Resorcinol → m-(p-Toluidino)phenol

HRID 896406Notes

Reaction equation

HRID 896406 reaction equation
[NH2:1][C:2]1[CH:7]=[CH:6][C:5]([CH3:8])=[CH:4][CH:3]=1.[C:9]1([CH:16]=[CH:15][CH:14]=[C:12](O)[CH:11]=1)[OH:10].Cl.NC1C=CC(C)=CC=1.[OH-].[Na+]>C(OCC)C>[CH3:8][C:5]1[CH:6]=[CH:7][C:2]([NH:1][C:12]2[CH:11]=[C:9]([OH:10])[CH:16]=[CH:15][CH:14]=2)=[CH:3][CH:4]=1

Participants

6

Reactant 4

HCID 5054ResorcinolHCID 7813p-ToluidineHCID 10891Benzenamine, 4-methyl-, hydrochloride (1:1)HCID 14798Sodium Hydroxide

Product 1

HCID 109096m-(p-Toluidino)phenolYield 74.1%

Reagents, catalysts & solvents 1

HCID 3283Diethyl EtherSolvent

Conditions

Temperature
160 °C

Procedure

A reaction mixture of p-toluidine (13.4 g, 126.2 mol), resorcinol (10 g, 90.8 mmol) and p-toluidine HCl (1.3 g, 9.0 mmol) was heated at 160° C. for 48 h with an oil bath. After cooling to room temperature, the reaction mixture in 500 mL of diethyl ether was treated with 2N NaOH to give precipitated materials and filtered under reduced pressure. The collected solid was treated with glacial acetic acid until completely dissolved, and the solution was extracted with diethyl ether (2×200 mL). The ether layer was washed with water (2×150 mL), dried over MgSO4, and concentrated under reduced pressure to give a dark-brown oil, which was purified by flash column chromatography using EtOAc/hexane (40:60). The resulting oil was crystallized from CH2Cl2/hexane to yield 13.4 g (74%) of the title compound as a dark brown solid. Mp 86-88° C. (lit 91° C. )

Workup

  1. temperatureAfter cooling to room temperature
  2. customto give
  3. customprecipitated materials
  4. filtrationfiltered under reduced pressure
  5. additionThe collected solid was treated with glacial acetic acid
  6. dissolutionuntil completely dissolved
  7. extractionthe solution was extracted with diethyl ether (2×200 mL)
  8. washThe ether layer was washed with water (2×150 mL)
  9. dry with materialdried over MgSO4
  10. concentrationconcentrated under reduced pressure
  11. customto give a dark-brown oil, which
  12. customwas purified by flash column chromatography
  13. customThe resulting oil was crystallized from CH2Cl2/hexane

Sources & evidence

ORD record
ord-8894b74d7c574733bce2a928a581a1f7
Source dataset
uspto-grants-2005_07
Patent number
US06919357B2

Reaction notes

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