Crotyl chloride → HCID 67331219, compound

HRID 2408252Notes

Reaction equation

HRID 2408252 reaction equation
CC([O-])(C)C.[K+].[C:7]1([CH:13]([OH:17])[C:14]([CH3:16])=[CH2:15])[CH:12]=[CH:11][CH:10]=[CH:9][CH:8]=1.[CH2:18](Cl)[CH:19]=[CH:20][CH3:21]>C1COCC1.[I-].C([N+](CCCC)(CCCC)CCCC)CCC>[CH2:18]([O:17][CH:13]([C:7]1[CH:12]=[CH:11][CH:10]=[CH:9][CH:8]=1)[C:14]([CH3:16])=[CH2:15])[CH:19]=[CH:20][CH3:21]

Participants

6

Reactant 3

HCID 11589Crotyl chlorideHCID 1382112-Methyl-1-phenylprop-2-en-1-olHCID 23665647Potassium tert-butoxide

Product 1

HCID 67331219HCID 67331219, compoundYield 83%

Reagents, catalysts & solvents 2

HCID 67553Tetrabutylammonium IodideCatalystHCID 8028TetrahydrofuranSolvent

Conditions

Temperature
5 °C

Procedure

Solid potassium tert-butylate (26 g, 0.228 mol) was added portion-wise (ca 15 min) to a solution of 1-phenyl-2-methyl-2-propen-1-ol (90% pure from Alfa Aesar, 25 g, 0.152 mol) in dry THF (300 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 (2.9 g, 0.08 mol) was added followed by crotyl chloride (41.3 g, 0.456 mol) drop-wise. The reaction was warmed up to room temperature overnight and poured onto water (500 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. After column chromatography on silica gel (eluent: heptanes/ethyl acetate 25:1) the product was purified by bulb-to-bulb distillation (100° C./0.001 mbar). A 3:1 mixture of E/Z isomers was obtained (95% pure, 26.78 g, yield=83%).

Workup

  1. temperatureThe reaction was warmed up to room temperature overnight
  2. additionpoured onto water (500 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. distillationAfter column chromatography on silica gel (eluent: heptanes/ethyl acetate 25:1) the product was purified by bulb-to-bulb distillation (100° C./0.001 mbar)
  10. additionA 3:1 mixture of E/Z isomers
  11. customwas obtained (95% pure, 26.78 g, yield=83%)

Sources & evidence

ORD record
ord-05d2ef5f32ae4dbaadad0786241b99a9
Source dataset
uspto-grants-2014_08
Patent number
US08815792B2

Reaction notes

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