Sulfuric Acid → HCID 22242330, compound

HRID 892281Notes

Reaction equation

HRID 892281 reaction equation
[OH:1][C:2]1[CH:3]=[C:4]([C:10](=[O:18])[CH2:11][C:12]2[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=2)[CH:5]=[CH:6][C:7]=1[O:8][CH3:9].S([O-])([O-])(=O)=O.C([N+](CCCC)(CCCC)CCCC)CCC.C([N+](CCCC)(CCCC)CCCC)CCC.[N+:58]([O-])([O:60]C(C)C)=[O:59].S(=O)(=O)(O)O>ClCCl>[OH:1][C:2]1[C:3]([N+:58]([O-:60])=[O:59])=[C:4]([C:10](=[O:18])[CH2:11][C:12]2[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=2)[CH:5]=[CH:6][C:7]=1[O:8][CH3:9]

Participants

6

Reactant 4

HCID 1118Sulfuric AcidHCID 15575Isopropyl nitrateHCID 11433187Bis(tetrabutylammonium) sulphateHCID 12259970HCID 12259970, compound

Product 1

HCID 22242330HCID 22242330, compound

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

To a stirred solution of 1-(3-hydroxy4-methoxyphenyl-2-phenyl-ethanone (8.57 g, 35.4 mmol) in dichloromethane (90 mL) at room temperature was added tetrabutylammonium sulphate (0.6 g, 5 mol %) followed by isopropyl nitrate (7.44 g, 70.8 mmol). Sulphuric acid (96%, 8.5 mL) was then added dropwise causing a gently exothermic reaction, and after stirring for forty minutes, the reaction mixture was poured onto water (250 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 triturated with a small volume of diethylether (20 mL) to afford orange crystals, (6.9 g, 68%) of m.p. 176–177° C., identified by NMR as the ortho-nitrated title product. Concentration of the mother liquors and subsequent trituration with diethyl ether (15 mL) allowed the isolation of a small amount of a minor product, which was recrystallised from a dichloromethane/heptane mixture to give yellowish crystals of m.p. 142–143° C., corresponding (TLC) to a standard of the para-nitrated product, 1-(3-hydroxy-4-methoxy-6-nitrophenyl)-2-phenyl-ethanone (1.22 g, 12%). (80% combined yield, Ortho:Para selectivity, 5.7:1)

Workup

  1. customa gently exothermic reaction
  2. additionthe reaction mixture was poured onto water (250 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 triturated with a small volume of diethylether (20 mL)
  10. customto afford orange crystals, (6.9 g, 68%) of m.p. 176–177° C.

Sources & evidence

ORD record
ord-699c1616ed4040ee828b7ae948e47551
Source dataset
uspto-grants-2006_02
Patent number
US07005553B2

Reaction notes

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