Ammonium Chloride → HCID 17862628, compound

HRID 1766913Notes

Reaction equation

HRID 1766913 reaction equation
[CH3:1][C:2]1[CH:11]=[CH:10][CH:9]=[C:8]([CH3:12])[C:3]=1[C:4]([O:6][CH3:7])=[O:5].BrN1C(=O)CCC1=O.BrCC1C=CC=C(C)[C:24]=1[C:25]([O:27]C)=[O:26].C([O-])(=O)C.[Na+].[Cl-].[NH4+]>ClC(Cl)C.CS(C)=O.[W].N(C(C)(C)C#N)=NC(C)(C)C#N.CCCCCC.C(OCC)(=O)C>[C:25]([O:27][CH2:1][C:2]1[CH:11]=[CH:10][CH:9]=[C:8]([CH3:12])[C:3]=1[C:4]([O:6][CH3:7])=[O:5])(=[O:26])[CH3:24]

Participants

12

Reactant 5

HCID 25517Ammonium ChlorideHCID 67184N-bromobutanimideHCID 517045Sodium AcetateHCID 519028Methyl 2,6-dimethylbenzoateHCID 10263795Methyl 2-(bromomethyl)-6-methylbenzoate

Product 1

HCID 17862628HCID 17862628, compoundYield 80%

Reagents, catalysts & solvents 6

HCID 6547AzobisisobutyronitrileCatalystHCID 23964TungstenCatalystHCID 679Dimethyl SulfoxideSolventHCID 63651,1-DichloroethaneSolventHCID 8058HexaneSolventHCID 8857Ethyl AcetateSolvent

Procedure

To a solution of methyl 2,6-dimethylbenzoate (described in J. Am. Chem. Soc., 99, 6405 (1977); 23.4 g, 143 mmol) in dichloroethane (200 ml) were added N-bromosuccinimide (25.46 g, 143 mmol) and α,α′-azobisisobutyronitrile (234.8 mg, 1.43 mmol), and the mixture was irradiated with visible light (tungsten lamp, 375 W) for 1 hour. After cooling the reaction mixture, the precipitated material was filtered off, and the solvent was distilled off under reduced pressure. The obtained oily residue was subjected to chromatography on a silica gel (200 g) column (eluent; ethyl acetate:hexane=1:10) to give an oily mixture containing ca. 50% methyl 2-(bromomethyl)-6-methylbenzoate. The mixture was dissolved in dimethyl sulfoxide (150 ml), and sodium acetate (16.4 g, 0.2 mol) was added thereto. The resulting mixture was stirred at room temperature for 2 hours, then a saturated aqueous solution of ammonium chloride was added thereto, and the product was extracted with ethyl acetate. The organic layer was washed with a saturated aqueous solution of sodium chloride, and the solvent was distilled off under reduced pressure to give an oily residue. The residue was subjected to chromatography on a silica gel (200 g) column (eluent; ethyl acetate:hexane=1:10˜1:3) to give methyl 2-(acetoxymethyl)-6-methylbenzoate (8.09 g, more than 80% content) as a colorless oil. The obtained methyl 2-(acetoxymethyl)-6-methylbenzoate was used for the following reaction without further purification.

Workup

  1. temperatureAfter cooling the reaction mixture
  2. filtrationthe precipitated material was filtered off
  3. distillationthe solvent was distilled off under reduced pressure
  4. customto give an oily mixture
  5. extractionthe product was extracted with ethyl acetate
  6. washThe organic layer was washed with a saturated aqueous solution of sodium chloride
  7. distillationthe solvent was distilled off under reduced pressure
  8. customto give an oily residue

Sources & evidence

ORD record
ord-0df24f7aa1c64fe1996194712fc00a35
Source dataset
uspto-grants-2007_06
Patent number
US07230023B2

Reaction notes

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