Hydroxylamine → HCID 20320276, compound

HRID 866299Notes

Reaction equation

HRID 866299 reaction equation
[C:1]([C:5]1[CH:10]=[CH:9][CH:8]=[C:7]([C:11]([CH3:14])([CH3:13])[CH3:12])[C:6]=1[OH:15])([CH3:4])([CH3:3])[CH3:2].[C:16]1([OH:22])[CH:21]=[CH:20]C=CC=1.C[O-].[Na+].C(OC)(=O)C=C.OS(O)(=O)=O.NO.[CH3:39][NH:40][CH2:41][CH2:42][OH:43]>CO>[OH:43][CH2:42][CH2:41][N:40]([CH3:39])[C:16](=[O:22])[CH:21]([C:9]1[CH:10]=[C:5]([C:1]([CH3:4])([CH3:3])[CH3:2])[C:6]([OH:15])=[C:7]([C:11]([CH3:14])([CH3:13])[CH3:12])[CH:8]=1)[CH3:20]

Participants

9

Reactant 7

HCID 787HydroxylamineHCID 996PhenolHCID 1118Sulfuric AcidHCID 7294Methyl Acrylate2×HCID 80162-(Methylamino)ethanolHCID 314052,6-Di-tert-butylphenolHCID 10942334Sodium Methoxide

Product 1

HCID 20320276HCID 20320276, compoundYield 95%

Reagents, catalysts & solvents 1

HCID 887MethanolSolvent

Conditions

Temperature
75 °C

Procedure

To a 5000 cc round bottom flask under nitrogen was charged 618.0 g (3.0 moles) 2,6-di-t-butylphenol. To the molten phenol at about 40° C was added 18.0 g (0.33 mole) fresh sodium methoxide powder. The reaction mixture was heated to 75° C with stirring, then cooled back to 60° C. Then was added 284 g. (300 cc, 3.3 moles) methyl acrylate over a 30 minute period. The reaction exothermed and temperature was held at about 80° C with cooling. After the addition was completed the batch was heated 3 hours at 60° C. The reaction was then cooled to 50° C and 9.0 cc conc. H2SO4 was added with stirring as the temperature rose to 60° C. Unreacted methyl acrylate was removed by distillation at reduced pressure. The product was distilled at 128° -130° C (0.3 mm) and recrystallized from hexane to afford 714 g. white crystals, m.p. 66° C. The ester was converted to the aminoalcohol by heating the ester at 150° C for 3 hours with a 100% excess of N-methylethanolamine, while concurrently removing methanol. Excess amine was removed by vacuum distillation at 150° C. The stripped residue product was a sticky glass at room temperature. The yield was about 95%.

Workup

  1. temperaturecooled back to 60° C
  2. additionThen was added 284 g
  3. customwas held at about 80° C
  4. temperaturewith cooling
  5. additionAfter the addition
  6. temperaturewas heated 3 hours at 60° C
  7. temperatureThe reaction was then cooled to 50° C
  8. stirringwith stirring as the temperature
  9. customrose to 60° C
  10. customwas removed by distillation at reduced pressure
  11. distillationThe product was distilled at 128° -130° C (0.3 mm)
  12. customrecrystallized from hexane
  13. customto afford 714 g
  14. customExcess amine was removed by vacuum distillation at 150° C
  15. customat room temperature

Sources & evidence

ORD record
ord-f03cb0f404a846859f181132d1cb9905
Source dataset
uspto-grants-1978_07
Patent number
US04098709

Reaction notes

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