Hydrochloric Acid → HCID 18991981, compound

HRID 375731Notes

Reaction equation

HRID 375731 reaction equation
[OH:1][C:2]1[C:3]([CH3:13])=[C:4]([CH:9]=[C:10]([OH:12])[CH:11]=1)[C:5]([O:7][CH3:8])=[O:6].[CH2:14](Br)[CH:15]=[CH2:16].[H-].[Na+].Cl>CN(C)C=O>[CH2:16]([O:1][C:2]1[C:3]([CH3:13])=[C:4]([CH:9]=[C:10]([OH:12])[CH:11]=1)[C:5]([O:7][CH3:8])=[O:6])[CH:15]=[CH2:14].[CH2:16]([O:12][C:10]1[CH:11]=[C:2]([OH:1])[C:3]([CH3:13])=[C:4]([CH:9]=1)[C:5]([O:7][CH3:8])=[O:6])[CH:15]=[CH2:14]

Participants

7

Reactant 4

HCID 313Hydrochloric AcidHCID 7841Allyl bromideHCID 24758Sodium hydrideHCID 18991986HCID 18991986, compound

Product 2

HCID 18991981HCID 18991981, compoundHCID 18992115HCID 18992115, compound

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Procedure

To a solution of 27.3 g of methyl 3,5-dihydroxy-2-methylbenzoate and 21.8 g of allyl bromide in 300 ml of dimethylformamide were added portionwise, within 30 minutes, 8.64 g of a 55% dispersion of sodium hydride in mineral oil, the temperature being held between 10° and 20° C. The mixture was stirred at room temperature for 3 hours, and then poured into ice-water. The pH was adjusted to about 3 by the addition of 3N hydrochloric acid, and the mixture was extracted with 600 ml of ethyl acetate. The organic layer was washed 5 times with 100 ml of water, dried over sodium sulfate, and the solvent was evaporated in vacuo. The residue was chromatographed on silica gel using ethyl acetate/methylene chloride/hexane (1:1:3, v/v/v) as eluent, and the purified products were crystallized from ethyl acetate/hexane to afford 4.1 g of methyl 3-allyloxy-5-hydroxy-2-methylbenzoate, m.p. 86°-88° C., and 5.61 g of methyl 5-allyloxy-3-hydroxy-2-methylbenzoate, m.p. 84°-87° C.

Workup

  1. custombeing held between 10° and 20° C
  2. extractionthe mixture was extracted with 600 ml of ethyl acetate
  3. washThe organic layer was washed 5 times with 100 ml of water
  4. dry with materialdried over sodium sulfate
  5. customthe solvent was evaporated in vacuo
  6. customThe residue was chromatographed on silica gel
  7. customthe purified products were crystallized from ethyl acetate/hexane

Sources & evidence

ORD record
ord-f48675c75d4543409e5c0627fd5267e7
Source dataset
uspto-grants-1996_01
Patent number
US05486466

Reaction notes

Loading…