Ethyl Acetate → 5-Chloro-2-(chloromethyl)pyridine

HRID 2101415Notes

Reaction equation

HRID 2101415 reaction equation
[Cl:1][C:2]1[CH:3]=[CH:4][C:5]([CH2:8]O)=[N:6][CH:7]=1.S(Cl)([Cl:12])=O.CCOC(C)=O.C([O-])([O-])=O.[Na+].[Na+]>ClCCl.CN(C=O)C.O>[Cl:1][C:2]1[CH:3]=[CH:4][C:5]([CH2:8][Cl:12])=[N:6][CH:7]=1

Participants

8

Reactant 4

HCID 8857Ethyl AcetateHCID 10340Sodium CarbonateHCID 24386Thionyl ChlorideHCID 20537893(5-Chloropyridin-2-yl)methanol

Product 1

HCID 145171515-Chloro-2-(chloromethyl)pyridineYield 89.4%

Reagents, catalysts & solvents 3

HCID 6228DimethylformamideCatalystHCID 962WaterSolventHCID 6344DichloromethaneSolvent

Procedure

To a stirring solution of (5-chloropyridin-2-yl)methanol (840 mg, 5.8 mmol) in dichloromethane (10 mL) at 0° C. under argon was added thionyl chloride (0.64 mL, 8.77 mmol), followed by 4 drops of DMF (white precipitate formed). The reaction mixture was allowed to stir at room temperature for 1 h. The reaction mixture was concentrated to a white solid. The solid thus obtained was cooled in an ice bath before EtOAc (20 mL) and water (20 mL) and then 10% aqueous Na2CO3 solution (20 mL) were added. The organic layer was separated, washed with brine, dried (MgSO4), filtered and concentrated to obtain 840 mg of the title compound as a light brown gum. HPLC/MS: retention time=2.392 min, [M+H]+=162.

Workup

  1. concentrationThe reaction mixture was concentrated to a white solid
  2. customThe solid thus obtained
  3. customThe organic layer was separated
  4. washwashed with brine
  5. dry with materialdried (MgSO4)
  6. filtrationfiltered
  7. concentrationconcentrated

Sources & evidence

ORD record
ord-4adb6cc5a2d14aec86b32ebb7f904f94
Source dataset
uspto-grants-2009_08
Patent number
US07572808B2

Reaction notes

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