Phenol → 2-Anilino-6-quinoxalinol

HRID 567731Notes

Reaction equation

HRID 567731 reaction equation
C1(O)C=CC=CC=1.[NH:8]([C:15]1[CH:24]=[N:23][C:22]2[C:17](=[CH:18][CH:19]=[C:20]([O:25]C)[CH:21]=2)[N:16]=1)[C:9]1[CH:14]=[CH:13][CH:12]=[CH:11][CH:10]=1.[Na].C(S)C>CN(C=O)C>[NH:8]([C:15]1[CH:24]=[N:23][C:22]2[C:17](=[CH:18][CH:19]=[C:20]([OH:25])[CH:21]=2)[N:16]=1)[C:9]1[CH:10]=[CH:11][CH:12]=[CH:13][CH:14]=1

Participants

6

Reactant 4

HCID 996PhenolHCID 6343EthanethiolHCID 5360545SodiumHCID 101988822-Anilino-6-methoxy-quinoxaline

Product 1

HCID 1355124612-Anilino-6-quinoxalinol

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Conditions

Temperature
110 °C

Procedure

By the method of Feutrill, G. I.; Mirrington, R. N. Tet. Lett. 1970, 1327; the aryl methyl ether is converted to the phenol derivative. To 2-anilino-6-methoxy-quinoxaline (0.27 g, 1.07 mmol) under argon in DMF is added the sodium salt of ethanethiol (0.19 g, 2 mmol). The reaction mixture is heated to 110° C overnight. The mixture is concentrated and partitioned between EtOAc and H20/5% tartaric acid such that the pH of the aqueous layer is approximately 4. The organic layer is washed with H2O (4×), then with 2.5% NaOH (4×). The basic layers combined, washed with EtOAc (2×), re-acidified with 5% tartaric acid, and washed with multiple portions of EtOAc. The organic layers are combined, washed with brine, dried (Na2SO4), and concentrated. The resulting solid is chromatographed (50% EtOAc/hexanes). An analytical sample is obtained by triturating the product with Et2O to provide a yellow powder (m.p. 211-213° C.). Anal. for C14H11N3P: C, 70.88; H, 4.67; N, 17.71; Found: C, 70.64; H, 4.85; N, 17.58.

Workup

  1. concentrationThe mixture is concentrated
  2. custompartitioned between EtOAc and H20/5% tartaric acid such that the pH of the aqueous layer
  3. washThe organic layer is washed with H2O (4×)
  4. washwashed with EtOAc (2×), re-acidified with 5% tartaric acid
  5. washwashed with multiple portions of EtOAc
  6. washwashed with brine
  7. dry with materialdried (Na2SO4)
  8. concentrationconcentrated
  9. customThe resulting solid is chromatographed (50% EtOAc/hexanes)
  10. customAn analytical sample is obtained
  11. customby triturating the product with Et2O

Sources & evidence

ORD record
ord-ef1bfa4d42e34bbd81fa3398a241253b
Source dataset
uspto-grants-2001_01
Patent number
US06180632B2

Reaction notes

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