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

HRID 892280ノート

反応式

HRID 892280 の反応式
[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]

参加物

6

反応物 3

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

生成物 1

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

試薬・触媒・溶媒 2

HCID 94433Tetrabutylammonium hydrogen sulfate触媒HCID 6344Dichloromethane溶媒

実験手順

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)

後処理

  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.

出典と根拠

ORDレコード
ord-a4ed2aa6b5e64ce1bb4c7aab058a73ea
出典データセット
uspto-grants-2006_02
特許番号
US07005553B2

反応ノート

読み込み中…