4-Aminophenol → HCID 118372886, compound

HRID 2282070Notes

Reaction equation

HRID 2282070 reaction equation
[C:1]([C:3]1[C:27](F)=[CH:26][CH:25]=[CH:24][C:4]=1[O:5][C:6]1[CH:13]=[CH:12][CH:11]=[C:10]([O:14][C:15]2[CH:20]=[CH:19][CH:18]=[C:17](F)[C:16]=2[C:22]#[N:23])[C:7]=1[C:8]#[N:9])#[N:2].[NH2:29][C:30]1[CH:35]=[CH:34][C:33]([OH:36])=[CH:32][CH:31]=1.C(=O)([O-])[O-].[K+].[K+].[NH2:43][C:44]1[CH:45]=[C:46]([OH:50])[CH:47]=[CH:48][CH:49]=1>>[NH2:29][C:30]1[CH:35]=[CH:34][C:33]([O:36][C:17]2[C:16]([C:22]#[N:23])=[C:15]([CH:20]=[CH:19][CH:18]=2)[O:14][C:10]2[CH:11]=[CH:12][CH:13]=[C:6]([O:5][C:4]3[CH:24]=[CH:25][CH:26]=[C:27]([O:50][C:46]4[CH:47]=[CH:48][CH:49]=[C:44]([NH2:43])[CH:45]=4)[C:3]=3[C:1]#[N:2])[C:7]=2[C:8]#[N:9])=[CH:32][CH:31]=1

Participants

5

Reactant 4

HCID 4034-AminophenolHCID 11430Potassium Carbonate2×HCID 115683-AminophenolHCID 118372882HCID 118372882, compound

Product 1

HCID 118372886HCID 118372886, compoundYield 48.5%

Procedure

Into a 250 mL round bottom flask equipped with stir bar, condenser and nitrogen inlet was charged 2,6-bis(2-cyano-3-fluorophenoxy)benzonitrile (8.00 g, 21.4 mmol), 4-aminophenol (2.34 g, 21.4 mmol), potassium carbonate (3.56 g, 25.8 mmol) and N-methyl-1-pyrrolidone (NMP, 140 mL). The mixture was stirred at 100° C. for 24 hours until GC/MS showed no remaining reactant. It was allowed to cool to room temperature, followed by the addition of 3-aminophenol (2.34 g, 21.4 mmol) and potassium carbonate (3.56 g, 25.8 mmol). The mixture was stirred at 100° C. for 24 hours until GC/MS showed no remaining reactant. It was filtered and then the filtrate was poured into about 500 mL of saturated NaCl aqueous solution, followed by extraction with ethyl acetate (3×500 mL). The organic layer was combined and washed with distilled water (3×500 mL). It was then dried over sodium sulfate and filtered. Carbon black was added to the solution, which was then stirred at 65° C. for 30 minutes. It was passed through a Celite filter to remove carbon, and the solvent was removed by a rotary evaporator. A small amount of NMP residue in the product was removed by refluxing it in ethanol (75 mL). Product was collected by filtration and dried overnight at 80° C. in a vacuum oven to afford 5.73 g (48.5%) of a beige solid, m.p. 196.2-197.8° C. 1H-NMR (DMSO-d6): 5.16 (s, 2H, Ar—H), 5.37 (s, 2H, Ar—H), 6.29-6.31 (dd, 1H, Ar—H), 6.34-6.35 (t, 1H, Ar—H), 6.46-6.47 (dd, 1H, Ar—H), 6.60-6.65 (m, 3H, Ar—H), 6.78-6.80 (d, 1H, Ar—H), 6.88-6.93 (t, 3H, Ar—H), 6.96-6.98 (d, 1H, Ar—H), 7.07-7.15 (m, 3H, Ar—H), 7.58-7.62 (t, 1H, Ar—H), 7.64-7.68 (t, 1H, Ar—H), 7.78-7.80 (t, 1H, Ar—H). Elemental analysis: Calcd: C, 71.86; H, 3.84; N, 12.70. Found: C, 71.50; H, 3.87; N, 12.64.

Workup

  1. customInto a 250 mL round bottom flask equipped
  2. stirringThe mixture was stirred at 100° C. for 24 hours until GC/MS
  3. stirringThe mixture was stirred at 100° C. for 24 hours until GC/MS
  4. filtrationIt was filtered
  5. additionthe filtrate was poured into about 500 mL of saturated NaCl aqueous solution
  6. extractionfollowed by extraction with ethyl acetate (3×500 mL)
  7. washwashed with distilled water (3×500 mL)
  8. dry with materialIt was then dried over sodium sulfate
  9. filtrationfiltered
  10. additionCarbon black was added to the solution, which
  11. stirringwas then stirred at 65° C. for 30 minutes
  12. filtrationfilter
  13. customto remove carbon
  14. customthe solvent was removed by a rotary evaporator
  15. customA small amount of NMP residue in the product was removed
  16. temperatureby refluxing it in ethanol (75 mL)
  17. filtrationProduct was collected by filtration
  18. customdried overnight at 80° C. in a vacuum oven

Sources & evidence

ORD record
ord-c9ff8c0bd2224c9a9a6e5ab43eccaa11
Source dataset
uspto-grants-2015_09
Patent number
US09139696B1

Reaction notes

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