Phenol → HCID 19384988, compound

HRID 2399878Notes

Reaction equation

HRID 2399878 reaction equation
F[B-](F)(F)F.[C:6]([NH:9][C:10]1[C:15]([Cl:16])=[CH:14][C:13]([N+]#N)=[CH:12][C:11]=1[Cl:19])(=[O:8])[CH3:7].C1([OH:26])C=CC=CC=1>O.[N+]([O-])([O-])=O.[Cu+2].[N+]([O-])([O-])=O.[Cu-]=O>[C:6]([NH:9][C:10]1[C:15]([Cl:16])=[CH:14][C:13]([OH:26])=[CH:12][C:11]=1[Cl:19])(=[O:8])[CH3:7]

Participants

6

Reactant 2

HCID 996PhenolHCID 19384994HCID 19384994, compound2×

Product 1

HCID 19384988HCID 19384988, compoundYield 35%

Reagents, catalysts & solvents 3

HCID 18616Cupric nitrateCatalystHCID 178419072HCID 178419072, compoundCatalystHCID 962WaterSolvent

Procedure

4-Acetamido-3,5-dichlorobenzenediazonium tetrafluoroborate was converted to the corresponding phenol according to the procedure of T. Cohen, et. al., J. Org. Chem., 42, 2053-2058 (1977). Thus, 22 g (94 rnmol) of copper (II) nitrate was dissolved in 100 mL of water and 300 mg (0.94 mmol) of 4-acetamido-3,5-dichlorobenzenediazonium tetrafluoroborate was added. Copper (I) oxide (405 mg, 2.8 mmol) was added. The mixture was stirred for 35 min, then filtered through Celite, diluted with 1N aqueous sodium bisulfate, and extracted with 4 portions of dichloromethane and 8 portions of ethyl acetate. The combined organic phases were dried over magnesium sulfate and concentrated. Purification by flash chromatography (silica, 50% ethyl acetate/hexanes) gave 72 mg (35%)of 4-acetamido-3,5-dichlorophenol. This compound was convened to the title compound in a manner analogous to that of Example 1: 1H NMR (400 MHz, CDCl3) δ6.97 (s, 2H), 4.21 (dd, 1H), 3.86 (dd, 1H), 3.32 (m, 1H), 2.91 (t, 1H), 2.73 (dd, 1H), 2.20 (s, 3H).

Workup

  1. filtrationfiltered through Celite
  2. additiondiluted with 1N aqueous sodium bisulfate
  3. extractionextracted with 4 portions of dichloromethane and 8 portions of ethyl acetate
  4. dry with materialThe combined organic phases were dried over magnesium sulfate
  5. concentrationconcentrated
  6. customPurification by flash chromatography (silica, 50% ethyl acetate/hexanes)

Sources & evidence

ORD record
ord-181d904c95e3423a9ecc45d3d30edae5
Source dataset
uspto-grants-1995_09
Patent number
US05451677

Reaction notes

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