Diethyl Ether → HCID 23439827, compound

HRID 1609452Notes

Reaction equation

HRID 1609452 reaction equation
[Br:1][CH2:2][CH2:3][CH2:4][CH2:5]C(OCC)=O.[Mg].CI.[Cl-].[NH4+].[O:16]1[CH:21]=[CH:20][CH2:19][CH2:18][CH2:17]1.[C:22]1(C)C=CC(S([O-])(=O)=O)=CC=1.[NH+]1C=CC=CC=1.CC[O:41][CH2:42][CH3:43]>O.ClCCl>[Br:1][CH2:2][CH2:3][CH2:4][CH2:5][C:42]([CH3:43])([O:41][CH:21]1[CH2:20][CH2:19][CH2:18][CH2:17][O:16]1)[CH3:22]

Participants

10

Reactant 7

HCID 3283Diethyl Ether3×HCID 6328Methyl iodideHCID 80803,4-dihydro-2H-pyranHCID 25517Ammonium ChlorideHCID 84580Ethyl 5-bromovalerateHCID 466102Benzenesulfonic acid, 4-methyl-, compd. with pyridine (1:1)HCID 5462224Magnesium

Product 1

HCID 23439827HCID 23439827, compound

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 6344DichloromethaneSolvent

Procedure

To a stirred, ice-cooled solution of ethyl 5-bromopentanoate (18.7 ml) in dried ether (100 ml) was added dropwise over 1 hour a filtered solution of Grignard reagent, prepared from magnesium (10 g) and methyl iodide 25 ml) in dried ether (200 ml). After a further 30 minutes on the ice-bath, the reaction mixture was allowed to warm to room temperature over 30 minutes before being poured onto a stirred, ice-cooled solution of ammonium chloride (30 g) in water (200 ml). After the vigorous reaction had subsided, the ether layer was separated, and the aqueous layer was extracted with more ether. The combined ether layers were washed consecutively with water and saturated aqueous sodium chloride, dried, and concentrated in vacuo to give the crude intermediate (6-bromo-2-methyl-2-hexanol) as a pale yellow oil. This was dissolved in dichloromethane (100 ml), then 3,4-dihydro-2H-pyran (8.9 ml) and pyridinium p-toluenesulfonate (0.8 g) were added at room temperature. After 1 hour, the reaction solution was diluted with ether (250 ml) and extracted consecutively with saturated aqueous sodium hydrogen carbonate (150 ml), water (100 ml) and saturated aqueous sodium chloride (100 ml). After drying and removal of the solvent in vacuo, the product was purified by chromatography (150 g silica gel, 10% ether in petroleum ether as eluant) to give the desired compound as a colourless oil.

Workup

  1. additionbefore being poured onto a stirred, ice-
  2. customAfter the vigorous reaction
  3. customthe ether layer was separated
  4. extractionthe aqueous layer was extracted with more ether
  5. washThe combined ether layers were washed consecutively with water and saturated aqueous sodium chloride
  6. customdried
  7. concentrationconcentrated in vacuo
  8. customto give the crude intermediate (6-bromo-2-methyl-2-hexanol) as a pale yellow oil
  9. extractionextracted consecutively with saturated aqueous sodium hydrogen carbonate (150 ml), water (100 ml) and saturated aqueous sodium chloride (100 ml)
  10. customAfter drying
  11. customremoval of the solvent in vacuo
  12. customthe product was purified by chromatography (150 g silica gel, 10% ether in petroleum ether as eluant)

Sources & evidence

ORD record
ord-d76d9f884ab742c99f6b46e5462a8fb5
Source dataset
uspto-grants-1995_03
Patent number
US05401732

Reaction notes

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