Hydrochloric Acid → 2-Chloro-3-(3-chlorobenzoyl)-6-ethylpyridine

HRID 368968Notes

Reaction equation

HRID 368968 reaction equation
[Mg].Br[C:3]1[CH:4]=[C:5]([Cl:9])[CH:6]=[CH:7][CH:8]=1.[Cl:10][C:11]1[C:16]([C:17]#N)=[CH:15][CH:14]=[C:13]([CH2:19][CH3:20])[N:12]=1.[Cl-].[NH4+].Cl.[O:24]1CCCC1>>[Cl:10][C:11]1[C:16]([C:17](=[O:24])[C:3]2[CH:8]=[CH:7][CH:6]=[C:5]([Cl:9])[CH:4]=2)=[CH:15][CH:14]=[C:13]([CH2:19][CH3:20])[N:12]=1

Participants

7

Reactant 6

HCID 313Hydrochloric AcidHCID 79281-Bromo-3-chlorobenzeneHCID 8028TetrahydrofuranHCID 25517Ammonium ChlorideHCID 5462224MagnesiumHCID 219304332-Chloro-6-ethylnicotinonitrile

Product 1

HCID 232844892-Chloro-3-(3-chlorobenzoyl)-6-ethylpyridineYield 22%

Procedure

Magnesium (2.72 g, 112 mmol) was added to a tetrahydrofuran (200 ml) solution of 3-bromochlorobenzene (22.1 g, 115 mmol), and the mixture was stirred at room temperature. Since spontaneous exothermic reaction occurred, the stirring was continued until the exothermicity was ceased. The reaction solution was cooled to -20° C., mixed with 2-chloro-3-cyano-6-ethylpyridine (9.33 g, 56 mmol) and then stirred for 16 hours at room temperature. The reaction solution was mixed with saturated ammonium chloride aqueous solution and stirred for 30 minutes at room temperature and then mixed with 1 N hydrochloric acid and extracted with ethyl acetate. The organic layer was dried over anhydrous magnesium sulfate, magnesium-sulfate was removed by filtration and then the filtrate was concentrated under a reduced pressure. Thereafter, the resulting residue was purified by silica gel column chromatography (hexane-ethyl acetate) to give 2-chloro-3-(3-chlorobenzoyl)-6-ethylpyridine (3.48 g, 22%) as a pale yellow oily material.

Workup

  1. customSince spontaneous exothermic reaction
  2. temperatureThe reaction solution was cooled to -20° C.
  3. stirringstirred for 16 hours at room temperature
  4. stirringstirred for 30 minutes at room temperature
  5. extractionextracted with ethyl acetate
  6. dry with materialThe organic layer was dried over anhydrous magnesium sulfate, magnesium-sulfate
  7. customwas removed by filtration
  8. concentrationthe filtrate was concentrated under a reduced pressure
  9. customThereafter, the resulting residue was purified by silica gel column chromatography (hexane-ethyl acetate)

Sources & evidence

ORD record
ord-dde86781619949e4b9cc33ec682b99d2
Source dataset
uspto-grants-2000_10
Patent number
US06136810

Reaction notes

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