Ethyl 4-chloroacetoacetate → Ethyl 2-hydroxy-6-methylbenzoate

HRID 2306129Notes

Reaction equation

HRID 2306129 reaction equation
[CH:1](=O)/[CH:2]=[CH:3]/[CH3:4].C([O-])(=O)C.[Na+].Cl[CH2:12][C:13](=[O:20])[CH2:14][C:15]([O:17][CH2:18][CH3:19])=[O:16]>C(O)(=O)C>[OH:20][C:13]1[CH:12]=[CH:1][CH:2]=[C:3]([CH3:4])[C:14]=1[C:15]([O:17][CH2:18][CH3:19])=[O:16]

Participants

5

Reactant 3

HCID 69484Ethyl 4-chloroacetoacetateHCID 447466CrotonaldehydeHCID 517045Sodium Acetate

Product 1

HCID 584222Ethyl 2-hydroxy-6-methylbenzoateYield 65%

Reagents, catalysts & solvents 1

HCID 176Acetic AcidSolvent

Procedure

A stirred mixture of crotonaldehyde (21.0 g, 0.30 mol) and anhydrous sodium acetate (25.0 g, 0.30 mol) in glacial acetic acid is heated to reflux temperature under N2, treated dropwise with ethyl chloroacetoacetate (41.1 g, 95%, 0.25 mol) over a 2.25 hr. period, heated at reflux temperature for 16 hr., cooled to room temperature and concentrated in vacuo to give a residue. The residue is partitioned between ethyl acetate and water. The organic phase is diluted with hexanes, washed sequentially with water and aqueous NaHCO3 and concentrated in vacuo to give the title product as an oil, 41.0 g, 71.4% purity (65% yield), characterized by NMR analysis.

Workup

  1. temperatureis heated
  2. temperatureto reflux temperature under N2
  3. temperatureperiod, heated
  4. temperatureat reflux temperature for 16 hr
  5. concentrationconcentrated in vacuo
  6. customto give a residue
  7. customThe residue is partitioned between ethyl acetate and water
  8. additionThe organic phase is diluted with hexanes
  9. washwashed sequentially with water and aqueous NaHCO3
  10. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-0fdcb5e684be41e8aaaccd04b2a0ed6d
Source dataset
uspto-grants-2002_08
Patent number
US06441219B1

Reaction notes

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