14].[Cl-].[NH4+]>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]>[CH2:12]([C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][N:3]=1)[C:13]([CH3:16])([CH3:15])[CH3:14]

Participants

6

Reactant 4

HCID 6344DichloromethaneHCID 79732-BromopyridineHCID 25517Ammonium ChlorideHCID 178445885HCID 178445885, compound

Product 1

HCID 5643522-Neopentylpyridine

Reagents, catalysts & solvents 1

HCID 178418228Bis(cyclopenta-1,4-dien-1-yl(diphenyl)phosphane);dichloropalladium;iron(2+)Catalyst

Procedure

2-Bromopyridine (Aldrich, 0.48 mL, 5.0 mmol) and [1,1′-bis(diphenylphosphino)ferrocene]dichloropalladium(II), complex with dichloromethane (1:1) (Aldrich, 200 mg, 0.25 mmol) were added to the neopentylzinc chloride suspension. The resulting suspension was stirred at rt for 21 h, whereupon saturated ammonium chloride solution (25 mL) was added. The mixture was extracted with ethyl acetate (3×). The combined organic extracts were dried (Na2SO4), filtered and concentrated under reduced pressure. The residue was dissolved in methylene chloride, and washed with 1 N HCl. The aqueous layer was separated, basified with 10 N NaOH (aq), and extracted with CH2Cl2. The organic layer was dried (Na2SO4), filtered and concentrated under reduced pressure to give 2-neopentylpyridine as an oil: Rf=0.33 in 5% MeOH/CH2Cl2.

Workup

  1. additionwas added
  2. extractionThe mixture was extracted with ethyl acetate (3×)
  3. dry with materialThe combined organic extracts were dried (Na2SO4)
  4. filtrationfiltered
  5. concentrationconcentrated under reduced pressure
  6. dissolutionThe residue was dissolved in methylene chloride
  7. washwashed with 1 N HCl
  8. customThe aqueous layer was separated
  9. extractionextracted with CH2Cl2
  10. dry with materialThe organic layer was dried (Na2SO4)
  11. filtrationfiltered
  12. concentrationconcentrated under reduced pressure

Sources & evidence

ORD record
ord-8fd1dc0460154899a4501a52f576ba33
Source dataset
uspto-grants-2010_01
Patent number
US07645780B2

Reaction notes

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