Hydrochloric Acid → 3-Tert-butyl-1-methyl-6,6-di(p-tolyl)fulvene

HRID 13982

反応式

HRID 13982 の反応式
[OH-].[K+].[C:3]([C:7]1[CH:8]=[C:9]([CH3:12])[CH2:10][CH:11]=1)([CH3:6])([CH3:5])[CH3:4].[CH3:13][C:14]1[CH:28]=[CH:27][C:17]([C:18]([C:20]2[CH:25]=[CH:24][C:23]([CH3:26])=[CH:22][CH:21]=2)=O)=[CH:16][CH:15]=1.Cl>C(COC)OC>[C:3]([C:7]1[CH:8]=[C:9]([CH3:12])[C:10](=[C:18]([C:20]2[CH:25]=[CH:24][C:23]([CH3:26])=[CH:22][CH:21]=2)[C:17]2[CH:27]=[CH:28][C:14]([CH3:13])=[CH:15][CH:16]=2)[CH:11]=1)([CH3:6])([CH3:5])[CH3:4]

参加物

6

反応物 4

HCID 313Hydrochloric AcidHCID 14797Potassium HydroxideHCID 691484,4'-DimethylbenzophenoneHCID 153463033-tert-Butyl-1-methylcyclopenta-1,3-diene

生成物 1

HCID 866095443-Tert-butyl-1-methyl-6,6-di(p-tolyl)fulvene

試薬・触媒・溶媒 1

HCID 80711,2-Dimethoxyethane溶媒2 回

実験手順

In a 200 ml three-necked flask equipped with a magnetic stirrer chip and three-way cock thoroughly purged with nitrogen, 1.56 g of powdery potassium hydroxide (27.8 mmol) and 100 ml of dehydrated dimethoxy ethane were added in a nitrogen atmosphere. To the suspension, 2.46 g of 3-tert-butyl-1-methyl-cyclopentadiene (18.0 mmol) was gradually added dropwise at room temperature and stirred under reflux for 2 hr. To the reaction solution, a solution prepared by dissolving 3.99 g of 4,4′-dimethylbenzophenone (19.0 mmol) in 40 ml of dehydrated dimethoxy ethane was gradually added and stirred under reflux for 3 days. To the reaction mixture, 50 ml of a hydrochloric acid aqueous solution (1N) was gradually added dropwise in an ice bath, and stirred at room temperature for some time. The organic phase was separated by adding diethyl ether and washed with a saturated sodium bicarbonate aqueous solution, water and saturated brine. The organic phase was dried with anhydrous magnesium sulfate, and thereafter the drying agent was filtered off and the solvent was distilled off from the filtrate under reduced pressure to give a dark red liquid. The liquid was purified by a column chromatography using 170 g of silica gel (developing solvent: n-hexane) and the developing solvent was distilled off under reduced pressure, and thereby the aimed compound was obtained in an amount of 2.55 g (7.76 mmol) as a red solid (yield: 43%).

後処理

  1. customIn a 200 ml three-necked flask equipped with a magnetic stirrer chip and three-way cock
  2. additionwere added in a nitrogen atmosphere
  3. temperatureunder reflux for 2 hr
  4. customTo the reaction solution, a solution prepared
  5. additionwas gradually added
  6. stirringstirred
  7. temperatureunder reflux for 3 days
  8. stirringstirred at room temperature for some time
  9. customThe organic phase was separated
  10. additionby adding diethyl ether
  11. washwashed with a saturated sodium bicarbonate aqueous solution, water and saturated brine
  12. dry with materialThe organic phase was dried with anhydrous magnesium sulfate
  13. filtrationthe drying agent was filtered off
  14. distillationthe solvent was distilled off from the filtrate under reduced pressure
  15. customto give a dark red liquid
  16. customThe liquid was purified by a column chromatography
  17. distillationthe developing solvent was distilled off under reduced pressure

出典と根拠

ORDレコード
ord-c892edcd9c8749fba6f8f3eca9722647
出典データセット
uspto-grants-2010_06
特許番号
US07728078B2

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