Hexamethylenetetramine → 4-tert-Butyl-2-hydroxybenzaldehyde

HRID 2214838Notes

Reaction equation

HRID 2214838 reaction equation
F[C:2](F)(F)[C:3]([OH:5])=O.[C:8]([C:12]1[CH:13]=[C:14]([OH:18])C=[CH:16][CH:17]=1)([CH3:11])([CH3:10])[CH3:9].C1N2CN3CN(C2)CN1C3>O>[C:8]([C:12]1[CH:13]=[C:14]([OH:18])[C:2](=[CH:16][CH:17]=1)[CH:3]=[O:5])([CH3:11])([CH3:10])[CH3:9]

Participants

5

Reactant 3

HCID 4101HexamethylenetetramineHCID 6422Trifluoroacetic acidHCID 11450Phenol, 3-(1,1-dimethylethyl)-

Product 1

HCID 137652724-tert-Butyl-2-hydroxybenzaldehydeYield 56%

Reagents, catalysts & solvents 1

HCID 962WaterSolvent2×

Conditions

Temperature
80 °C

Procedure

A five liter three-neck round bottom flask equipped with overhead mechanical stirrer and condenser was charged with trifluoroacetic acid (2.4 L). A mixture of 3-tert-butylphenol (412 g, 2.8 mole) and HMTA (424 g, 3.0 mole) was added portion-wise causing an exotherm. With cooling, the temperature was maintained under 80° C. The reaction was heated at 80° C. for one-hour, then cooled, and water (2 L) added. After 0.5 hour additional water (4 L) was added and the mixture was extracted with ethyl acetate (6 L). The organic extract was washed with water and brine. The resulting organic phase was divided into 2 L volumes and each diluted with water (1 L), and solid NaHCO3 added until the mixture was neutralized. The organic phases were isolated and combined, dried over MgSO4, filtered and concentrated in vacuo yielding an oil. This oil was distilled at 95° C. (0.8 mm) yielding the desired salicylaldehyde as an oil (272.9 g, 56%) which was of sufficient purity to be used without further purification.

Workup

  1. customA five liter three-neck round bottom flask equipped with overhead mechanical stirrer and condenser
  2. additionwas added portion-wise
  3. temperatureWith cooling
  4. temperatureThe reaction was heated at 80° C. for one-hour
  5. temperaturecooled
  6. extractionthe mixture was extracted with ethyl acetate (6 L)
  7. extractionThe organic extract
  8. washwas washed with water and brine
  9. additioneach diluted with water (1 L), and solid NaHCO3
  10. additionadded until the mixture
  11. customThe organic phases were isolated
  12. dry with materialdried over MgSO4
  13. filtrationfiltered
  14. concentrationconcentrated in vacuo
  15. customyielding an oil
  16. distillationThis oil was distilled at 95° C. (0.8 mm)

Sources & evidence

ORD record
ord-6fbbb1b94ff64821919b2229cf603866
Source dataset
uspto-grants-2006_09
Patent number
US07109211B2

Reaction notes

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