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

HRID 2040800Notes

Reaction equation

HRID 2040800 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 condensor 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 (3.13 g) as a colourless crystalline powder, 1H NMR (CDCl3): δ 9.83 (s, 1H), 7.58-7.53 (m, 2H), 5.30 (s br, 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. temperaturethe mixture is refluxed for 3 h
  4. additiondiluted with water (100 mL)
  5. extractionextracted with EA
  6. extractionextract
  7. washis washed with sat. aq. NaHCO3
  8. dry with materialdried over MgSO4
  9. customevaporated
  10. dissolutionThe remaining solid is dissolved in EA
  11. additiontreated with heptane
  12. customcrystallisation
  13. customThe solid material is collected
  14. customdried

Sources & evidence

ORD record
ord-896f475e6a9b4d269d99547cf0bfa799
Source dataset
uspto-grants-2013_11
Patent number
US08580824B2

Reaction notes

Loading…