Sulfuric Acid → HCID 538048、化合物

HRID 1647354ノート

反応式

HRID 1647354 の反応式
[C:1]([O:4][C:5](=[O:7])[CH3:6])(=O)[CH3:2].S(=O)(=O)(O)O.[CH2:13]1[CH:18]2CC3[O:22][C:23](=O)[CH:16]([CH2:17]2)[CH2:15][CH:14]1[CH2:21]3>C1CCCCC1>[C:5]([O:4][CH:1]1[CH:18]2[CH2:17][CH:16]3[CH2:15][CH:14]([CH2:21][CH:2]1[C:23]3=[O:22])[CH2:13]2)(=[O:7])[CH3:6]

参加物

5

反応物 3

HCID 1118Sulfuric Acid2 回HCID 7918Acetic AnhydrideHCID 5567274-Oxatricyclo[4.3.1.13,8]undecan-5-one

生成物 1

HCID 538048HCID 538048、化合物

試薬・触媒・溶媒 1

HCID 8078Cyclohexane溶媒

実験手順

A mixture containing 4-Oxahomoadamantane-5-one (12.5 grams, 75.3 mmol), 40 mL acetic anhydride, and 100 mL cyclohexane was charged to a 250-mL round-bottom flask and heated to reflux with a heating mantle. Concentrated sulfuric acid (0.52 grams, 5.4 mmol) was added dropwise from the top of the condenser with magnetic stirring. After 40 hours of reflux, about 5% of the 4-Oxahomoadamantan-5-one was converted to the products. More concentrated H2SO4 was added (15.8 grams, 158 mmol) in the same fashion. This separated the reaction mixture into a top grayish layer of mostly cyclohexane and a black bottom layer. Refluxing was continued for additional 6 hrs, when GC analysis of the top layer showed that the reaction was complete. After cooling, the reaction mixture was transferred into a separatory funnel and the layers were separated. The dark bottom layer was extracted with 3×50 mL cyclohexane. The combined cyclohexane solutions was washed with 100 mL each of 1N NaOH and saturated brine. GC analysis of the solution showed >99% pure two isomers of 4-Acetoxyadamantanones. After drying over anhydrous Na2SO4, removal of solvent gave 4.03 gram of 4-Acetoxyadamantanone as a yellowish oil. Crushed ice was added to the conc. H2SO4 layer separated from the reaction mixture. The resulting solution was diluted with water to ≈500 mL and extracted with 4×100 mL CH2Cl2. The combined yellow CH2Cl2 solutions was washed with 1N NaOH (2 ×200 mL), water (100 mL), and saturated brine (100 mL). GC analysis of the solution showed that it was predominantly 4-Acetoxyadamantanone with small amounts of 4-Hydroxyadamantanones. Removal of solvent by rotary evaporation gave 7.24 grams of a red oil.

後処理

  1. additionwas charged to a 250-mL round-bottom flask
  2. temperatureheated
  3. temperatureto reflux with a heating mantle
  4. temperatureAfter 40 hours of reflux
  5. customThis separated the reaction mixture into a top grayish layer of mostly cyclohexane
  6. temperatureRefluxing
  7. temperatureAfter cooling
  8. customthe reaction mixture was transferred into a separatory funnel
  9. customthe layers were separated
  10. extractionThe dark bottom layer was extracted with 3×50 mL cyclohexane
  11. washThe combined cyclohexane solutions was washed with 100 mL each of 1N NaOH and saturated brine
  12. dry with materialAfter drying over anhydrous Na2SO4, removal of solvent

出典と根拠

ORDレコード
ord-f28620f5c3654093a6e772a9934732cf
出典データセット
uspto-grants-1995_07
特許番号
US05430193

反応ノート

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