Sulfuric Acid → (3-Hydroxy-4-methoxy-2-nitrophenyl)(phenyl)methanone

HRID 892280Notes

Reaction equation

HRID 892280 reaction equation
[OH:1][C:2]1[CH:3]=[C:4]([CH:13]=[CH:14][C:15]=1[O:16][CH3:17])[C:5]([C:7]1[CH:12]=[CH:11][CH:10]=[CH:9][CH:8]=1)=[O:6].[N+:18]([O-])([O:20]C(C)C)=[O:19].S(=O)(=O)(O)O>ClCCl.S([O-])(O)(=O)=O.C([N+](CCCC)(CCCC)CCCC)CCC>[OH:1][C:2]1[C:3]([N+:18]([O-:20])=[O:19])=[C:4]([CH:13]=[CH:14][C:15]=1[O:16][CH3:17])[C:5]([C:7]1[CH:12]=[CH:11][CH:10]=[CH:9][CH:8]=1)=[O:6]

Participants

6

Reactant 3

HCID 1118Sulfuric AcidHCID 15575Isopropyl nitrateHCID 41488933-Hydroxy-4-methoxybenzophenone

Product 1

HCID 22242329(3-Hydroxy-4-methoxy-2-nitrophenyl)(phenyl)methanone

Reagents, catalysts & solvents 2

HCID 94433Tetrabutylammonium hydrogen sulfateCatalystHCID 6344DichloromethaneSolvent

Procedure

To a stirred solution of 3-hydroxy-4-methoxybenzophenone (10.0 g, 43.8 mmol) in dichloromethane (100 mL) at room temperature was added tetrabutylammoniumhydrogen sulphate (0.74 g, 5 mol %) followed by isopropyl nitrate (11.5 g, 87.6 mmol). Sulphuric acid (96%, 10 mL) was then added dropwise causing a gently exothermic reaction, and, after stirring for forty minutes, the reaction mixture was poured onto water (300 mL). The phases were separated and the aqueous phase was extracted by dichloromethane (30 mL). The combined organic phases were washed with brine and dried over anhydrous sodium sulphate. Filtration and evaporation of the solvent (40° C., water aspirator pressure) afforded a solid residue which was recrystallised from a small volume of ethanol (96%, 10 mL) to afford yellow crystals, (7.97 g, 67%) of m.p. 137–139° C., identified by NMR as the ortho-nitrated title product. Concentration of the mother liquors and subsequent chromatography on silica gel using a petroleum ether:ethyl acetate solvent mixture (2:1) allowed the isolation of a small amount of a minor product, corresponding (TLC) to a standard of the para-nitrated product, 3-hydroxy4-methoxy-6-nitrobenzophenone (1.43 g, 12%), m.p. 154–156° C. (79% combined yield, Ortho:Para selectivity, 5.6:1)

Workup

  1. customa gently exothermic reaction
  2. additionthe reaction mixture was poured onto water (300 mL)
  3. customThe phases were separated
  4. extractionthe aqueous phase was extracted by dichloromethane (30 mL)
  5. washThe combined organic phases were washed with brine
  6. dry with materialdried over anhydrous sodium sulphate
  7. filtrationFiltration and evaporation of the solvent (40° C., water aspirator pressure)
  8. customafforded a solid residue which
  9. customwas recrystallised from a small volume of ethanol (96%, 10 mL)
  10. customto afford yellow crystals, (7.97 g, 67%) of m.p. 137–139° C.

Sources & evidence

ORD record
ord-a4ed2aa6b5e64ce1bb4c7aab058a73ea
Source dataset
uspto-grants-2006_02
Patent number
US07005553B2

Reaction notes

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