Acetic Acid → 3-Ethyl-4-hydroxy-5-methylbenzaldehyde

HRID 1958796Notes

Reaction equation

HRID 1958796 reaction equation
[CH2:1]([C:3]1[CH:8]=[CH:7][CH:6]=[C:5]([CH3:9])[C:4]=1[OH:10])[CH3:2].C1N2CN3CN(C2)CN1C3.[C:21](O)(=[O:23])C>O>[CH2:1]([C:3]1[CH:8]=[C:7]([CH:6]=[C:5]([CH3:9])[C:4]=1[OH:10])[CH:21]=[O:23])[CH3:2]

Participants

5

Reactant 3

HCID 176Acetic AcidHCID 4101HexamethylenetetramineHCID 5193332-Ethyl-6-methylphenol

Product 1

HCID 231592103-Ethyl-4-hydroxy-5-methylbenzaldehyde

Reagents, catalysts & solvents 1

HCID 962WaterSolvent

Procedure

A solution of 2-ethyl-6-methyl-phenol (8.40 g, 61.7 mmol) and hexamethylene tetraamine (12.97 g, 92.5 mmol) in acetic acid (60 mL) and water (14 mL) is heated to 115° C. The water is distilled off at 117° C. and collected with a Dean-Stark apparatus. Then the water separator is replaced by a reflux condenser and the mixture is refluxed for 3 h. The mixture is cooled to rt, diluted with water (100 mL) and extracted with EA. The org. extract is washed with sat. aq. NaHCO3, dried over MgSO4 and evaporated. The remaining solid is dissolved in EA and treated with heptane to initialize crystallisation. The solid material is collected and dried to give 3-ethyl-4-hydroxy-5-methyl-benzaldehyde as a colourless crystalline powder (3.13 g). 1H NMR (CDCl3): δ 9.83 (s, 1H), 7.58-7.53 (m, 2H), 5.30 (br s, 1H), 2.69 (q, J=7.6 Hz, 2H), 2.32 (s, 3H), 1.28 (t, J=7.6 Hz, 3H).

Workup

  1. distillationThe water is distilled off at 117° C.
  2. customcollected with a Dean-Stark apparatus
  3. customThen the water separator is replaced by a reflux condenser
  4. temperaturethe mixture is refluxed for 3 h
  5. additiondiluted with water (100 mL)
  6. extractionextracted with EA
  7. extractionextract
  8. washis washed with sat. aq. NaHCO3
  9. dry with materialdried over MgSO4
  10. customevaporated
  11. dissolutionThe remaining solid is dissolved in EA
  12. additiontreated with heptane
  13. customcrystallisation
  14. customThe solid material is collected
  15. customdried

Sources & evidence

ORD record
ord-fd61d0281c8e47a2a0ec5cc67495b300
Source dataset
uspto-grants-2013_04
Patent number
US08410151B2

Reaction notes

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