Piperonal → HCID 23050524, compound

HRID 1651828Notes

Reaction equation

HRID 1651828 reaction equation
[C:1]([O:5][CH2:6][CH:7]=[C:8]([CH3:10])[CH3:9])(=[O:4])[C:2]#[CH:3].C([Li])CCC.[CH2:16]1[O:26][C:25]2[CH:24]=[CH:23][C:20]([CH:21]=[O:22])=[CH:19][C:18]=2[O:17]1.[Cl-].[NH4+]>O1CCCC1>[OH:22][CH:21]([C:20]1[CH:23]=[CH:24][C:25]2[O:26][CH2:16][O:17][C:18]=2[CH:19]=1)[C:3]#[C:2][C:1]([O:5][CH2:6][CH:7]=[C:8]([CH3:10])[CH3:9])=[O:4]

Participants

6

Reactant 4

HCID 8438PiperonalHCID 25517Ammonium ChlorideHCID 14249453HCID 14249453, compoundHCID 178418339Butyllithium

Product 1

HCID 23050524HCID 23050524, compound

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Procedure

A solution of 10 g (72 mmol) of 3-methyl-2-butenyl propiolate in 100 ml of tetrahydrofuran was treated at -78° under argon with 47 ml of n-butyllithium (1.6M in hexane). The mixture was stirred at -78° for 10 minutes and then a solution of 10.9 g (72 mmol) of 3,4-methylenedioxybenzaldehyde in 120 ml of tetrahydrofuran was added within 30 minutes. The reaction mixture was stirred at -78° for a further 30 minutes then brought to room temperature and treated with 120 ml of saturated ammonium chloride solution. The aqeuous phase was extracted twice with ether; the organic phases were washed in succession with saturated sodium chloride solution and with water, dried over sodium 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 3-methyl-2-butenyl 4-hydroxy-4-[3,4-(methylenedioxy)phenyl]-2-butynoate as a yellow oil.

Workup

  1. stirringThe reaction mixture was stirred at -78° for a further 30 minutes
  2. customthen brought to room temperature
  3. extractionThe aqeuous phase was extracted twice with ether
  4. washthe organic phases were washed in succession with saturated sodium chloride solution and with water
  5. dry with materialdried over sodium sulphate
  6. concentrationconcentrated
  7. 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-f4a83daf87aa48edaae8b7c7c4ff99e5
Source dataset
uspto-grants-1990_05
Patent number
US04929741

Reaction notes

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