Piperonal → HCID 23050497, compound

HRID 1651845Notes

Reaction equation

HRID 1651845 reaction equation
[CH3:1][C:2]([CH3:9])=[CH:3][CH2:4][O:5][CH2:6][C:7]#[CH:8].C([Li])CCC.[CH2:15]1[O:25][C:24]2[CH:23]=[CH:22][C:19]([CH:20]=[O:21])=[CH:18][C:17]=2[O:16]1.[Cl-].[NH4+]>O1CCCC1>[OH:21][CH:20]([C:19]1[CH:22]=[CH:23][C:24]2[O:25][CH2:15][O:16][C:17]=2[CH:18]=1)[C:8]#[C:7][CH2:6][O:5][CH2:4][CH:3]=[C:2]([CH3:9])[CH3:1]

Participants

6

Reactant 4

HCID 8438PiperonalHCID 25517Ammonium ChlorideHCID 11469074HCID 11469074, compoundHCID 178418339Butyllithium

Product 1

HCID 23050497HCID 23050497, compound

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Procedure

A solution of 20 g (161 mmol) of 1-[(3-methyl-2-butenyl)oxy)-2-propyne in 200 ml of tetrahydrofuran was treated at -78° under argon with 111 ml of n-butyllithium (1.6M in hexane). The mixture was left to stir at -40° for 30 minutes, again cooled to -78° and a solution of 26.6 g (177 mmol) of 3,4-methylenedioxybenzaldehyde in 150 ml of tetrahydrofuran was then added within 40 minutes. The reaction mixture was stirred at -78° for a further 1 hour, then warmed to room temperature and subsequently treated with 150 ml of saturated ammonium chloride solution. The aqueous phase was extracted twice with ether. The combined organic phases were washed in succession with saturated sodium chloride solution and with water, dried over magnesium sulphate and concentrated. The residue was purified by flash chromatography on 1000 g of silica gel (elution agent methylene chloride/ethyl acetate 9:1). There was obtained 1-hydroxy-4-[(3-methyl-2-butenyl)oxy]-1-[3,4-(methylenedioxy)phenyl]-2-butyne as a yellow oil.

Workup

  1. waitThe mixture was left
  2. temperatureagain cooled to -78°
  3. stirringThe reaction mixture was stirred at -78° for a further 1 hour
  4. extractionThe aqueous phase was extracted twice with ether
  5. washThe combined organic phases were washed in succession with saturated sodium chloride solution and with water
  6. dry with materialdried over magnesium sulphate
  7. concentrationconcentrated
  8. customThe residue was purified by flash chromatography on 1000 g of silica gel (elution agent methylene chloride/ethyl acetate 9:1)

Sources & evidence

ORD record
ord-0295c8f2697d4948be95156cd87eff28
Source dataset
uspto-grants-1990_05
Patent number
US04929741

Reaction notes

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