Piperonal → HCID 5323761, compound

HRID 1735843Notes

Reaction equation

HRID 1735843 reaction equation
[CH:1]1[C:6]([CH:7]=[O:8])=[CH:5][C:4]2[O:9][CH2:10][O:11][C:3]=2[CH:2]=1.[CH3:12][Si:13](C#N)([CH3:15])[CH3:14].[C-:18]#[N:19].[K+].C1OCCOCCOCCOCCOCCOC1>CCOCC.C(=O)(O)[O-].[Na+].C(Cl)Cl>[CH3:12][Si:13]([CH3:15])([CH3:14])[O:8][CH:7]([C:6]1[CH:1]=[CH:2][C:3]2[O:11][CH2:10][O:9][C:4]=2[CH:5]=1)[C:18]#[N:19]

Participants

8

Reactant 4

HCID 8438Piperonal2×HCID 9032Potassium CyanideHCID 2855718-Crown-6HCID 82115Trimethylsilyl cyanide

Product 1

HCID 5323761HCID 5323761, compound

Reagents, catalysts & solvents 3

HCID 3283Diethyl EtherSolventHCID 6344DichloromethaneSolventHCID 516892Sodium BicarbonateSolvent

Procedure

To a nitrogen flushed magnetically stirred 3 L single neck round bottom flask fitted with a nitrogen inlet was charged 285 g (1.9 mol) of piperonal, 200 g (2.0 mol) of trimethylsilylcyanide, 0.2 g of potassium cyanide, 0.2 g of 18-crown-6 and 500 mL of methylene chloride. The mixture was stirred at ambient temperature for 75 min, during which time the reaction exothermed to 35° C. A second charge of 5 g of piperonal was added and the reaction stirred an additional 75 min. The reaction mixture was diluted with ether and 250 mL of saturated sodium bicarbonate solution was added. The mixture was stirred for 20 min before partitioning. The organic layer was washed with another 250 mL portion of saturated sodium bicarbonate, twice with brine (300 mL), dried with sodium surfate, filtered and concentrated, leaving 489.6 g (481.4 g theoretical yield) of the title compound as a pale yellow oil. This was used as is without purification in the next step.

Workup

  1. customTo a nitrogen flushed magnetically stirred 3 L single neck round bottom flask
  2. customfitted with a nitrogen inlet
  3. customthe reaction exothermed to 35° C
  4. additionwas added
  5. stirringthe reaction stirred an additional 75 min
  6. additionwas added
  7. stirringThe mixture was stirred for 20 min
  8. custombefore partitioning
  9. washThe organic layer was washed with another 250 mL portion of saturated sodium bicarbonate, twice with brine (300 mL)
  10. dry with materialdried with sodium surfate
  11. filtrationfiltered
  12. concentrationconcentrated
  13. customleaving

Sources & evidence

ORD record
ord-90293e24b9d3432b81ad81007ee07637
Source dataset
uspto-grants-1996_07
Patent number
US05538991

Reaction notes

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