Water → 2-Chloro-9,10-dihydro-9,10-methano-9-anthracenecarboxylic acid

HRID 1490180ノート

反応式

HRID 1490180 の反応式
[Cl:1][C:2]1[CH:15]=[CH:14][C:13]2[CH:12]3[CH2:16][C:5]([CH:17]=[O:18])([C:6]4[C:11]3=[CH:10][CH:9]=[CH:8][CH:7]=4)[C:4]=2[CH:3]=1.CC(C)=[O:21].OS(O)(=O)=O.O=[Cr](=O)=O.O>CC(C)=O.[O-2].[O-2].[O-2].[Cr+6]>[Cl:1][C:2]1[CH:15]=[CH:14][C:13]2[CH:12]3[CH2:16][C:5]([C:17]([OH:21])=[O:18])([C:6]4[C:11]3=[CH:10][CH:9]=[CH:8][CH:7]=4)[C:4]=2[CH:3]=1

参加物

6

反応物 3

HCID 962WaterHCID 196986392-Chloro-9-formyl-9,10-dihydro-9,10-methanoanthraceneHCID 131709961Jones' reagent

生成物 1

HCID 196986472-Chloro-9,10-dihydro-9,10-methano-9-anthracenecarboxylic acid

試薬・触媒・溶媒 2

HCID 10219390chromium (VI) trioxide触媒HCID 180Acetone溶媒

実験手順

To a cooled solution (0° C.) of 2-chloro-9-formyl-9,10-dihydro-9,10-methanoanthracene (described in example 1i) (20.0 g, 78.5 mmol) in acetone (260 mL) was added Jones reagent (24 mL; 27 g chromium trioxide, 23 mL water diluted up to 100 mL of reagent solution) in portions. The reagent was added until an orange color persists. The reaction, containing a significant amount of reduced chromium salts, was warmed to room temperature. The solvents were removed in vacuo and replaced with water (300 mL) saturated with sodium chloride. The aqueous phase was extracted with ethyl acetate (3×300 mL). Combined organic extracts were extracted with 2.5N NaOH (3×400 mL). The basic aqueous extracts were acidified with 3N HCl, saturated with sodium chloride, and extracted with ethyl acetate (4×300 mL). Combined organic extracts were dried over anhydrous magnesium sulfate, filtered, and reduced to a off-white solid. The procedure yielded 26.66 g (quantitative) of the title compound. No additional purification was required. 1H NMR (D6 -DMSO, 300 MHz) 13.2 (donfield) 7.46 (br s, 1H), 7.36 (m, 3H), 7.02 (m, 3 H), 4.45 (s, 1H), 2.67 (s, 2H) MS (CI, CH4) m/z 271 (M+1,100), 273 (34), 299 (M+29,17), 253 (33), 243 (22), 227 (20)

後処理

  1. additionThe reagent was added until an orange color persists
  2. customThe reaction
  3. customThe solvents were removed in vacuo
  4. extractionThe aqueous phase was extracted with ethyl acetate (3×300 mL)
  5. extractionCombined organic extracts were extracted with 2.5N NaOH (3×400 mL)
  6. extractionextracted with ethyl acetate (4×300 mL)
  7. dry with materialCombined organic extracts were dried over anhydrous magnesium sulfate
  8. filtrationfiltered

出典と根拠

ORDレコード
ord-2804b883e6144d78b08b8a5489636972
出典データセット
uspto-grants-1997_10
特許番号
US05681840

反応ノート

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