Acetic Acid → N-[2-(2-pyridyl)ethyl]-2-methyl-4-hydroxyaniline

HRID 980973Notes

Reaction equation

HRID 980973 reaction equation
[CH3:1][C:2]1[CH:8]=[C:7]([OH:9])[CH:6]=[CH:5][C:3]=1[NH2:4].C(O)(=O)C.[CH:14]([C:16]1[CH:21]=[CH:20][CH:19]=[CH:18][N:17]=1)=[CH2:15].C(=O)(O)[O-].[Na+]>C1(C)C=CC=CC=1.CO>[N:17]1[CH:18]=[CH:19][CH:20]=[CH:21][C:16]=1[CH2:14][CH2:15][NH:4][C:3]1[CH:5]=[CH:6][C:7]([OH:9])=[CH:8][C:2]=1[CH3:1]

Participants

7

Reactant 4

HCID 176Acetic AcidHCID 75212-VinylpyridineHCID 178194-Amino-m-cresolHCID 516892Sodium Bicarbonate

Product 1

HCID 15597532N-[2-(2-pyridyl)ethyl]-2-methyl-4-hydroxyanilineYield 25.8%

Reagents, catalysts & solvents 2

HCID 887MethanolSolventHCID 1140TolueneSolvent

Procedure

A mixture of 50.0 g (0.4 mole) of 2-methyl-4-hydroxyaniline, 2.4 g of glacial acetic acid and 125.0 ml of anhydrous methyl alcohol was heated to reflux with stirring and 63.1 g (0.6 mole) of 2-vinylpyridine was added dropwise to the mixture. The resultant reaction mixture was maintained at reflux for approximately forty-eight hours, cooled to ambient temperature and added to a mixture of aqueous sodium bicarbonate and toluene. The water layer was separated from to toluene layer and the water layer was extracted a second time with toluene. The two toluene layers were combined, washed with saturated aqueous sodium chloride solution and dried over anhydrous sodium sulfate. The solid, which crystallized from the toluene upon standing, was collected by filtration, washed with hexane and dried to obtain 23.6 g of N-[2-(2-pyridyl)ethyl]-2-methyl-4-hydroxyaniline (Formula VI: R1 =R9 =H; R2 =CH3 ; R11 =OH), a pale beige-colored solid which melted at 137.5° to 139.5° C. after recrystallization from toluene. Significant infrared maxima appeared at 3200 cm-1 (OH;m) and 1601 cm-1 (C=C;m). The nuclear magnetic resonance spectrum was in accord with the assigned structure.

Workup

  1. temperaturewas heated
  2. temperatureto reflux
  3. customThe resultant reaction mixture
  4. temperaturewas maintained
  5. temperatureat reflux for approximately forty-eight hours
  6. customThe water layer was separated from to toluene layer
  7. extractionthe water layer was extracted a second time with toluene
  8. washwashed with saturated aqueous sodium chloride solution
  9. dry with materialdried over anhydrous sodium sulfate
  10. customThe solid, which crystallized from the toluene
  11. filtrationwas collected by filtration
  12. washwashed with hexane
  13. customdried

Sources & evidence

ORD record
ord-732fbbb3115b451dbd36e0487cad2332
Source dataset
uspto-grants-1987_01
Patent number
US04639750

Reaction notes

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