Water → 2-Chloro-4-(chloromethyl)pyridine

HRID 907553Notes

Reaction equation

HRID 907553 reaction equation
[Cl:1][C:2]1[CH:7]=[C:6]([CH3:8])[CH:5]=[CH:4][N:3]=1.[Cl:9]N1C(=O)CCC1=O.O>C(#N)C.C(OOC(=O)C1C=CC=CC=1)(=O)C1C=CC=CC=1.C(O)(=O)C>[Cl:9][CH2:8][C:6]1[CH:5]=[CH:4][N:3]=[C:2]([Cl:1])[CH:7]=1

Participants

7

Reactant 3

HCID 962WaterHCID 31398ChlorosuccinimideHCID 772482-Chloro-4-methylpyridine

Product 1

HCID 111265732-Chloro-4-(chloromethyl)pyridineYield 100%

Reagents, catalysts & solvents 3

HCID 176Acetic AcidCatalystHCID 7187Benzoyl PeroxideCatalystHCID 6342AcetonitrileSolvent

Procedure

A mixture of 2-chloro-4-methyl-pyridine (7.28 g, 57.1 mmol), N-Chlorosuccinimide (11.4 g, 85.3 mmol), benzoyl peroxide (276 mg, 1.13 mmol), and acetic acid (200 μL, 3.5 mmol) in acetonitrile (30 mL) was heated at reflux for 2.5 h. The mixture was allowed to cool to room temperature, then poured into water (10 mL) and extracted with EtOAc. The organic phase was washed with brine, dried over MgSO4, and concentrated in vacuo at 35° C., yielding the crude product of 4-(chloromethyl)-2-chloropyridine (9.25 g) as an oil. The crude oil was carried on to the hydrolysis step without further purification.

Workup

  1. temperaturewas heated
  2. temperatureat reflux for 2.5 h
  3. extractionextracted with EtOAc
  4. washThe organic phase was washed with brine
  5. dry with materialdried over MgSO4
  6. concentrationconcentrated in vacuo at 35° C.

Sources & evidence

ORD record
ord-7ef665fbc30c45d3b741cdb285820ea6
Source dataset
uspto-grants-2011_09
Patent number
US08013156B2

Reaction notes

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