Sodium hydride → 3-(4-Chlorobenzyl)hexane-2,4-dione

HRID 2266457Notes

Reaction equation

HRID 2266457 reaction equation
[CH3:1][C:2](=[O:8])[CH2:3][C:4](=[O:7])[CH2:5][CH3:6].[H-].[Na+].Br[CH2:12][C:13]1[CH:18]=[CH:17][C:16]([Cl:19])=[CH:15][CH:14]=1>CN(C)C=O.Cl>[Cl:19][C:16]1[CH:17]=[CH:18][C:13]([CH2:12][CH:3]([C:4](=[O:7])[CH2:5][CH3:6])[C:2](=[O:8])[CH3:1])=[CH:14][CH:15]=1

Participants

6

Reactant 3

HCID 24758Sodium hydrideHCID 693291-(Bromomethyl)-4-chlorobenzeneHCID 763552,4-Hexanedione

Product 1

HCID 687829303-(4-Chlorobenzyl)hexane-2,4-dione

Reagents, catalysts & solvents 2

HCID 313Hydrochloric AcidSolventHCID 6228DimethylformamideSolvent3×

Procedure

A solution of hexane-2,4-dione (5.7 g) in N,N-dimethylformamide (20 mL) was added dropwise over a period of 15 minutes to a stirred suspension of sodium hydride (60% in oil, 2.2 g) in N,N-dimethylformamide (60 mL) at −5° C. The mixture was stirred a room temperature for 30 minutes and then a solution of 1-bromomethyl-4-chlorobenzene (11 g) in N,N-dimethylformamide (20 mL) was added dropwise over a period of 20 minutes. The resulting mixture Was stirred at room temperature for 17 hours and then diluted with 1.0 M aqueous hydrochloric acid (100 mL). The mixture was extracted with diethyl ether and the combined extracts, washed with 1.0 M aqueous hydrochloric acid and saturated aqueous sodium chloride solution and then dried over magnesium sulfate. The solvent was removed under reduced pressure and purification of the residue by column chromatography on silica gel, eluting with a mixture of pentane and toluene (1:1 to 1:2 to 0:1 by volume) gave title compound (55:45 mixture of keto-enol tautomers) as a white solid, 2.6 g.

Workup

  1. stirringThe resulting mixture Was stirred at room temperature for 17 hours
  2. extractionThe mixture was extracted with diethyl ether
  3. washthe combined extracts, washed with 1.0 M aqueous hydrochloric acid and saturated aqueous sodium chloride solution
  4. dry with materialdried over magnesium sulfate
  5. customThe solvent was removed under reduced pressure and purification of the residue by column chromatography on silica gel
  6. washeluting with a mixture of pentane and toluene (1:1 to 1:2 to 0:1 by volume)

Sources & evidence

ORD record
ord-0a80a89fdb4b493ca2271616ac1dd9f0
Source dataset
uspto-grants-2010_12
Patent number
US07858640B2

Reaction notes

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