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

HRID 2408248

Reaction equation

HRID 2408248 reaction equation
[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]

Participants

7

Reactant 3

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

Product 1

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

Reagents, catalysts & solvents 3

HCID 67553Tetrabutylammonium IodideCatalyst2×HCID 8028TetrahydrofuranSolvent2×HCID 15413tert-Butyl methyl etherSolvent

Procedure

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

Workup

  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

Sources & evidence

ORD record
ord-563d9c62427f4feea5896d68521d16c0
Source dataset
uspto-grants-2014_08
Patent number
US08815792B2

Linked notes

Loading…