Hydrochloric Acid → 3-(Acetyloxy)-4-methyl-2-methylenepentanenitrile

HRID 2181393Notes

Reaction equation

HRID 2181393 reaction equation
[OH:1][CH:2]([CH:7]([CH3:9])[CH3:8])[C:3](=[CH2:6])[C:4]#[N:5].N1C=CC=CC=1.[C:16](Cl)(=[O:18])[CH3:17].Cl>O.C(Cl)Cl>[C:4]([C:3](=[CH2:6])[CH:2]([O:1][C:16](=[O:18])[CH3:17])[CH:7]([CH3:9])[CH3:8])#[N:5]

Participants

7

Reactant 4

HCID 313Hydrochloric Acid2×HCID 1049PyridineHCID 6367Acetyl chlorideHCID 112404803-Hydroxy-4-methyl-2-methylenepentanenitrile

Product 1

HCID 152629853-(Acetyloxy)-4-methyl-2-methylenepentanenitrileYield 98.7%

Reagents, catalysts & solvents 2

HCID 962WaterSolvent2×HCID 6344DichloromethaneSolvent2×

Procedure

A nitrogen-purged 5 L, three-necked, round-bottom flask with overhead stirring is charged with 50 g (0.4 mol) of 3-hydroxy-4-methyl-2-methylenepentanenitrile, 0.4 L of methylene chloride, and 80 mL (1 mol) of pyridine. The solution is cooled at 10° C. to 15° C. in an ice bath. Using a 500 mL graduated addition funnel, a mixture of 100 mL of methylene chloride and 43 mL (0.6 mol) of acetyl chloride is added slowly while maintaining the reaction temperature at 25° C.±5° C. The reaction is stirred at 22° C.±3° C. for about one additional hour. The reaction solution is poured into a 4 L separators funnel containing 85 mL (1.0 mol) of hydrochloric acid and 750 mL of water. The lower organic layer is washed again with a solution of 20 mL (0.2 mol) of HCl and 250 mL of water. The organic layer is dried over anhydrous magnesium sulfate (20 g), filtered, and concentrated by rotary evaporation to provide 66 g of acetic acid 2-cyano-1-isopropyl-allyl ester as a yellow oil which may be used in the next step without further purification.

Workup

  1. customA nitrogen-purged 5 L
  2. temperatureThe solution is cooled at 10° C. to 15° C. in an ice bath
  3. additionaddition funnel
  4. additionis added slowly
  5. temperaturewhile maintaining the reaction temperature at 25° C.±5° C
  6. stirringThe reaction is stirred at 22° C.±3° C. for about one additional hour
  7. additionThe reaction solution is poured into a 4 L separators funnel
  8. dry with materialThe organic layer is dried over anhydrous magnesium sulfate (20 g)
  9. filtrationfiltered
  10. concentrationconcentrated by rotary evaporation

Sources & evidence

ORD record
ord-c2a3fb0e48444c6297588b90f8bdd279
Source dataset
uspto-grants-2005_05
Patent number
US06891059B2

Reaction notes

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