2-Aminophenol → HCID 20431560, compound

HRID 2413039Notes

Reaction equation

HRID 2413039 reaction equation
[NH2:1][C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][C:3]=1[OH:8].[C:9]([O:18]C)(=O)[C:10]([CH2:12][C:13](OC)=[O:14])=[CH2:11].O(C(C)C)C(C)C.[NH4+:27].[OH-]>CCOC(C)=O>[OH:8][C:3]1[CH:4]=[CH:5][CH:6]=[CH:7][C:2]=1[NH:1][C:9]([CH:10]1[CH2:11][NH:27][C:13](=[O:14])[CH2:12]1)=[O:18]

Participants

6

Reactant 4

HCID 58012-AminophenolHCID 7914Diisopropyl EtherHCID 14923Ammonium HydroxideHCID 69240Dimethyl itaconate

Product 1

HCID 20431560HCID 20431560, compound

Reagents, catalysts & solvents 1

HCID 8857Ethyl AcetateSolvent

Procedure

A mixture of 21.8 g. (0.2 mole) of o-aminophenol and 31.6 g. (0.2 mole) of dimethyl itaconate in a 500 ml. round bottomed flask was heated to 190° for 1 hr. and volatile by-products were allowed to escape. The residue was taken up in 150 ml. of boiling EtOAc and diluted with 300 ml. of (i-Pr)2O. After the solution had cooled, it was clarified by filtration, evaported to a volume of 100 ml., and chilled at 5°. The tan crystalline solid was collected on a filter, and dried in air to give 22 g. of crude hydroxy ester, m.p. 120°-124°. Conversion of 5.0 g. (0.0212 mole) of the foregoing hydroxy ester was accomplished by stirring with 50 ml. of concentrated NH4OH at 25° for 24 hrs. Volatile material was removed by distillation at 95°/50 mm and the red glassy residue was taken up in a small amount of EtOAc-MeOH and allowed to stand. Crystals were deposited on standing. They were collected, and recrystallized from i-PrOH-EtOAc to give 3.12 g. of the desired product, m.p. 133°-135°, which was further purified by recrystallization from CH3CN using activated carbon, yield 1.9 g. m.p. 135°-138°. This material was used without further purification as starting material for Procedure 6.

Workup

  1. additionA mixture of 21.8 g
  2. temperatureround bottomed flask was heated to 190° for 1 hr
  3. temperatureAfter the solution had cooled
  4. filtrationit was clarified by filtration
  5. temperature, and chilled at 5°
  6. customThe tan crystalline solid was collected on a filter
  7. customdried in air
  8. customto give 22 g
  9. customVolatile material was removed by distillation at 95°/50 mm
  10. customThey were collected
  11. customrecrystallized from i-PrOH-EtOAc
  12. customto give 3.12 g
  13. customof the desired product, m.p. 133°-135°, which was further purified by recrystallization from CH3CN using activated carbon, yield 1.9 g
  14. customThis material was used without further purification

Sources & evidence

ORD record
ord-ba286327a07e470ba4dbecc3cb09c64f
Source dataset
uspto-grants-1985_01
Patent number
US04495352

Reaction notes

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