Sulfuric Acid → 4-Hydroxy-2'-nitrobutyrophenone

HRID 342189Notes

Reaction equation

HRID 342189 reaction equation
[N+:1]([C:4]1[CH:9]=[CH:8][CH:7]=[CH:6][C:5]=1[C:10]#[C:11][CH2:12][CH2:13][OH:14])([O-:3])=[O:2].[OH:15]S(O)(=O)=O>O1CCCC1.O>[N+:1]([C:4]1[CH:9]=[CH:8][CH:7]=[CH:6][C:5]=1[C:10](=[O:15])[CH2:11][CH2:12][CH2:13][OH:14])([O-:3])=[O:2]

Participants

5

Reactant 2

HCID 1118Sulfuric Acid2×HCID 117454514-(2-Nitrophenyl)but-3-yn-1-ol

Product 1

HCID 109767084-Hydroxy-2'-nitrobutyrophenoneYield 37%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 8028TetrahydrofuranSolvent

Conditions

Temperature
60 °C

Procedure

A mixture of HgO (0.21 g, 1.0 mmol) in 50 ml of 0.12N H2SO4 is heated to 60° C., treated dropwise with a solution of 4-(o-nitrophenyl)-3-butyne-1-ol (3.70 g, 19.4 mmol) in 25 ml of tetrahydrofuran over a 10 minute period, held at 60° C. for 3 hours, treated with additional HgO (0.84 g, 3.9 mmol) suspended in 25 ml of 0.12N H2SO4, held at 60° C. for 4 hours, cooled to room temperature and diluted with water. The resultant aqueous mixture is extracted with ether. The extracts are combined, washed with brine, dried over Na2SO4 and concentrated in vacuo to give a residue. The residue is purified by flash column chromatography (silica gel; gradient 1:1→2:1 ethyl acetate: hexanes as eluent) to give the title product as a brown oil, 1.48 g, 37% yield, identified by NMR and mass spectral analyses.

Workup

  1. additiontreated with additional HgO (0.84 g, 3.9 mmol)
  2. waitheld at 60° C. for 4 hours
  3. temperaturecooled to room temperature
  4. extractionThe resultant aqueous mixture is extracted with ether
  5. washwashed with brine
  6. dry with materialdried over Na2SO4
  7. concentrationconcentrated in vacuo
  8. customto give a residue
  9. customThe residue is purified by flash column chromatography (silica gel; gradient 1:1→2:1 ethyl acetate: hexanes as eluent)

Sources & evidence

ORD record
ord-00c644a877304e7c9b86507b26f1e67f
Source dataset
uspto-grants-1999_01
Patent number
US05856576

Reaction notes

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