Crotyl chloride → 1-[1-(2-Butenyloxy)-2-methyl-2-propenyl]-4-methylbenzene

HRID 2408250

Reaction equation

HRID 2408250 reaction equation
CC([O-])(C)C.[K+].[CH3:7][C:8]1[CH:13]=[CH:12][C:11]([CH:14]([OH:18])[C:15]([CH3:17])=[CH2:16])=[CH:10][CH:9]=1.[CH2:19](Cl)[CH:20]=[CH:21][CH3:22]>C1COCC1.[I-].C([N+](CCCC)(CCCC)CCCC)CCC>[CH2:19]([O:18][CH:14]([C:11]1[CH:12]=[CH:13][C:8]([CH3:7])=[CH:9][CH:10]=1)[C:15]([CH3:17])=[CH2:16])[CH:20]=[CH:21][CH3:22]

Participants

6

Reactant 3

HCID 11589Crotyl chlorideHCID 23665647Potassium tert-butoxideHCID 540233242-Methyl-1-(4-methylphenyl)prop-2-en-1-ol

Product 1

HCID 673307901-[1-(2-Butenyloxy)-2-methyl-2-propenyl]-4-methylbenzeneYield 93%

Reagents, catalysts & solvents 2

HCID 67553Tetrabutylammonium IodideCatalystHCID 8028TetrahydrofuranSolvent

Conditions

Temperature
5 °C

Procedure

Solid potassium tert-butylate (47 g, 0.411 mol) was added portion-wise (ca 15 min) to a solution of 1-(4-methylphenyl)-2-methyl-2-propen-1-ol (96% pure, 46.27 g, 0.274 mol) in dry THF (500 ml) at room temperature under nitrogen (exothermic to 30° C.). After 1 more hour at room temperature, the reaction was cooled to 5° C. and tetra butyl ammonium iodide (5.2 g, 0.014 mol) was added followed by crotyl chloride (74.4 g, 0.822 mol) drop-wise. The reaction was warmed up to room temperature overnight and poured onto water (800 ml). The reaction was extracted twice with ethyl acetate. Each organic phase was washed with water and brine. Combined extracts were dried over solid anhydrous sodium sulfate. The solid was filtered off, rinsed with diethyl ether and the solvents were removed under vacuum. The product was purified by distillation under vacuum through a 20-cm Widmer column A 3:1 mixture of E/Z isomers was obtained (96% pure, 57.58 g, yield=93%). B.P.=74° C./0.005 mbar

Workup

  1. temperatureThe reaction was warmed up to room temperature overnight
  2. additionpoured onto water (800 ml)
  3. extractionThe reaction was extracted twice with ethyl acetate
  4. washEach organic phase was washed with water and brine
  5. dry with materialCombined extracts were dried over solid anhydrous sodium sulfate
  6. filtrationThe solid was filtered off
  7. washrinsed with diethyl ether
  8. customthe solvents were removed under vacuum
  9. distillationThe product was purified by distillation under vacuum through a 20-cm Widmer column
  10. additionA 3:1 mixture of E/Z isomers
  11. customwas obtained (96% pure, 57.58 g, yield=93%)

Sources & evidence

ORD record
ord-0305722cefa24fb6832fcaebd9654088
Source dataset
uspto-grants-2014_08
Patent number
US08815792B2

Linked notes

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