Ammonia → 6-Octenoic acid, 7-methyl-3-oxo-, ethyl ester

HRID 223761Notes

Reaction equation

HRID 223761 reaction equation
N.[Na].[C:3]([CH2:6][C:7]([O:9][CH2:10][CH3:11])=[O:8])(=[O:5])[CH3:4].Cl[CH2:13][CH:14]=[C:15]([CH3:17])[CH3:16]>O.[Na].C(O)(=O)C.CCOCC>[CH3:16][C:15]([CH3:17])=[CH:14][CH2:13][CH2:4][C:3](=[O:5])[CH2:6][C:7]([O:9][CH2:10][CH3:11])=[O:8]

Participants

9

Reactant 4

HCID 222AmmoniaHCID 8868Ethyl AcetoacetateHCID 104291-Chloro-3-methyl-2-buteneHCID 5360545Sodium

Product 1

HCID 105121656-Octenoic acid, 7-methyl-3-oxo-, ethyl esterYield 38.4%

Reagents, catalysts & solvents 4

HCID 5360545SodiumCatalystHCID 176Acetic AcidSolventHCID 962WaterSolventHCID 3283Diethyl EtherSolvent2×

Procedure

A mixture of 1.4 g of ferric nitrate in 1200 ml of liquid ammonia was formed at -60° C. and was then stirred for 5 minutes after which 2 g of sodium were added thereto at -60° C. The mixture was stirred for 10 minutes and 104 g of sodium were added at -55°±5° C. over 21/2 hours. The mixture was stirred at -55° C. for one hour. 300 g of ethyl acetylacetate were added thereto over 30 minutes at less than -30° C. 1000 ml of ether at -20° C. were added to the mixture which was then stirred for 5 minutes. 289 g of 1-chloro-3-methyl-2-butene were added over 30 minutes at less than -25° C. and the mixture stood at room temperature for 17 hours. 1000 ml of ether were progressively added at less than +15° C. followed by a solution of 250 ml of acetic acid in 1000 ml of water. The decanted aqueous phase was extracted with ether and the combined organic phases were washed with 2 N hydrochloric acid, then with water, dried over sodium sulfate and evaporated to dryness under reduced pressure. The residue was rectified under reduced pressure to obtain 175.5 g of ethyl 7-methyl-3-oxo-6-octenoate with a boiling point of 98° to 107° C. at 3 mm Hg.

Workup

  1. customwas formed at -60° C.
  2. additionwere added
  3. customat -60° C
  4. stirringThe mixture was stirred at -55° C. for one hour
  5. waitover 30 minutes at less than -30° C
  6. stirringwas then stirred for 5 minutes
  7. waitthe mixture stood at room temperature for 17 hours
  8. extractionThe decanted aqueous phase was extracted with ether
  9. washthe combined organic phases were washed with 2 N hydrochloric acid
  10. dry with materialwith water, dried over sodium sulfate
  11. customevaporated to dryness under reduced pressure

Sources & evidence

ORD record
ord-50b368ca872148daab3d3596c875b61e
Source dataset
uspto-grants-1982_10
Patent number
US04356187

Reaction notes

Loading…