Sulfuric Acid → (4S)-4,8-dimethyl-7-nonen-2-one

HRID 585036

反応式

HRID 585036 の反応式
[CH3:1][C@@H:2]([CH2:7][CH2:8][CH:9]=[C:10]([CH3:12])[CH3:11])[CH2:3][CH:4]([OH:6])[CH3:5].CC(C)=O.OS(O)(=O)=O.O=[Cr](=O)=O.S(=O)(=O)(O)O.S([O-])(O)=O.[Na+]>[O-2].[O-2].[O-2].[Cr+6].[Cr+6].O.CC(C)=O>[CH3:1][C@@H:2]([CH2:7][CH2:8][CH:9]=[C:10]([CH3:11])[CH3:12])[CH2:3][C:4](=[O:6])[CH3:5]

参加物

9

反応物 4

HCID 1118Sulfuric AcidHCID 12084285(4S)-4,8-dimethyl-7-nonen-2-olHCID 23665763Sodium BisulfiteHCID 131709961Jones' reagent

生成物 1

HCID 11446560(4S)-4,8-dimethyl-7-nonen-2-one収率 81.8%

試薬・触媒・溶媒 4

HCID 29131Chromium(6+)触媒HCID 10219390chromium (VI) trioxide触媒HCID 180Acetone溶媒HCID 962Water溶媒

実験手順

Acetone (2,000 ml) and (4S)-4,8-dimethyl-7-nonen-2-ol (240 g) synthesized in Synthetic Example 1—1 were placed in a 5-liter, 4-necked flask equipped with a dropping funnel, thermometer, condenser, and stirrer. Jones reagent {prepared from water (520 ml), concentrated sulfuric acid (165 g), and chromium trioxide (112 g)} placed in the dropping funnel was added dropwise over a period of 4 hours under cooling with ice. After the dropwise addition, the mixture was stirred for 2 hours. Then, sodium hydrogen sulfite was added gradually until the orange color of chromium (VI) disappeared. The liquid was then separated and the bottom layer was extracted with petroleum ether (1,000 ml). Since the liquid again separated into two layers when the extract was combined with the previous upper layer, the lower layer was added to the previous lower layer and further extracted three times with 500 ml of petroleum ether. After combining the petroleum ether layers and washing with a saturated brine, a saturated aqueous sodium hydrogen carbonate solution and again with a saturated brine, the solvent was evaporated. The resulting concentrated oil was distilled with a Widmer distiller to obtain 194 g of (4S)-4,8-dimethyl-7-nonen-2-one (b.p.: 63° C./133 Pa).

後処理

  1. customequipped with a dropping funnel
  2. additionwas added dropwise over a period of 4 hours
  3. temperatureunder cooling with ice
  4. additionAfter the dropwise addition
  5. customThe liquid was then separated
  6. extractionthe bottom layer was extracted with petroleum ether (1,000 ml)
  7. customSince the liquid again separated into two layers when the extract
  8. additionthe lower layer was added to the previous lower layer
  9. extractionfurther extracted three times with 500 ml of petroleum ether
  10. washwashing with a saturated brine
  11. customa saturated aqueous sodium hydrogen carbonate solution and again with a saturated brine, the solvent was evaporated
  12. concentrationThe resulting concentrated oil
  13. distillationwas distilled with a Widmer distiller

出典と根拠

ORDレコード
ord-2927d3f3cae5426d8b92f46419fdca76
出典データセット
uspto-grants-2005_08
特許番号
US06930083B2

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