Phosphoric Acid → 1-[1-(Allyloxy)-2-methyl-2-propenyl]-4-methylbenzene

HRID 2408248

反応式

HRID 2408248 の反応式
[CH3:1][C:2]1[CH:7]=[CH:6][C:5]([CH:8]([OH:12])[C:9]([CH3:11])=[CH2:10])=[CH:4][CH:3]=1.[CH2:13](Cl)[CH:14]=[CH2:15].P(=O)(O)(O)O>C1COCC1.[I-].C([N+](CCCC)(CCCC)CCCC)CCC.CC(OC)(C)C>[CH2:15]([O:12][CH:8]([C:5]1[CH:6]=[CH:7][C:2]([CH3:1])=[CH:3][CH:4]=1)[C:9]([CH3:11])=[CH2:10])[CH:14]=[CH2:13]

参加物

7

反応物 3

HCID 1004Phosphoric AcidHCID 7850Allyl chloride2 回HCID 540233242-Methyl-1-(4-methylphenyl)prop-2-en-1-ol

生成物 1

HCID 673304211-[1-(Allyloxy)-2-methyl-2-propenyl]-4-methylbenzene収率 80.2%

試薬・触媒・溶媒 3

HCID 67553Tetrabutylammonium Iodide触媒2 回HCID 8028Tetrahydrofuran溶媒2 回HCID 15413tert-Butyl methyl ether溶媒

実験手順

Solid sodium tert-butylate (66.65 g, 0.589 mol) was dissolved under nitrogen in dry THF (350 ml) and 1-(4-methylphenyl)-2-methyl-2-propen-1-ol (41.16 g, 0.239 mol) in dry THF (25 ml) was added in 15 minutes without external cooling. The reaction was further stirred at room temperature for 50 minutes. Tetra butyl ammonium iodide (5.04 g, 0.014 mol) was added followed by allyl chloride (40 g, 0.518 mol) in 25 minutes (exothermic to 47° C.). The reaction was stirred for 24 hours, before adding more tetra butyl ammonium iodide (2.30 g, 0.006 mol) and allyl chloride (9.30 g, 0.120 mol). After stirring for 24 hours at room temperature, the reaction was poured onto ice, diluted with MTBE and acidified with aqueous phosphoric acid. The organic phase was washed with brine, saturated aqueous sodium bicarbonate and brine and dried over solid anhydrous sodium sulfate. The solid was filtered off, rinsed with MTBE and solvents were removed under vacuum. The product was purified by distillation through a 35-cm Fisher column. 38.78 g of the desired allyl ether were obtained (yield=80%). B.P.=79° C./1.6 mbar

後処理

  1. custom(exothermic to 47° C.)
  2. stirringThe reaction was stirred for 24 hours
  3. stirringAfter stirring for 24 hours at room temperature
  4. additionthe reaction was poured onto ice
  5. washThe organic phase was washed with brine, saturated aqueous sodium bicarbonate and brine
  6. dry with materialdried over solid anhydrous sodium sulfate
  7. filtrationThe solid was filtered off
  8. washrinsed with MTBE and solvents
  9. customwere removed under vacuum
  10. distillationThe product was purified by distillation through a 35-cm Fisher column

出典と根拠

ORDレコード
ord-563d9c62427f4feea5896d68521d16c0
出典データセット
uspto-grants-2014_08
特許番号
US08815792B2

関連ノート

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