Methyl acetoacetate → 4-Pentenoic acid, 2-acetyl-, methyl ester

HRID 1389623Notes

Reaction equation

HRID 1389623 reaction equation
[CH2:1](Cl)[CH:2]=[CH2:3].[C:5]([O:11][CH3:12])(=[O:10])[CH2:6][C:7]([CH3:9])=[O:8].C(Br)C=C>CCCCCCCC[N+](CCCCCCCC)(CCCCCCCC)C.[Cl-]>[C:5]([CH:6]([C:7](=[O:8])[CH3:9])[CH2:3][CH:2]=[CH2:1])([O:11][CH3:12])=[O:10]

Participants

5

Reactant 3

HCID 7757Methyl acetoacetate2×HCID 7841Allyl bromideHCID 7850Allyl chloride

Product 1

HCID 1071874-Pentenoic acid, 2-acetyl-, methyl esterYield 30%

Reagents, catalysts & solvents 1

HCID 21218Trioctylmethylammonium chlorideCatalyst

Procedure

In J. Org. Chem., Vol. 39, No. 22, 1974 at page 3271, an article by Durst & Liebeskind entitled, "Phase Transfer Catalysis. The Acetoacetic Ester Condensation" indicates that reaction of allyl chloride with methyl acetoacetate gives rise to a 30% yield of 4-carbomethoxy-1-hexen-5-one and reaction of methyl acetoacetate with allyl bromide in the presence of an Aliquat 336® catalyst gives rise to a 94.7% yield of 4-carbomethoxy-1-hexen-5-one. The reaction is carried out however in the presence of anhydrous benzene which gives rise to the danger of causing minute traces of benzene to exist in the final desired product which is to be used for its organoleptic properties in perfumery. The potential presence of such solvent is unacceptable in the perfumery field.

Workup

  1. customgives rise

Sources & evidence

ORD record
ord-4e0e99d994964850bdcf7e4c1254d49e
Source dataset
uspto-grants-1981_01
Patent number
US04245122

Reaction notes

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